Part IIB. X-Ray Diffraction Powder Data for Eighty-Three Narcotics

Title

Part IIB. X-Ray Diffraction Powder Data for Eighty-Three Narcotics

Sections

Contents
INTRODUCTION
EXPERIMENTAL
RESULTS
NOTES ON INDIVIDUAL NARCOTICS
ACKNOWLEDGEMENTS

Details

Author: W. H. Barnes , Helen M. Sheppard
Pages: 27 to 68
Creation Date: 1954/01/01

PHYSICAL METHODS FOR THE IDENTIFICATION OF NARCOTICS (Cont.)

Part IIB. X-Ray Diffraction Powder Data for Eighty-Three Narcotics

W. H. Barnes Division of Physics, National Research Council, Ottawa, Canada
Helen M. Sheppard Division of Physics, National Research Council, Ottawa, Canada

Contents

Page
Introduction
27
Experimental
27
Results
29
Notes on Individual Narcotics
29
Codeine (anhydrous free base), Codeine Monohydrate (free base), and Dihydrocodeinone (free base)
29
Codeine Phosphate
29
Cotarnine (free base)
31
o-Diphenoloxymorphine (free base)
31
Diamorphine (free base), Diamorphine Hydrochloride Monohydrate, Morphine Monohydrate (free base), Morphine Hydrochloride (anhydrous) and Morphine Hydrochloride Trihydrate
31
Dihydromorphinone (free base) and Dihydromorphinone Hydrochloride
32
Mescaline Sulphate Dihydrate
33
dl-Methadone Hydrobromide and dl-Methadone Hydrochloride
33
Metopon (free base) and Metopon Hydrochloride
34
Morphine Sulphate
34
Narcotine Hydrochloride
35
Pethidine Hydrochloride
36
dl-&alpha-Prodine Hydrochloride and dl-&beta-Prodine Hydrochloride
36
Protopine (free base)
36
Thebenine Hydrochloride Monohydrate
37
Note added in proof
37
Acknowledgements
37
References
37
Alphabetical Index
38
Innermost Line Index
40
Numerical (Hanawalt) Index
41
Tabulated ( d, I/I 1) Data
46
Figures
59

INTRODUCTION

Relatively few data for the identification of narcotics by the X-ray diffraction powder method are available in the literature. The basic principles and techniques of the method have been outlined in the preceding paper ([2] ) 1 of this group of articles on Physical Methods for the Identification of Narcotics. The primary object of the present paper is to provide tabulated data and characteristic X-ray diffraction powder photographs for eighty-three narcotics, including some hydrates and a few optical isomers and their racemoids. At the same time a number of notes on particular compounds, with the investigation of which difficulties or special points of interest were encountered, are included in the hope that they may be of interest to other laboratories.

All samples, with the exception of two protopine preparations, were supplied by Dr. C. G. Farmilo, and their authentication is discussed elsewhere ([3] ).

At least two X-ray diffraction powder photographs were taken of each sample, although, for various reasons, additional ones were obtained in many cases. Whenever possible the product of more than one laboratory or pharmaceutical manufacturer was included. Although the majority of specimens were first crushed and then mounted on the end of a pyrex-glass fibre by means of Household Cement, a large proportion of the duplicate patterns were obtained from specimens taken up in capillary tubes directly from their original containers, thus avoiding any possible effect of mechanical grinding or of contact with the adhesive or its solvent. Furthermore, time intervals of at least a few weeks to more than one year elapsed between photographs of different specimens of each sample so that some opportunity automatically was provided for observing any alteration during storage. More than 300 X-ray diffraction powder photographs were taken during the course of the present investigation. The best pattern for each narcotic (in some cases more than one) was measured at least twice and almost invariably by different individuals.

EXPERIMENTAL

For specimens mounted on the ends of glass fibres, quantities of the order of 0.15 to 0.2 mg. were employed. Each was ground in a mullite mortar, or in a well-type microscope slide with a miniature glass pestle. A small portion of the fine powder was placed on another microscope slide together with separate drops of Household (Duco) Cement[2] and isoamyl acetate. The end of a thin pyrex-glass fibre was touched to the cement and then to the powder. If the cement was too viscous it was dipped in the isoamyl acetate before taking up the powder. By judicious application of the fibre to the cement, isoamyl acetate, and powder, and with the aid of a needle held in the other hand, specimens of suitable size could be built up on the end of the fibre. The whole operation was carried out most conveniently under a stereoscopic microscope.

X-ray diffraction tests of a number of adhesives in this laboratory several years ago led to the adoption of Household Cement because it gives no diffraction lines, and only a minimum intensity of scattered radiation, compared with many other adhesives commonly employed. Since the quantity required to mount a specimen (powder or single-crystal) is very small, no difficulty has been experienced in its use even with organic compounds soluble in acetone. Unfortunately it is supplied only in lead tubes which are intended to be opened by means of a screw that pierces a lead membrane closing a threaded plug in the top of the tube. Abrasion of the threads during this procedure usually contaminates the cement with small particles of lead which results in the diffraction pattern of lead appearing on the film if any of the particles are picked up during mounting of the specimen. Attention recently has been drawn to this fact in the literature ([9] ) where slitting the tube down the side and transferring the contents to a glass container has been recommended. This has been standard practice in this laboratory for the past six years except that the bottoms of the inverted tubes are cut off with a pair of sharp scissors; the tube then opens easily and the cement is poured into a glass jar with screw top. The cement may be thinned with acetone, amyl acetate, or isoamyl acetate; the last has the least rapid rate of evaporation and its use permits a longer time for manipulation when preparing the specimen before the cement hardens.

For the preparation of specimens in thin-walled capillary tubes the following method ([10] ) was employed. The capillary tubes were made by drawing down Corning special glass tubing 7070 (16 mm., outer diameter; 13 mm., inner diameter) and selecting straight sections, approximately 1 to 1.5 cm. long, 0.018 inch outer diameter, 0.001 to 0.002 inch wall thickness. 3 A rubber "policeman" with the oblique blade trimmed to a right angle was fitted to the end of a seven-inch length of glass tubing which was connected by rubber tubing to one arm of a glass Y-tube, the leg of which was joined by rubber tubing to a trap and thence to a water suction pump. The glass tubing carrying the rubber policeman was handled in the same way as a pen or pencil, and a small hole was blown in the tubing at the spot normally covered by the index finger. An adjustable screw clamp on a short length of rubber tubing attached to the other arm of the Y-tube could be regulated to adjust the degree of suction obtained through the glass "pencil" tube when the pump was operating. The capillary tube was inserted in a hole, made by a heated needle, in the rubber policeman. Suction could then be applied to, or cut off from, the capillary tube by covering, or uncovering, the hole in the glass tubing with the index finger. To fill the capillary tube a wisp of cotton was first drawn into one end, the capillary was reversed in the rubber policeman, and the powdered sample was drawn in and could be tamped down with a glass fibre. In this laboratory the wisp of cotton normally is removed and the ends of the tube may then be sealed in a flame or closed with soft wax or plasticine. Samples may be picked up from an oven, or from an atmosphere of known relative humidity in a desiccator, and then sealed immediately to prevent acquisition of moisture. Efflorescent hydrates or other substances may be crystallized rapidly with constant stirring to ensure small particle size, and then drawn up into the capillary tube together with excess solvent. This capillary-tube method requires less time than mounting the sample on a glass fibre and usually results in sharper, better resolved, powder patterns. It does require, however, somewhat more material than the minimum that can be handled effectively with a glass-fibre mount.

The photographs for the present investigation were taken with two identical cylindrical cameras (North American Philips Co.) of 114.6 mm. diameter, using Straumanis film mounting. Film shrinkage corrections were calculated, but, since they were always less than ± 0.25%, they were not applied to the film measurements. The X-ray apparatus was a General Electric XRD-1 unit with an X-ray tube furnished with two beryllium windows and a cobalt target (&lambda(K&alpha)=l.790?). The radiation was filtered with iron foil. With this equipment the largest measurable value of d (i.e., the "cutoff") is 20A. Exposure times of 15 to 20 hours were adopted to ensure somewhat overexposed films for reproduction; 5 to 10 hours would have been sufficient for ordinary identification purposes in most cases. The negatives were not intensified.

The photographs were measured with a standard powder-film measuring device (North American Philips Co.) having a vernier reading to 0.05 mm. Film measurements (in mm.) were converted to 0 values (1 mm. on the film corresponds to 2 &theta:1o) and the interplanar spacings ( d) were then read from tables ([13] ). All films were measured at least twice and individual lines for which significant differences in d values occurred were remeasured; otherwise the average of the two measurements was adopted.

Intensities relative to the strongest line of each pattern ( 1/I 1) were estimated visually on a scale of 100. Doubtful, or exceedingly faint, lines ( I/I 1<1) were omitted on the grounds that it is less confusing for such lines not to be included in tabulated data even if real than it is to report them when they may be spurious. Owing to the rapid decrease in intensity with increasing values of 2 &theta, only lines corresponding to 2 &theta&le90o were measured in most cases.

RESULTS

The tabulated d and I/I 1 data are given at the end of this paper preceded by an Alphabetical Index, an "Innermost Line" Index, anda Numerical ( Hanawalt) Index, and followed by reproductions of the diffraction photographs. Each pattern has been assigned a number (1 to 83, inclusive) according to the sequence in the Alphabetical Index; these numbers precede the names of the substances in the Tabulated( d, I/I 1) Data and follow them in the "Innermost Line" Index and in the Numerical Index. They are identical with the numbers of the figures from fig. 1 to fig. 83, inclusive; figs. 84 to 90 illustrate special points arising from the Notes on Individual Narcotics (see next section).

For the figures, the powder photographs have been trimmed to 1 in. X 4[1] / 2 in. symmetrically about the hole whose centre corresponds approximately to 2 &theta=0o, in order to conserve space and because, for the narcotics, the lines generally become very faint or are not observable beyond the length chosen; the outer edges of the patterns correspond approximately to d = 1.89? Some loss of detail is inevitable because they must be viewed by reflected light instead of by transmitted light as for the original negatives, and because they have passed through several reproduction processes, viz., a contact print on film, a contact print on paper from this intermediate negative, and the steps required to transform the paper print through the "cut" for printing to the final reproduction. This ensures, however, that each figure will have the same appearance (dark diffraction arcs on a light background) as the original X-ray diffraction photograph and the result is not only more "natural" in appearance but makes direct comparison with an original negative much more satisfactory.

NOTES ON INDIVIDUAL NARCOTICS

Codeine (anhydrous free base), Codeine Monohydrate (free base), and Dihydrocodeinone (free base).

The sample of codeine (free base), as received, gave a powder pattern (fig. 84) consisting of a mixed set of smooth and grainy diffraction lines. Examination under the stereoscopic microscope revealed the presence of small prisms, some completely and some only partially opaque, in a mass of finely-divided material. Individual opaque prisms, without crushing, gave excellent powder photographs with smooth lines while those that were partially transparent yielded patterns comprising spots characteristic of single crystals together with lines characteristic of powdered materials, but the single-crystal spots did not appear to originate with the same crystalline phase as that responsible for the powder lines. A portion of the original sample, therefore, was recrystallized from absolute alcohol and another portion from distilled water. In each case the crystals were mechanically ground and powder photographs were taken. The pattern given by the crystals from absolute alcohol (fig. 8) was identical with the set of smooth lines in the original photograph (fig. 84); that given by the crystals from water (fig. 9) was identical with the set of grainy lines. A single-crystal study by X-ray diffraction methods, and comparison with existing crystallographic data ([11] ), enabled the crystals from absolute alcohol to be identified as the anhydrous base and those from water as the monohydrate.

Crystals of codeine monohydrate are efflorescent. The sample examined must originally have contained a large number of prismatic crystals of the monohydrate, many of which had lost their water of crystallization by the time the diffraction photographs were taken. This feature should be borne in mind in cases involving the identification of codeine.

In view of the similarity of the patterns for codeine (anhydrous free base) (fig. 8) and for dihydrocodeinone (free base) (fig. 17), a single-crystal examination of the latter also was carried out. From the shape, dimensions, and symmetry of the unit cell determined by such a study, the spacings of all sets of planes that could give rise to observable powder diffraction lines may be calculated; they can then be compared with the spacings of those lines actually observed. All possible lines may not be represented in the powder pattern because their relative intensity may be too low, but, providing the sample consists of a single crystalline phase, no lines should appear on the powder photograph that correspond to spacings not predicted on the basis of the unit cell data for that phase. It is obviously desirable that all powder patterns should be authenticated from single-crystal data. In practice, however, it is frequently difficult to grow suitable crystals, and, in any event, the establishment of the unit cell constants for a large number of substances for purposes of routine checking of their powder patterns can be very time-consuming.

It should be noted, however, that the present spacings for codeine (anhydrous free base), codeine monohydrate (free base), and dihydrocodeinone (free base) have been verified from single-crystal data for values of d from the maximum observed (which also is the maximum possible) to approximately 3.00?. The data for codeine (anhydrous free base) are in very good agreement with the measurements of Gross and Oberst ([4] ).

Codeine Phosphate

Codeine phosphate hydrates have been reported ([7] , [12] ) with 1, 1?, and 2 moles water per mole anhydrous salt, and the higher ones, at least, are said to be efflorescent. Samples of codeine phosphate from three different commercial sources (A, B, C) were examined. The patterns obtained from A and B when first received are shown in figs. 85 and 86, respectively; that from C was identical with that from B. The importance of the water content had not become apparent at the time when the first pattern of A was obtained, but C contained 0.75 mole water when received. After seventeen months, the pattern from A exhibited marked differences from the original (at this time the water content was determined as 1.4 mole), and further minor alterations were observed after a further period of three months. It was not possible to investigate possible changes in the original patterns of B and C over such an extended length of time, but that from B after three months was virtually identical with the initial one.

Two reproducible patterns, however, were obtained from both A and B, (a) by heating either sample in an oven at 70oC, and (b) by recrystallizing either sample from distilled water. These patterns constitute figs. 10 and 11, respectively. Furthermore, the phase responsible for the pattern of fig. 10 could be transformed into that giving fig. 11 by recrystallization of the "dried" sample from water and this, in turn, could be reconverted to the original phase (fig. 10) by heating the "wet" sample in an oven at 70oC.

No change in the pattern of the dried material (fig. 10) was observed even after seven days at 60oC followed by two days at 70oC. A water determination by Mrs. P. M. Oestreicher on the dried material showed that it was anhydrous.

The phase recrystallized from water is highly efflorescent. This was demonstrated by patterns obtained from freshly crystallized material (A and B) when precautions were not taken to ensure the presence of excess water with the specimens. It was difficult, therefore, to obtain a reliable estimate of crystal-water and it is assumed, therefore, that fig. 11 represents the pattern of the fully hydrated phase, namely, the dihydrate.

As a guide towards the identification of codeine phosphate, tabulated data ( d > 3.00?) for some of the patterns obtained from mixtures intermediate between the anhydrous salt and the dihydrate are given in the accompanying Table of Patterns of Mixtures of Codeine Phosphate Hydrates. Detailed analysis of these data indicates that there probably are several hydrate phases involved. The dihydrate appears to be one of the constituents of sample A (as originally received) and also seventeen months later; it is the principal (but not the sole) constituent of samples A and B recrystallized from water without adequate precautions against efflorescence. On the other hand the pattern of samples B and C (as originally received) represents a principal phase that has not been identified. The anhydrous salt may be present in this pattern and in the later one from sample A. Attempts to disentangle the composite patterns represented in the Table, however, are not likely to be successful without detailed knowledge of the possible phases. It is apparent that the codeine phosphate water system requires a systematic phase rule investigation.

Patterns (for d>3.00?) of Mixtures of Codeine Phosphate Hydrates

Sample A
Original
After 17 mos.
Incomplete hydration
Sample B
Original
Incomplete hydration
dI/I 1dI/I 1dI/I 1dI/I 1dI/I 1
16.44016.33516.55016.54016.635
8.02257.91307.89357.77507.9235
7.0257.1515B7.065B7.241007.065B
6.611006.591006.611006.73206.57100
6.06156.35556.09206.55406.0710
5.81106.0885.81256.36755.8445
5.48305.78705.46456.0715.4835
5.12355.46205.25105.83755.2430
4.83155.12455.06455.70305.0445
4.52604.85104.82405.61304.8245
4.20604.51504.50455.40404.5240
3.99754.1920B4.37105.07124.3940
3.8813.97704.2050B4.79154.2150B
3.58753.8640B4.0824.64604.095
3.4415B3.57903.98604.42153.9845
3.27203.42703.8924.32403.892
3.1633.2853.57604.19403.741
3.08203.1653.50304.1053.5745
3.0253.045B3.41254.00153.5145
3.28153.921003.4420
3.2253.7253.293
3.1683.65603.216
3.0953.575603.171
3.01403.42603.092
3.36603.0235
3.291
3.2240
3.1740
3.1140
3.058

Experience with codeine phosphate patterns suggests that, if the powder photograph of an "unknown", by comparison with the tabulated data for the anhydrous salt (no. 10) or the dihydrate (no. 11), or with the data in the Table of Patterns of Mixtures of Codeine Phosphate Hydrates, indicates the possible presence of codeine phosphate, a portion of the sample should be placed in an oven at 70oC for at least 24 hours, and then taken up directly from the oven in a capillary tube the ends of which should be sealed immediately, preferably in a flame. If the "unknown" is codeine phosphate the pattern from this specimen will be that of fig. 10. Alternatively, a portion of the sample may be dissolved in distilled water, heated gently (at 60oC to 70oC) until, after removal from the source of heat, crystallization commences before the temperature falls to that of the room. The mixture should be stirred vigorously and the crystals crushed against the side of the vessel as crystallization proceeds in order to ensure small particle size. When the creamy mixture is at room temperature it should be drawn into a capillary tube, care being taken that excess water is present, and the tube should be sealed immediately with vacuum wax. The powder pattern from this material (the dihydrate) will be that of fig. 11 if the "unknown" is, in fact, codeine phosphate.

Conversion to the anhydrous form rather than to the dihydrate is recommended because of the rapid efflorescence of the latter unless proper precautions are taken. Once obtained, the anhydrous form does not absorb moisture from the atmosphere very rapidly so that ample time, without special care, is available for preparation of the specimen for the powder camera. For example, the typical "anhydrous" pattern was given by two specimens of codeine phosphate (sample B) taken from an oven after one and two days, respectively, at 70°C and exposed to the air of the laboratory for 15 minutes (room temperature, 25.5°C; relative humidity, 48 per cent) and 30 minutes (room temperature, 26°C; relative humidity, 49 per cent), respectively. In both cases, the capillary tubes were flame-sealed after the specimens were introduced. In another test no change in the "anhydrous" pattern was observed after a sample was first converted to the anhydrous phase in an oven at 70°C and then was stored for almost 3 days in an atmosphere of controlled relative humidity, 32.3 per cent, in a desiccator above a saturated solution of CaCl 2.6H 2O, in contact with the solid, at 20°C.

Cotarnine (free base)

Two different commercial preparations were investigated; the first (A) was dull brick-red in colour, the second (B) was pale yellow. Both samples gave the same pattern (fig. 12) when received, but two powder photographs of A taken seventeen months after the original one showed two additional faint lines, d = 10.3?, I/ I 1 = 3 and d = 8.4?, I/ I 1 = 2, which, however, did not appear on powder photographs of B after a lapse of two months. Small portions of both samples were dissolved in distilled water and allowed to recrystallize at room temperature. In both cases the crystals (with excess water) were taken up in capillary tubes which then were sealed. The diffraction patterns from both specimens (including that from A whose pattern had developed the two "extra" lines) were identical with the original one (fig. 12). It is possible that the two unidentified lines may have been the strongest ones of the pattern of a trace of some product derived from cotarnine at room temperature by a slow rate of loss of the elements of water but from which cotarnine may be reconstituted by recrystallization from aqueous solution. They may, of course, merely have been due to a small quantity of an impurity which was detected only in one specimen.

On heating the dark-coloured sample (A) in an oven at 70 °C for twenty-seven hours, its colour altered through a very dark red to a deep purple. A powder photograph of the material at this stage showed only a single broad halo at 2 &theta~ 25°, indicating an amorphous product. Therefore, a portion of the pale yellow preparation (B) was placed in an oven at 70°C and samples were removed for powder photographs (in sealed capillary tubes) at the end of 6 hours, 3 days, and 5 days, respectively. At the end of three days, the colour had passed through dark yellow to the dull brick-red shade characteristic of tile original sample A; beyond this time further colour changes were similar to those observed for A. The three successive powder patterns showed a progressive weakening and broadening of the diffraction lines with a gradual increase in the intensity of the general background of the film and the emergence of the broad halo at 2 &theta~ 25°. At the end of five days only the eight strongest lines of the original pattern (fig. 12) appeared (with greatly diminished intensity) in the powder photograph, together with two or three extremely faint lines of doubtful validity not attributable to cotarnine. The colour changes that cotarnine undergoes at 70°C thus appear to be due to thermal decomposition into an amorphous product, and the difference in colour of the two original samples indicates that such decomposition may occur slowly even at room temperature. Since the two lines that appeared in the photographs of sample A after seventeen months at room temperature were not observed in the photographs of sample B at successive stages of heating at 70°C, two types of decomposition or change may be involved.

No difficulty, however, need be anticipated in the identification of cotarnine providing the possible presence of very faint extraneous lines due to ageing are borne in mind; such lines, in fact, probably would not be observable in a normal exposure time. The thermal decomposition products, which appear to be responsible for the colour of cotarnine samples, add no diffraction lines of any significance to the photographs and the principal lines due to cotarnine are identifiable until decomposition has reached a very advanced stage and the colour of the sample has become very dark.

o-Diphenoloxymorphine (free base)

The only sample of this morphine derivative available for the present investigation gave a pattern consisting of a single, broad, diffuse halo characteristic of an amorphous material. No data, therefore, suitable for identification purposes were obtained.

Diamorphine (free base), Diamorphine Hydrochloride Monohydrate, Morphine Monohydrate (free base), Morphine Hydrochloride (anhydrous), and Morphine Hydrochloride Trihydrate

Gross and Oberst ([4] ) state that "a single pattern is acceptable identification when exact coincidence with a reference is obtained, but the use of two patterns of an alkaloid (one of the base and one of its hydrochloride salt) renders the result conclusive". This appears to reflect the convention usual in most schemes of inorganic qualitative chemical analysis of conducting a confirmatory test for each ion identified. The X-ray diffraction powder method, however, is essentially of the "fingerprint" type because the chance of exact coincidence of the patterns from two different crystalline phases, particularly among organic compounds, is insignificant, except in the special case of d- and l-anti- podes. Furthermore, the use of two patterns really serves to double the work of identification because each must be identified separately.

The procedure suggested for obtaining the confirmatory pattern also is open to serious objections. According to Gross and Oberst ([4] ), "Such reactions are readily carried out topochemically as follows: After a pattern of the free base is obtained, the mounted sample may be exposed to hydrochloric acid fumes for a short time. This converts the base to the hydrochloride salt (as shown by the absence of the diffraction lines of the base), and the second diffraction pattern may be obtained. If the starting material were the hydrochloride, exposure to ammonia fumes will convert it to the free base". In the first place, the "absence of the diffraction lines of the base" merely indicates that the base is no longer present in sufficient quantity for its pattern to be registered in the time required to record that of the new constituent; it gives no information about either the original base or the new substance. In the second place, the proposed reactions do not always proceed in the simple manner assumed, as shown by tests carried out on morphine (free base, and hydrochloride) and on diamorphine (heroin) (free base, and hydrochloride).

Experiments were performed ( a) with mounted specimens (glass fibres and Household Cement) suspended from the stoppers of vials containing a drop or two of concentrated hydrochloric acid or concentrated ammonia solution, and ( b) with the specimen in one well of a two-well microscope slide and a drop of the reagent in the other, the slide being enclosed in a covered Petri dish. Starting with morphine hydrochloride trihydrate (the usual form of the commercial preparation), exposure to NH 3 fumes for two or three minutes caused partial conversion to morphine monohydrate (free base) with the formation of NH 4Cl; transformation to the free base was complete in less than 30 minutes.

Similar treatment of the free base (monohydrate), either in the form of a fresh commercial sample or prepared (as above) from the hydrochloride, with fumes from concentrated HCl solution, however, gave a product the pattern of which (fig. 47) was not that of morphine hydrochloride trihydrate (fig. 48). This pattern was again obtained when the product was dissolved in concentrated hydrochloric acid and the solution allowed to evaporate to dryness. That the new substance was either anhydrous morphine hydrochloride or a lower hydrate became evident ( a) when it was recrystallized from distilled water and then gave the pattern of the trihydrate and ( b) when it gave the pattern of morphine monohydrate (free base) (together with that of NH 4Cl) when exposed to the fumes of concentrated NH 3 solution. The same substance (morphine hydrochloride, anhydrous or lower hydrate), as shown by its diffraction pattern, was obtained on treatment of morphine monohydrate (free base) with dry HCl gas; a water determination carried out by Mrs. P. M. Oestreicher established it as the anhydrous form.

The foregoing results may be summarized as follows:

morphin hydrochloride trihydrate
NH 3
morphine monohydrate (free base) + NH 4Cl
H 2O
NH 3
HCl
morphine hydrochloride (anhydrous)

Attempts to obtain anhydrous morphine hydrochloride by storage of the trihydrate in a desiccator under vacuum and by heating in an oven at 50°C gave substances whose patterns did not correspond with that of anhydrous morphine hydrochloride, although a loss of three moles of water occurred.

The results obtained when diamorphine (heroin) (free base) and diamorphine hydrochloride monohydrate were subjected to concentrated HCl fumes and to NH 3 fumes, respectively, were entirely different from those of the corresponding tests with morphine. The diamorphine (free base) exposed to HCl fumes in a closed Petri dish gave a pattern that was not that of diamorphine hydrochloride monohydrate and which underwent no change when the product was recrystallized from distilled water, thus indicating that it was not simply anhydrous diamorphine hydrochloride. Further exposure of the same sample to HCl fumes in a closed vial finally gave a product from which the pattern of anhydrous morphine hydrochloride was obtained together with a few faint lines due to some other substance, thus showing that continued exposure of diamorphine to HCl leads to deacetylation.

Prolonged exposure of diamorphine hydrochloride monohydrate to NH 3 fumes at first resulted in no change in pattern (other than the appearance of lines due to NH 4Cl) and finally in the emergence of additional lines not attributable to the presence of the free base.

These vapour treatments, therefore, cannot be recommended as general aids to the identification either of the free bases or of their hydrochloride salts.

The present powder diffraction data are in good agreement with those of Gross and Oberst ([4] ) for morphine monohydrate (free base) but not for morphine hydrochloride. It is possible that their sample of the latter was a mixture of the trihydrate and the anhydrous salt. Agreement is very poor also for both diamorphine (heroin, diacetylmorphine) (free base) and for diamorphine hydrochloride monohydrate.

Dihydromorphinone (free base) and Dihydromorphinone Hydrochloride

No difficulty was experienced in obtaining duplicate patterns from two commercial preparations of dihydromorphinone (dilaudid) hydrochloride. Although recognizable as probably the same as that observed by Gross and Oberst ([4] ) there are many discrepancies between the measured values for corresponding interplanar spacings.

No data for dihydromorphinone (free base) are included in the present paper. Several laboratory specimens prepared by Dr. C. G. Farmilo from the hydrochloride by the action of ammonia were investigated. The diffraction patterns of the products, however, showed so many variations that it became obvious that a separate study of the free base should be undertaken. Some of the patterns undoubtedly represent pure substances; others certainly are due to mixtures. One showed some superficial resemblance to the data given by Gross and Oberst ([4] ). Some indication was obtained that the product may depend on the pH of the solution resulting from the addition of ammonia to the aqueous solution of the hydrochloride. It is suspected also that ketoenol tautomerism may be involved.

Mescaline Sulphate Dihydrate

The present data are in very good agreement with those for mescaline sulphate in the A.S.T.M. Index (1). The latter were obtained from patterns given by copper radiation and with an apparatus "cut-off" of 9.3?; the strongest line ( d = 6.72 ?), therefore, also is the "innermost" line, whereas the present pattern extends the data to d = 19.6 ?. In spite of the different wavelengths employed, the order of the strongest lines is virtually the same; 6.72, 4.82, 3.61, 3.46, 3.28 ?, each with I/ I 1 = 100 as recorded on the A.S.T.M. card (no. 4.0157); 6.72, 4.81, 3.29, 3.96, 3.60 ?, with I/ I 1 = 100, 90, 85, 80, 80, respectively, for the present pattern, thus resulting only in a different allocation of the "third" line.

dl-Methadone Hydrobromide and dl-Methadone Hydrochloride

The present data for dl-methadone hydrochloride are in very good agreement with those obtained by Hubach and Jones (8) for a sample from a different commercial source. With copper radiation the spacings of the three strongest lines of their pattern are 7.46? (v.v.s.), 4.55? (v.v.s), 6.45? (v.s.); with cobalt radiation the spacings of the three strongest lines of the present pattern are 4.56? (100), 7.49? (90), 6.47? (60), thus merely interchanging the "first" and "second" lines.

The patterns and numerical data for dl-methadone hydrobromide (fig. 35) are strikingly similar to those for dl-methadone hydrochloride (fig. 37). Although single-crystal data have not yet been obtained, it is probable that the two salts are isomorphous and have unit cells of comparable dimensions. If so, then, relative to the size of the methadone molecule itself, the substitution of Cl for Br should have only a small effect on the spatial requirement of the methadone hydrohalide molecule, and hence the interplanar spacings, and relative reflection intensities, of corresponding sets of planes in the two structures should be very similar.

In the case of isomorphous NH 4Cl and NH 4Br the effect of the halide ion on the unit cell dimensions, and thus on the observed values of d, is much more pro- nounced because the radius of the ammonium ion actually is smaller than that of either halide ion and the diffraction patterns of the two salts are readily distinguishable. They form, however, mixed crystals (crystalline solid solutions) the interplanar spacings of which have values intermediate between the corresponding ones of the pure ammonium halides depending on the relative atomic proportions of each halogen.

Since the ammonium halides can often be identified more readily than the hydrohalide salt of a large organic molecule, it is sometimes convenient to convert the latter to the free base and the ammonium salt by treatment with ammonia, and then to identify the ammonium halide. This can be done very rapidly by dissolving the organic salt in distilled water, adding a slight excess of concentrated NH 3 solution, and gently evaporating the solution to dryness. The method of Gross and Oberst ([4] ) of exposing the mounted sample to NH 3 fumes also is very convenient for this purpose when interest is centered on the ammonium salt rather than on the organic base. A rapid (1/2 hour) exposure with copper radiation usually is sufficient to record the strongest lines of the ammonium halide pattern, and these are sufficient to decide between the bromide and the chloride.

One commercial preparation (A) of dl-methadone hydrochloride and two laboratory preparations (B,C) of the corresponding hydrobromide were examined. Of the latter, the second (C) was prepared by Dr. C. G. Farmilo from the hydrochloride (sample A) by precipitation of the free base and complete removal of ammonium chloride, as indicated by silver nitrate tests of the effluent wash water. The free base was then converted to the hydrobromide by treatment with hydrobromic acid (analytical reagent grade).

Identical patterns were obtained from two specimens of the hydrochloride (A) and for a (powdered) single crystal obtained by recrystallization from distilled water. Measurements of the pattern of the ammonium salt released by the action of NH 3 on a specimen of the hydrochloride were in excellent agreement with the precision data of Havinghurst, Mack and Blake ([6] ) for NH 4Cl.

Identical patterns also were obtained from specimens of the pure hydrobromide (C) as received and after recrystallization from distilled water. The pattern for the ammonium salt released by the action of NH 3 also was in excellent agreement with the data of Havinghurst, Mack and Blake ([6] ) for NH 4Br.

In the case of the hydrobromide sample B, however, although the patterns obtained from two specimens selected at random from the original container were virtually identical with that from sample C, specimens prepared by crushing ( a) several crystals, ( b) two individual crystals, ( c) one crystal, obtained by recrystallization from water, gave patterns of increasing resemblance to that from the hydrochloride. In each case the patterns of the ammonium salts were obtained and measured. The results for the interplanar spacings are shown in the accompanying table of Comparison of Interplanar Spacings of Ammonium Halides Obtained from Samples A,B,C with those of NH 4Cl and NH 4Br.

The data in columns 5 and 6 are from short-exposure films and are, therefore, not as complete as those in the other columns because only the lines of higher relative intensity were sufficiently strong for accurate measurement.

Comparison of Interplanar Spacings of Ammonium Halides Obtained from Samples A, B, C with those of NH 4 Cl and NH 4 Br

B (recrystallized from water)
NH 4Br( 6)CBcomposite2 crystals1 crystalA
4.054.044.024.003.943.923.863.87
2.862.852.842.832.782.763.743.73
2.342.342.322.312.28
2.232.23
2.022.022.012.001.971.961.941.93
1.811.811.801.791.761.731.731.73
1.651.651.641.631.611.601.581.58
1.431.431.421.42
1.371.37
1.351.351.341.34
1.291.29
1.281.281.271.27
1.221.22
1.221.221.211.21
1.171.17
1.171.171.161.16
1.121.12
1.121.121.121.11
1.071.07
1.081.081.081.07
1.041.03

From the data for the ammonium salts it is apparent that sample B, although largely the hydrobromide, does contain some of the hydrochloride. The evidence also suggests the presence of mixed crystals, methadone-H (Br,Cl), since the patterns from the various specimens prepared from sample B appear to be intermediate between those of the pure hydrobromide (sample C) and the pure hydrochloride (sample A), rather than mixtures of the two. Furthermore, the crushed single crystal not only gave the pattern most closely approaching that of pure dl-methadone hydrochloride but that of the corresponding ammonium salt (see table, column 6) most closely approaches that of NH 4Cl. It should be pointed out, however, that the ammonium salt obtained by the addition of ammonia to a mixture of the hydrochloride and the hydrobromide would itself be a solid solution, NH 4(Br,Cl), regardless of whether the original material consisted of a mixture of pure hydrochloride and pure hydrobromide crystals or whether it was composed of mixed hydro-(bromide, chloride) crystals.

In cases of possible ambiguity due to suspected isomorphism, or mixed crystal formation, among the hydrohalide salts of a narcotic base, it is convenient in the first place simply to identify the narcotic as the hydrohalide salt, and then to liberate the ammonium halide and identify the halogen in a subsequent step.

Parenthetically, attention may be drawn to the fact that while the pattern of dl-methadone hydrochloride (fig. 37) is not the same as that of the d- (and l-) antipode (fig. 36), the patterns of the free base in the d-, l-, and dl-forms are identical (fig. 34).

Metopon (free base) and Metopon Hydrochloride

The present interplanar spacings for metopon hydrochloride are in good agreement with those given by Gross and Oberst ([4] ).

Metopon (free base), however, was somewhat troublesome. The first pattern (fig. 87) was obtained from a mechanically ground specimen and was not entirely satisfactory because several of the lines were unusually broad. A second pattern from another specimen of the same sample, but in a capillary tube and not ground, was normal in appearance (see fig. 43) but a few moderately strong lines in the original pattern were missing and there was a marked difference in the relative intensities of other lines. A third pattern, however, was identical with the second. The time intervals between patterns were approximately four months between the first and second, and two weeks between the second and the third. Since the water content corresponded to 1.8 moles it was suspected that a mixture of dihydrate and a lower hydrate, or the anhydrous base, might be involved. Accordingly, the last remaining portion of the original sample (not more than 0.1 mg.) was kept at 70°C in an oven for four days, after which it was taken up in a capillary tube which was then sealed with wax. A pattern identical with the second and third was obtained. Since there was insufficient material to recrystallize from water, the capillary tube was opened, distilled water was introduced, and it was resealed with wax. The "wet" specimen gave the same pattern as the dry. The specimen was pushed out of the capillary tube with a glass fibre and divided into two portions. Both were crushed separately and were mounted on separate glass fibres with Household Cement; one specimen was intentionally subjected to more vigorous grinding. The resulting patterns closely resembled the original one (fig. 87); that from the more vigorously ground specimen being virtually identical with it. The specimens were so small that better resolution of the diffraction lines was obtained and it became obvious that the breadth of some of the lines in the original pattern (fig. 87) was due simply to unresolved pairs of lines. Mechanical grinding of metopon (free base), therefore, apparently causes some alteration in the substance, probably a polymorphic transformation.

Numerical data for the suspected polymorph are not included in the present paper because it is not certain that complete transformation was achieved. Sufficient material was not available for more exhaustive tests but it seems desirable to avoid mechanical grinding of any "unknown" suspected to be metopon (free base).

Morphine Sulphate

Two commercial preparations (A,B) were examined. The patterns from each varied between that for the pentahydrate (fig. 52) and that for the dihydrate (fig. 51), the intermediate ones (e.g., fig. 88) representing mixtures of the two phases, depending on conditions of temperature and relative humidity. The original samples gave the pentahydrate pattern and no change of the material in the stoppered bottles was observed over a period of fifteen months providing the specimens for X-ray diffraction photographs were taken up in capillary tubes without grinding. Crushing the samples, or merely spreading them on a microscope slide and exposing them to the air of the room, sometimes resulted in partial or complete change of the pentahydrate to the dihydrate or vice versa, depending on the relative humidity prevailing in the laboratory. Thus, during a period of high temperature and low humidity a sample of the pentahydrate changed to the dihydrate overnight whereas no transformation of another specimen of the pentahydrate occurred after six days at a time when the relative humidity was much higher. Controlled relative humidities (at 20°C of 32.3 per cent and 20 per cent, respectively), had no effect on the pentahydrate over periods of several days. In the presence of anhydrous CaCl 2 a partial transformation of the pentahydrate to the dihydrate was observed but anomalous results were obtained in a P 20 5 desiccator ( i. e., from no detectable change to almost complete conversion to the dihydrate with different specimens).

The dihydrate remained unchanged after storage for a week over P 20 5. It was, however, converted into the pentahydrate in less than 30 minutes when exposed to the air of the laboratory at a temperature of 21°C and a relative humidity of 50 per cent.

The pentahydrate can always be assured by the addition of a trace of water to the capillary tube containing the sample, and the dihydrate can always be obtained from the pentahydrate by heating for a few hours (conveniently overnight) at 60°C or 70°C. No change in the observed patterns of specimens of the dihydrate occurred after they had been kept continuously in an oven at 70°C for as long as six weeks.

If the pattern of an "unknown" appears to be a mixture of morphine sulphate dihydrate and morphine sulphate pentahydrate, it is recommended that the specimen be converted fully into one or the other for final identification. In either case the sealed capillary-tube method should be used.

The present data for morphine sulphate dihydrate and for morphine sulphate pentahydrate are in reasonably good agreement with the measurements of Gross and Oberst ([4] ), although it is probable that their 3.84? spacing for the dihydrate corresponds to that of 3.93? in the present pattern because the relative intensity of the latter is much higher than that of the line representing d = 3.85?. The absence of the 6.50? line ( I/I 1 = 60) from the data of Gross and Oberst for the pentahydrate apparently is due to its non-resolution from the 6.21? line ( cf., their fig. 2). Finally, the presence of the 7.16? line (the second strongest of the dihydrate pattern) in their data for the pentahydrate suggests a trace of the dihydrate in the pentahydrate specimen; the strongest line (6.24?) of the dihydrate would not be resolved from the strongest line (6.21?) of the pentahydrate on their films.

Narcotine Hydrochloride

Narcotine hydrochloride was particularly troublesome and, like codeine phosphate, warrants a more thorough investigation than was possible during the present survey. It has been reported ([7] ,[12] ) as crystallizing with ?, 1, 3, and 4 moles of H 20 and is known to form basic salts. Two commercial samples (A,B) were examined.

Sample A consisted of very small anhedral crystal fragments. Of seven specimens selected at random over a period of nineteen months, four (including one heated to 64°C for 22 hours) gave identical patterns (fig. 58), the photographs from two showed a very faint additional line, and that from one exhibited a large number of "extra" lines indicating a mixture of the phase giving rise to the original pattern and some other constituent. Crushing the specimens, or heating them at 64°C, had no effect on the patterns. The results, therefore, suggest that sample A is essentially a pure phase, narcotine hydrochloride (I) (fig. 58) with a small proportion of another phase (or other phases), the size of the specimens used for the X-ray diffraction patterns being too small to ensure the same relative proportions of the different constituents in each specimen.

Three specimens of sample B ( a, ground and mounted with Household Cement on a glass fibre; b, heated for 22 hours at 64°C; c, taken up in a capillary tube from the original container) gave patterns which, although not identical, were very much alike and were very similar to the complex (mixture) pattern obtained from one specimen of sample A. That from the unground specimen ( c) consisted of a mixture of smooth and grainy lines, the former corresponding to those of the narcotine hydrochloride (I) pattern of sample A. The larger crystal fragments responsible for the grainy lines could be hand-picked from the sample under a stereoscopic microscope. Several of these were selected and were washed individually with carbon tetrachloride to disengage fine particles adhering to them. Each was crushed to a fine powder and a diffraction pattern was obtained. From the results, two patterns, narcotine hydrochloride (II), (fig. 59) and narcotine hydrochloride (III) (fig. 60), were isolated, and it was found that virtually all the "extra" lines in the complex pattern from one specimen of sample A were due to narcotine hydrochloride (II) while the presence of a trace of narcotine hydrochloride (III) would account for most of the others. One of the crushed specimens giving the narcotine hydrochloride (II) pattern was extruded from its capillary tube and was reground; the resulting pattern showed a few minor changes in relative intensities but no radical differences from the first pattern.

It thus appears that both commercial samples (A, B) represent mixtures of at least three phases. Sample A is essentially narcotine hydrochloride (I) with a small proportion of narcotine hydrochloride (II) and probably a trace of narcotine hydrochloride (III); sample B contains a much larger proportion of narcotine hydrochloride (II) with some narcotine hydrochloride (III). Detailed comparison of all the patterns indicates that there may be at least one other phase present.

Attempts to identify the phases (probably different hydrates) responsible for the patterns designated narcotine hydrochloride (I), (II), and (III) were not successful. Exposure to air saturated with water vapour and recrystallization from dilute hydrochloride acid produced substances whose patterns could not be correlated with any of those previously obtained. It is clear that a prolonged and detailed study may be necessary. Since the water content of sample A (0.6 mole) was much less than that of sample B (1.17 mole), narcotine hydrochloride (I) presumably is a lower hydrate.

The data for the narcotine hydrochlorides (I, II, III) probably are the least reliable of those presented in the present paper. Those for narcotine hydrochloride (I), although repeatedly obtained, are based on (small) composite specimens of sample A; the pattern, therefore, may contain some weak lines from an unidentified phase, although this is believed to be unlikely. The patterns for narcotine hydrochlorides (II) and (III) should represent pure phases (including, of course, the possibility of mixed crystals) because they were obtained from individual fragments that appeared to be single crystals. Unfortunately it was impossible to remove all adhering particles of powder from their surfaces without breaking them, so that some weak lines may be due to other phases. The mass of the unremovable particles, however, appeared to be negligible compared with that of the crystal fragments, and, as a further precaution, lines in the diffraction patterns having relative intensities ( I/I 1) <2 have not been included in the tabulated data.

Although there is a close similarity between the three strongest lines of narcotine hydrochloride (II) and those of narcotine hydrochloride (III), there are too many major differences in the patterns as a whole to leave any doubt that they represent different phases. They may be isomorphous, and mixed crystal formation may be involved.

Pethidine Hydrochloride

The present data for pethidine (demerol) hydrochloride were obtained from two identical patterns given by separate specimens of a single commercial sample. No unusual features or difficulties were encountered with this substance but the observed spacings are in very poor agreement with those given by Gross and Oberst ([4] ).

dl-&alpha-Prodine Hydrochloride and dl-&beta-Prodine Hydrochloride

One sample each of dl-&alpha-prodine hydrochloride and of dl- &beta-prodine hydrochloride were examined. There was reason to assume that both had been prepared and separated by the method of Ziering and Lee ([14] ). Two specimens of the &alpha-form gave identical patterns (fig. 75), as did two specimens from the sample alleged to be the &beta-form. The latter pattern, however, from an unground specimen, consisted of a set of very grainy lines (identified as due to the &alpha-form) and a set of less grainy lines presumably due to the &beta-form; the pattern from a ground specimen is shown in fig. 89.

Under the stereoscopic microscope it was possible to separate crystals of two different habits from the much smaller anhedral crystal fragments of which the sample of dl-&beta-prodine hydrochloride largely was composed. Although both monoclinic, the superficial appearance of the larger crystals was that of rectangular plates while that of the smaller ones was of elongated pseudohexagonal plates. Single-crystal photographs showed that the two types of crystals represent different structures. Powder photographs of crushed single crystals of both types, washed with amyl acetate to remove adhering fragments, led to the identification of the pseudorectangular plates with the original sample of the &alpha-form, and the pseudo-hexagonal plates with the second constitutent of the sample of the &beta-form.

From the method of separation of the &alpha-form from the &beta-form ([14] ) it is perhaps not surprising that the latter should contain an appreciable proportion of the former.

Protopine (free base)

The first two diffraction photographs of a commercial sample of protopine indicated a mixture of crystalline phases because the second showed a very few grainy lines in addition to the smooth lines observed in the first pattern. A third specimen (not ground) gave a composite pattern (fig. 90) of smooth and grainy lines. Microscopic examination revealed the presence of clear crystal fragments in a mass of much smaller material. Through the courtesy of Dr. L. Marion, a pure authenticated sample of protopine crystals extracted from Adlumia fungosa, and a second commercial sample from the same firm as the original, were obtained. A single crystal X-ray diffraction study of the former and a powder photograph of the latter demonstrated their identity and showed that, while the grainy lines in the patterns from the original material were due to protopine, the smooth lines were not. From the single-crystal data the protopine powder data were authenticated from the maximum d observed (which is also the maximum possible) to d = 2.90?.

The second constituent of the original sample was not identified. It is unlikely to be a decomposition product because three clear crystals of protopine exhibited no visual microscopic evidence of any change whatsoever after a period of three days in an oven at 70 degrees C. In the absence of any evidence that protopine forms hydrates, it is suspected that the unidentified phase represents another alkaloid not separated from the protopine during isolation of the latter. Information could not be obtained about the source material for the first protopine preparation, otherwise it would have been feasible to obtain patterns of other alkaloids that might be expected to have been isolated with the protopine. The pattern from the "unknown" does not match that of cryptopine or that of any other narcotic included in the present survey.

Thebenine Hydrochloride Monohydrate

Six specimens from a single sample of thebenine hydrochloride monohydrate gave identical patterns (fig. 83), except for a weak ( 1/1 1 = 3) line corresponding to d = 12.7? that was present in one of the photographs. This line has been omitted from the tabulated data. It cannot be due to thebaine (free base) (from which thebenine hydrochloride may be prepared ([12] )) nor to thebaine hydrochloride; it probably represents a trace of some other alkaloid present in such small amount that enough for the appearance of one very weak line was present only in one specimen of the thebenine hydrochloride monohydrate sample examined.

Note Added in Proof (September 1954)

The authentication of the patterns for some of the narcotics (codeine (anhydrous free base), codeine monohydrate (free base), dihydrocodeinone (free base), protopine) on the basis of single-crystal data has been extended to dl-methadone hydrobromide, dl-methadone hydrochloride, dl-alphaprodine hydrochloride, dl-betaprodine hydrochloride, papaverine (free base), and papaverine hydrochloride, since this paper was completed in 1953 (see Barnes, W. H. and Forsyth, W. J., Unit Cell, Space Group, and Indexed X-Ray Diffraction Powder Data for Certain Narcotics. I-V., Can. J. Chem., 32, 984-995, 1954). Furthermore, a Fifth Set of Data Cards, recently issued by the American Society for Testing Materials (1), includes information on dl-methadone hydrobromide (Card 5-0128), dl-methadone hydrochloride (Card 5-0137), morphine sulphate pentahydrate (Card 5-0179), papaverine hydrochloride (Card 5-0279), and codeine phosphate dihydrate (Card 5-0345), supplied by Eli Lilly and Company, Indianapolis, Indiana, and obtained with Cu radiation. Agreement with the present results for dl-methadone hydrobromide, dl-methadone hydrochloride, and papaverine hydrochloride is good in so far as d values are concerned, although the Lilly data generally are slightly lower; there are greater differences among the I/I 1 estimations, in part perhaps owing to the different radiation employed. On the appropriate A.S.T.M. cards, &lambda=1.5374 (kX); for direct comparison with present values, the d's of these cards, therefore, should be increased by almost 0.3% (equivalent to the use of &lambda=l.5418?). In the case of papaverine hydrochloride no line of d=8.77 (A.S.T.M. Card 5-0279) should appear according to the single-crystal data.

The present results for morphine sulphate pentahydrate are in only fair agreement with those recorded on A.S.T.M. Card 5-0179. The d values of the latter (calculated with &lambda=1.5418, according to the card) in general are higher than the corresponding ones obtained in this laboratory, and by Gross and Oberst ([4] ), particularly in the (less accurately measurable) small 20 region.

There is very poor agreement (both for d and I/I 1) between the two sets of results for codeine phosphate dihydrate. The A.S.T.M. values for d (Card 5-0345) in some cases are higher, and in others lower, than corresponding ones presented in this paper; they resemble more closely the results obtained for Sample B (original) as shown in the Table of Patterns of Mixtures of Codeine Phosphate Hydrates (see p. 30) and believed to represent the pattern of a phase that was not identified. The discrepancy serves to illustrate further the difficulties inherent in the identification of codeine phosphate unless suitable precautions are observed.

ACKNOWLEDGEMENTS

Grateful acknowledgement is made to Mrs. Mary M. Taylor, Division of Applied Chemistry, National Research Laboratories, for assistance in measuring the films, and to Mr. W. J. Forsyth who took some of the powder photographs, made all the intermediate negatives and prints for reproduction, and assisted with the experimental work in connexion with the solution of some of the difficulties encountered with individual narcotics.

1

Numbers in parentheses refer to the list of References.

2

Where this cement is not available, a laboratory adhesive the composition of which is given in the Handbook of Chemistry and Physics([5] ), probably would be equally satisfactory.

3

A standard wire gauge is convenient for testing the outside diameter, and a copper wire of suitable gauge for the bore.

REFERENCES

American Society for Testing Materials. X-Ray Diffraction Data Cards and Index, Philadelphia, 1954.

Barnes, W. H. Physical Methods for the Identification of Narcotics, IIA. The X-Ray Diffraction Powder Method, Bulletin on Narcotics, Vol. VI, No. 1, 20-31, 1954.

Farmilo, C. G., Oestreicher, P. M., and Levi, L. Physical Methods for the Identification of Narcotics, Part IB. The Common Physical Constants for Identification of Ninety-five Narcotics and Related Compounds, Bulletin on Narcotics, Vol. VI, No. 1, 7-19, 1954.

Gross, S. T. and Oberst, F. W. Microanalysis of Opiates by X-Ray Diffraction, J. Lab. and Clinical Med., 32, 94-101, 1947.

Handbook of Chemistry and Physics (Chem. Rubber), Cleveland, 1950-51, p. 2706.

Havinghurst, R. J., Mack, E., and Blake, F. C. Precision Crystal Measurements on some Alkali and Ammonium Halides, J.A.C.S., 46, 2368-2374, 1924.

Henry, T. A. The Plant Alkaloids, (Churchill), London, 1939.

Hubach, C. E., and Jones, F. T., Methadon Hydrochloride, Optical Properties, Microchemical Reactions, and X-Ray Diffraction Data, Anal. Chem., 22, 595-598, 1950.

Levinson, A. A. and Hewitt, C. H. Lead Contamination in Duco Cement, American Mineral., 37 , 864-865, 1952.

Matthews, F. W., Capillary Specimens for X-Ray Diffraction Powder Analysis, Anal. Chem., 26 , 619, 1954.

Porter, M. W. and Spiller, R. C. The Barker Index of Crystals, (Heffer), Cambridge, 1951, vol. 1, part 2.

Small, L. F. Chemistry of the Opium Alkaloids, Supplement No. 103, Public Health Service, Washington, 1932.

Swanson, H. E. Tables for Conversion of X-Ray Diffraction Angles to Interplanar Spacing, App. Math. Ser. 10, National Bureau of Standards, Washington, 1950.

Ziering, A. and Lee, J. Piperidine Derivatives, V. 1,3-Dialkyl-4-aryl-4-acyloxypiperidines, J. Org. Chem., 12, 913, 1947; see under 1,3-Dimethyl-4-phenyl-4-propionoxypiperidine.

Alphabetical Index

The narcotics are listed alphabetically according to "common names" chosen for reasons given in another paper ([3] ), where the corresponding structural formulae, complete chemical names and synonyms also will be found. In arranging the index the prefixes d-, l-, dl-, have been ignored in determining the alphabetical sequence because identical X-ray diffraction powder patterns always are obtained from d- and l- antipodes and sometimes also from the corresponding dl-racemoid. When these prefixes (dextro-, levo-, race- (or racem-)) usually form part of the accepted name of the substance they have been changed to the corresponding letters ( d-, l-, dl-). Thus Dextromethorphan, Levomethorphan, Racemethorphan are listed as d-Methorphan, l-Methorphan, dl-Methorphan, respectively, and Dextrorphan, Levorphan, Racemorphan appear as d-Orphan, l-Orphan, dl-Orphan, respectively. (In the case of l-Orphan Tartrate Dihydrate a sample of the d-form was not available for the present investigation; its pattern, however, would be the same as that obtained from the l-antipode, and the data for the latter are listed, therefore, under " d-, and l-Orphan Tartrate Dihydrate".) The prefixes "alpha" and "beta" have been altered to " &alpha" and " &beta" and ignored in the alphabetical listing, in order to place Alphaprodine Hydrochloride and Betaprodine Hydrochloride in sequence under "Prodine Hydrochloride" (with the appropriate Greek letter prefix).

To avoid any ambiguity between the alkaloids and their salts, the names of the former are followed by the words free base in parentheses. Also, where the pattern for an anhydrous substance has been obtained in addition to that of a hydrate, the word anhydrous has been added in parentheses to the name of the alkaloid, and the degree of hydration has been incorporated in the name of the hydrate. Where the name of a non-hydrate occurs without the designation (anhydrous), the anhydrous form is implied except in the case of Papaverine Hydrochloride for which accurate water determinations were not available and in a few cases where the degree of hydration was uncertain.

Following the name of each narcotic in the alphabetical index is a number which corresponds with that of the reproduction of a typical powder photograph of the substance among the Figures. After this number are given in sequence the spacing ( d) of the first, second and third strongest lines and that of the "innermost line" ( i.e., maximum d observed), and then the relative intensity ( I/I 1) of the first, second and third strongest lines, and that of the "innermost line". Where the relative intensities of two (or three) of the strongest lines are equal, the A.S.T.M. convention (1) has been followed of using the descending order of the d values to fix the sequence 1, 2, 3. Thus, of two lines having I/I 1 = 100, that with the larger spacing is designated 1 and the other 2. Similarly if more than one line has the same relative intensity that would correspond to position 3 in the list, the line with the largest d is chosen.

Finally, the star after a name indicates that further information about that substance will be found in the Notes on Individual Narcotics.

d
I/I1
NameNo.123I.L.123I.L.
Acedicon® Hydrochloride
110.44.814.2211.6100807515
Acetoxyketobemidone Hydrochloride
25.764.906.3311.1100908560
Alphaprodine .... See Prodine
Apomorphine Hydrochloride
38.084.404.0311.2100908010
Benzylmorphine (free base)
47.585.804.118.5810010010090
Benzylmorphine Hydrochloride
59.783.635.359.781009080100
Betaprodine .... See Prodine
Cocaine (free base)
64.417.389.729.72100605050
Cocaine Hydrochloride
75.8810.73.0910.7100907590
Codeine (anhydrous free base)*
86.473.774.8910.1100756015
Codeine Monohydrate (free base)*
94.858.766.738.76100905090
Codeine Phosphate (anhydrous) *
106.303.866.7416.1100806520
Codeine Phosphate Dihydrate*
116.553.515.0617.0100604020
Cotarnine (free base)*
126.393.537.057.051001006060
Cryptopine (free base)
135.562.834.017.36100806040
Dextromethorphan .... See Methorphan.
Dextrorphan.... See Orphan
Diamorphine (free base)*
145.297.005.0810.7100755010
Diamorphine Hydrochloride Monohydrate*
159.035.177.2617.6100908010
Dihydrocodeine (free base)
166.337.106.169.63100808010
Dihydrocodeinone (free base)*
176.493.784.8310.1100754015
Dihydrocodeinone Bitartrate (Dihydrate?)
188.445.124.2816.6100908010
Dihydromorphine Monohydrate (free base)
196.017.414.1810.1100756020
Dihydromorphinone Hydrochloride*
206.656.064.579.621001008050
Dioxyline Phosphate
216.913.594.2412.4100504030
Ethylmorphine Hydrochloride
223.928.105.6911.2100808020
Ethylnarceine Hydrochloride
234.376.3412.612.6100907575
Ethylpethidine Hydrochloride
246.9313.34.4613.3100908090
Hydrastinine Hydrochloride Monohydrate
253.465.178.099.50100806040
Hydromorphone See Dihydromorphinone
Hydroxypethidine (free base)
264.557.505.3514.8100757560
Hydroxypethidine Hydrochloride
275.003.755.5313.9100757050
dl-Isomethadone Hydrochloride Monohydrate
287.255.835.2813.1100755015
Ketobemidone (free base)
294.498.445.088.7710060403
Ketobemidone Hydrochloride
305.093.673.819.46100756050
dl-Laudanine (free base)
316.794.304.089.69100606040
Levomethorphan See Methorphan
Levorphan See Orphan
Meconic Acid Trihydrate
323.249.862.489.86100605060
Mescaline Sulphate Dihydrate*
336.724.813.2919.6100908515
d-, l-, and dl-Methadone (free base)
348.366.744.709.4110090751
dl-Methadone Hydrobromide*
354.607.586.5212.6100908030
d-, and l-Methadone Hydrochloride
364.427.434.7312.4100403015
dl-Methadone Hydrochloride*
374.577.506.4812.4100907025
dl-Methorphan (free base)
383.906.645.1410.3100909020
d-, and l-Methorphan Hydrobromide Monohydrate
395.203.835.6313.7100906040
dl-Methorphan Hydrobromide Dihydrate
404.653.866.9418.3100504012
Methylketobemidone (free base)
414.285.987.698.56100908075
Methylketobemidone Hydrochloride
425.824.803.369.63100606025
Metopon (Dihydrate?) (free base)*
4310.15.599.1310.11009575100
Metopon Hydrochloride*
444.226.966.498.28100808015
a-Monoacetylmorphine (free base)
456.554.757.0710.4100757025
Morphine Hydriodide Dihydrate
463.894.726.0311.0100706050
Morphine Hydrochloride (anhydrous)*
476.795.954.168.1210080605
Morphine Hydrochloride Trihydrate*
486.113.9510.411.1100100851
Morphine Monohydrate (free base)*
495.987.426.6110.1100606030
Morphine-N-oxide (free base)
505.715.183.729.7310050503
Morphine Sulphate Dihydrate*
516.267.184.2814.3100404015
Morphine Sulphate Pentahydrate*
526.204.373.6815.0100908070
Morphine Tartrate Monohydrate
535.354.687.7915.3100504015
Morphothebaine Hydrochloride
5410.63.753.5410.6100100100100
Nalorphine Hydrochloride
555.067.336.9110.5100808020
Narceine (free base)
5613.84.145.0813.81005045100
Narcotine (free base)
573.497.646.2216.2100755025
Narcotine Hydrochloride (I)*
586.404.237.9714.8100807530
Narcotine Hydrochloride (II)*
598.186.7610.615.9100907530
Narcotine Hydrochloride (III)*
606.778.1611.616.4100656025
Neopine Hydrobromide
616.044.205.6412.2100908040
Opianic Acid
627.3911.13.3911.1100606060
dl-Orphan (free base)
635.844.156.228.28100756040
dl-Orphan Hydrobromide
645.533.943.3114.7100907520
d-, and l-Orphan Tartrate Dihydrate
658.234.135.699.3910075503
Oxycodone (free base)
665.885.217.7010.5100504020
Oxycodone Hydrochloride
6710.67.285.4411.610090752
Papaverine (free base)
685.793.733.8714.8100908510
Papaverine Hydrochloride
694.565.123.5710.1100757520
Pethidine (free base)
709.495.464.799.491008060100
Pethidine Hydrochloride*
718.043.614.678.041009075100
Phenadoxone (free base)
726.204.507.628.79100904525
Phenadoxone Hydrochloride
736.395.203.8412.81001009030
Pipidone Hydrochloride
747.084.944.1910.8100805040
dl- &alpha-Prodine Hydrochloride*
757.145.966.6915.1100807050
dl- &beta-Prodine Hydrochloride*
768.135.875.1011.2100707020
Propylketobemidone (free base)
7710.65.025.7710.61009050100
Protopine (free base) *
784.475.964.3610.7100908020
Pseudomorphine Trihydrate (free base)
796.548.764.449.23100757530
Racemethorphan See Methorphan
Racemorphan See Orphan
Sinomenine Hydrochloride Dihydrate
806.119.626.7511.5100757540
Thebaine (free base)
817.765.113.737.761009090100
Thebaine Hydrochloride
827.443.474.887.441006050100
Thebenine Hydrochloride Monohydrate*
834.453.4710.710.7100756060

INNERMOST LINE INDEX

The maximum spacing ( d for the "innermost line") observed among the narcotics investigated varied from almost 20? to approximately 7?. Measurement (with a pocket rule graduated in millimeters) of the diameter of the "innermost line" of the pattern of an "unknown" even when the film has only just cleared in the fixer often will serve to limit the choice of possible substances.

In the following index the narcotics are arranged in the order of the interplanar spacings represented by their innermost lines. It must be remembered that the patterns were obtained in a l14.6mm, diameter camera with Co radiation, and that the maximum spacing observable (the "cut-off") was 20 ?. Thus the lines with the largest spacings would not be observed with copper radiation or with a camera of smaller radius, while a larger camera or chromium radiation might reveal lines of d above the 20 ? limit. In the first case a similar index can be drawn up from the tabulated data by first determining the "cut-off" for the equipment at hand and taking the first line of lower d as the innermost line. It is improbable that more than the first few substances could have d's larger than the maximum observed but their presence in films obtained under conditions with a "cut-off" at higher values should cause no difficulty.

In the index, the d for the innermost line is followed by the relative intensity, I/I 1, for that line. It should be borne in mind, however, that these values are relative to 100 for the strongest line of that particular pattern; the intensities are not on an absolute scale. In six cases the relative intensity is very low (<5) and, therefore, the lines may not be observed if relatively short exposure times are used. Hence the next line of lower d (which is a strong line in each case) is included in the index; these entries are enclosed in square brackets.

The number after each name is the same as that in the Alphabetical Index and corresponds to the Figure Number of the corresponding diffraction pattern.

Innermost Line Index

dI/I 1NameNo.
19.615
Mescaline Sulphate Dihydrate
33
18.312
dl-Methorphan Hydrobromide Dihydrate
40
17.610
Diamorphine Hydrochloride Monohydrate
15
17.020
Codeine Phosphate Dihydrate
11
16.610
Dihydrocodeinone Bitartrate (Dihydrate?)
18
16.425
Narcotine Hydrochloride (III)
60
16.225
Narcotine (free base)
57
16.120
Codeine Phosphate (anhydrous)
10
15.930
Narcotine Hydrochloride (II)
59
15.315
Morphine Tartrate Monohydrate
53
15.150
dl- a-Prodine Hydrochloride
75
15.070
Morphine Sulphate Pentahydrate
52
14.860
Hydroxypethidine (free base)
26
14.830
Narcotine Hydrochloride (I)
58
14.810
Papaverine (free base)
68
14.720
dl-Orphan Hydrobromide
64
14.315
Morphine Sulphate Dihydrate
51
13.950
Hydroxypethidine Hydrochloride
27
13.8100
Narceine (free base)
56
13.740
d-, and l-Methorphan Hydrobromide Monohydrate
39
13.390
Ethylpethidine Hydrochloride
24
13.115
dl-Isomethadone Hydrochloride Monohydrate
28
12.830
Phenadoxone Hydrochloride
73
12.675
Ethylnarceine Hydrochloride
23
12.630
dl-Methadone Hydrobromide
35
12.430
Dioxyline Phosphate
21
12.415
d-, and l-Methadone Hydrochloride
36
12.425
dl-Methadone Hydrochloride
37
12.240
Neopine Hydrobromide
61
11.615
Acedicon® Hydrochloride
1
11.62
Oxycodone Hydrochloride
67
11.540
Sinomenine Hydrochloride Dihydrate
80
11.210
Apomorphine Hydrochloride
3
11.220
Ethylmorphine Hydrochloride
22
11.220
dl-&beta-Prodine Hydrochloride
76
11.160
Acetoxyketobemidone Hydrochloride
2
11.11
Morphine Hydrochloride Trihydrate
48
11.160
Opianic Acid
62
11.050
Morphine Hydriodide Dihydrate
46
10.840
Pipidone Hydrochloride
74
10.790
Cocaine Hydrochloride
7
10.710
Diamorphine (free base)
14
10.720
Protopine (free base)
78
10.760
Thebenine Hydrochloride Monohydrate
83
10.6100
Morphothebaine Hydrochloride
54
[10.6100
Oxycodone Hydrochloride 67]
10.6100
Propylketobemidone (free base)
77
10.520
Nalorphine Hydrochloride
55
10.520
Oxycodone (free base)
66
10.425
a-Monoacetylmorphine (free base)
45
[10.485
Morphine Hydrochloride Trihydrate
48]
10.320
dl-Methorphan (free base)
38
10.115
Codeine (anhydrous free base)
8
10.115
Dihydrocodeinone (free base)
17
10.120
Dihydromorphine Monohydrate (free base)
19
10.1100
Metopon (Dihydrate?) (free base)
43
10.130
Morphine Monohydrate (free base)
49
10.120
Papaverine Hydrochloride
69
9.8660
Meconic Acid Trihydrate
32
9.78100
Benzylmorphine Hydrochloride
5
9.733
Morphine-N-oxide (free base)
50
9.7250
Cocaine (free base)
6
9.6940
dl-Laudanine (free base)
31
9.6310
Dihydrocodeine (free base)
16
9.6325
Methylketobemidone Hydrochloride
42
9.6250
Dihydromorphinone Hydrochloride
20
9.5049
Hydrastinine Hydrochloride Monohydrate
25
9.49100
Pethidine (free base)
70
9.4650
Ketobemidone Hydrochloride
30
9.411
d-, l-, and dl-Methadone (free base)
34
9.393
d-, and l-Orphan Tartrate Dihydrate
65
9.2330
Pseudomorphine Trihydrate (free base)
79
8.7925
Phenadoxone (free base)
72
8.773
Ketobemidone (free base)
29
8.7690
Codeine Monohydrate (free base)
9
8.5890
Benzylmorphine (free base)
4
8.5675
Methylketobemidone (free base)
41
[8.4460
Ketobemidone (free base)
29]
[8.36100
d-, l-, and dl-Methadone (free base)
34]
8.2815
Metopon Hydrochloride
44
8.2840
dl-Orphan (free base)
63
[8.23100
d-, and l-Orphan Tartrate Dihydrate
65]
8.125
Morphine Hydrochloride (anhydrous)
47
8.04100
Pethidine Hydrochloride
71
7.76100
Thebaine (free base)
[7.7025
Morphine-N-oxide (free base)
50]
7.44100
Thebaine Hydrochloride
82
7.3640
Cryptopine (free base)
13
7.0560
Cotarnine (free base)
12
[6.79100
Morphine Hydrochloride (anhydrous)
47]

NUMERICAL (HANAWALT) INDEX AND TABULATED (d, I/I1) DATA

For the convenience of those familiar with the A.S.T.M. Index ([1] ) the data are listed numerically according to the same scheme employed in the "blue" pages of A.S.T.M. Special Technical Publication No. 48-D. The three strongest lines of each pattern are indexed three times according to spacings ( d), namely in the order 1-2-3, 2-1-3, and 3-1-2 where 1,2,3 refer to the relative strength of the three strongest lines. The first d of each of these triplets determines the Hanawalt Group in which the three lines are placed. Within each group the sets of lines are listed in descending order of d for the second line of the triplet; if the second lines have the same d, the order (descending) of the third line is used. On each line of type the three d values are printed in sequence followed by the corresponding values of I/I 1 in the same order and then by the name of the substance and the Figure Number (in parentheses). At the beginning of each Hanawalt Group is given the group number and the range of values of d (the first of each triplet) represented in the group.

For example, the three strongest lines of the pattern of Cocaine Hydrochloride represent values of d = 5.88? ( I/I 1 = 100), 10.7? ( I/I 1 = 90), and 3.09? ( I/I 1 = 75), respectively. Cocaine Hydrochloride, therefore, will be found indexed under (1) 5.88, 10.7, 3.09; 100, 90, 75, under (2) 10.7, 5.88, 3.09; 90, 100, 75, and under (3) 3.09, 5.88, 10.7; 75, 100, 90. The first entry occurs in Hanawalt Group 72 (5.99 to 5.75?) and at the top because 10.7? is the largest spacing observed for the second line among the substances listed. The second entry appears in Hanawalt Group 81 (10.9 to 10.0?) where it is the third from the top. The third entry is in Hanawalt Group 45 (3.09 to 3.05?).

To use the numerical index, the spacings of the three strongest lines of the powder pattern of the "unknown" are determined and a visual estimate of their relative intensities is made. The Hanawalt Group that includes the spacing of the strongest line of the pattern is found. Some allowance for possible errors in measurement must be made, say about 0.1? for d > 10?, about 0.05? for d between 10 and 5?, and 0.02 to 0.01? for d between 5 and 1?.

If d for the strongest line of an "unknown" pattern has a value close to that of one of the limits of a Hanawalt Group, the Group which it approaches should be included in the search. Thus Ketobemidone (free base) in Hanawalt Group 63 with d = 4.49? for the spacing of the strongest line, might on another measurement have been listed in Group 64 with d = 4.50 or 4.51?.

Having selected the Hanawalt Group (or Groups) in which the data for the "unknown" are to be expected, the second column is examined for a value of d equal (or almost equal) to that found for the second strongest line. If a reasonable match is obtained, the d's for the first and third lines and the relative intensities of all three lines in the index are compared with the observed data. If there is reasonable agreement, the complete pattern of the "unknown" is compared with the Tabulated ( d, I/I 1) Data (immediately following the numerical index) for the substance suspected, or the film may be compared directly with the corresponding Figure bearing in mind that some distortion (usually a slight expansion) may have occurred during the various stages through which it has passed from the original negative to the final reproduction. It is preferable to use cobalt radiation; otherwise allowance must be made for appreciable contraction or expansion of the pattern if a different radiation (such as copper or chromium) has been employed, and for possible variations in relative intensities.

If the three strongest lines of the "unknown" are not found in the numerical index, when a search is made in the Hanawalt Group for the strongest line, the search should be repeated in the Groups corresponding to the second and third strongest lines, respectively. This helps to circumvent differences in the appraisal of relative intensities by different observers.

In the tabulated data following the numerical index, powder lines that were abnormally broad in a particular pattern are indicated by "B" or "BB" after the value of I/I 1 for the particular lines concerned; such lines generally represent two, or more, that were not resolved.

Numerical Index

83. 13.9 to 12.0

13.36.934.469010080
Ethylpethidine Hydrochloride (24)
12.64.376.347510090
Ethylnarceine Hydrochloride (23)
13.84.145.081005045
Narceine (free base) (56)

Numerical Index

82. 11.9 to 11.0

11.17.393.396010060
Opianic Acid (62)
11.66.778.166010065
Narcotine Hydrochloride (III) (60)

Numerical Index

81. 10.9 to 10.0

10.68.186.767510090
Narcotine Hydrochloride (II) (59)
10.67.285.441009075
Oxycodone Hydrochloride (67)
10.46.113.9585100100
Morphine Hydrochloride Trihydrate (48)
10.75.883.099910075
Cocaine Hydrochloride (7)
10.15.599.131009575
Metopon (Dihydrate?) (free base) (43)
10.65.025.771009050
Propylketobemidone (free base) (77)
10.44.814.221008075
Acedicon® Hydrochloride (1)
10.74.453.476010075
Thebenine Hydrochloride Monohydrate (83)
10.63.753.54100100100
Morphothebaine Hydrochloride (54)

Numerical Index

80. 9.99 to 9.50

9.626.116.757510075
Sinomenine Hydrochloride Dihydrate (80)
9.724.417.385010060
Cocaine (free base) (6)
9.783.635.351009080
Benzylmorphine Hydrochloride (5)
9.863.242.486010050
Meconic Acid Trihydrate (32)

Numerical Index

79. 9.49 to 9.00

9.1310.15.597510095
Metopon (Dihydrate?) (free base) (43)
9.495.464.791008060
Pethidine (free base) (70)
9.035.177.261009080
Diamorphine Hydrochloride Monohydrate (15)

Numerical Index

78. 8.99 to 8.50

8.766.544.447510075
Pseudomorphine Trihydrate (free base) (79)
8.764.856.739010050
Codeine Monohydrate (free base) (9)

Numerical Index

77. 8.49 to 8.00

8.166.7711.66510060
Narcotine Hydrochloride (III) (60)
8.186.7610.61009075
Narcotine Hydrochloride (II) (59)
8.366.744.701009075
d-, l-, and dl-Methadone (free base) (34)
8.135.875.101007070
dl-&beta-Prodine Hydrochloride (76)
8.445.124.281009080
Dihydrocodeinone Bitartrate (Dihydrate?) (18)
8.444.495.086010040
Ketobemidone (free base) (29)
8.084.404.031009080
Apomorphine Hydrochloride (3)
8.234.135.691007550
d-, and l-Orphan Tartrate Dihydrate (65)
8.103.925.698010080
Ethylmorphine Hydrochloride (22)
8.043.614.671009075
Pethidine Hydrochloride (71)
8.093.465.176010080
Hydrastinine Hydrochloride Monohydrate (25)

Numerical Index

76. 7.99 to 7.50

7.976.404.237510080
Narcotine Hydrochloride (I) (58)
7.626.204.504510090
Phenadoxone (free base) (72)
7.705.885.214010050
Oxycodone (free base) (66)
7.585.804.11100100100
Benzylmorphine (free base) (4)
7.795.354.684010050
Morphine Tartrate Monohydrate (53)
7.765.113.731009090
Thebaine (free base) (81)
7.584.606.529010080
dl-Methadone Hydrobromide (35)
7.504.576.489010070
dl-Methadone Hydrochloride (37)
7.504.555.357510075
Hydroxypethidine (free base) (26)
7.694.285.988010090
Methylketobemidone (free base) (41)
'7.64
3.496.227510050
Narcotine (free base) (57)

Numerical Index

75. 7.49 to 7.00

7.3911.13.391006060
Opianic Acid (62)
7.2810.65.449010075
Oxycodone Hydrochloride (67)
7.269.035.178010090
Diamorphine Hydrochloride Monohydrate (15)
7.076.554.757010075
&alpha-Monoacetylmorphine (free base) (45)
7.056.393.5360100100
Cotarnine (free base) (12)
7.106.336.168010080
Dihydrocodeine (free base) (16)
7.186.264.284010040
Morphine Sulphate Dihydrate (51)
7.416.014.187510060
Dihydromorphine Monohydrate (free base) (19)
7.425.986.616010060
Morphine Monohydrate (free base) (49)
7.145.966.691008070
dl-&alpha-Prodine Hydrochloride (75)
7.255.835.281007550
dl-Isomethadone Hydrochloride Monohydrate (28)
7.005.295.087510050
Diamorphine (free base) (14)
7.335.066.918010080
Nalorphine Hydrochloride (55)
7.084.944.191008050
Pipidone Hydrochloride (74)
7.434.424.734010030
d-, and l-Methadone Hydrochloride (36)
7.384.419.726010050
Cocaine (free base) (6)
7.443.474.881006050
Thebaine Hydrochloride (82)

Numerical Index

74. 6.99 to 6.50

6.9313.34.461009080
Ethylpethidine Hydrochloride (24)
6.548.764.441007575
Pseudomorphine Trihydrate (free base) (79)
6.748.364.709010075
d-, 1-, and dl-Methadone (free base) (34)
6.768.1810.69010075
Narcotine Hydrochloride (II) (59)
6.778.1611.61006560
Narcotine Hydrochloride (III) (60)
6.697.145.967010080
dl-&alpha-Prodine Hydrochloride (75)
6.746.303.866510080
Codeine Phosphate (anhydrous) (10)
6.756.119.627510075
Sinomenine Hydrochloride Dihydrate (80)
6.656.064.5710010080
Dihydromorphinone Hydrochloride (20)
6.615.987.426010060
Morphine Monohydrate (free base) (49)
6.795.954.161008060
Morphine Hydrochloride (anhydrous) (47)
6.915.067.338010080
Nalorphine Hydrochloride (55)
6.734.858.765010090
Codeine Monohydrate (free base) (9)
6.724.813.291009085
Mescaline Sulphate Dihydrate (33)
6.554.757.071007570
&alpha-Monoacetylmorphine (free base) (45)
6.944.653.864010050
dl-Methorphan Hydrobromide Dihydrate (40)
6.524.607.588010090
dl-Methadone Hydrobromide (35)
6.794.304.081006060
dl-Laudanine (free base) (31)
6.964.226.498010080
Metopon Hydrochloride (44)
6.643.905.149010090
dl-Methorphan (free base) (38)
6.913.594.241005040
Dioxyline Phosphate (21)
6.553.515.061006040
Codeine Phosphate Dihydrate (11)

Numerical Index

73. 6.49 to 6.00

6.119.626.751007575
Sinomenine Hydrochloride Dihydrate (80)
6.017.414.181007560
Dihydromorphine Monohydrate (free base)(19)
6.267.184.281004040
Morphine Sulphate Dihydrate (51)
6.337.106.161008080
Dihydrocodeine (free base) (16)
6.066.654.5710010080
Dihydromorphinone Hydrochloride (20)
6.166.337.108010080
Dihydrocodeine (free base) (16)
6.225.844.156010075
dl-Orphan (free base) (63)
6.335.764.908510090
Acetoxyketobemidone Hydrochloride (2)
6.395.203.8410010090
Phenadoxone Hydrochloride (73)
6.484.577.507010090
dl-Methadone Hydrochloride (37)
6.204.507.621009045
Phenadoxone (free base) (72)
6.344.3712.69010075
Ethylnarceine Hydrochloride (23)
6.204.373.681009080
Morphine Sulphate Pentahydrate (52)
6.404.237.971008075
Narcotine Hydrochloride (I) (58)
6.494.226.968010080
Metopon Hydrochloride (44)
6.044.205.641009080
Neopine Hydrobromide (61)
6.113.9510.410010085
Morphine Hydrochloride Trihydrate (48)
6.033.894.726010070
Morphine Hydriodide Dihydrate (46)
6.303.866.741008065
Codeine Phosphate (anhydrous) (10)
6.493.784.831007540
Dihydrocodeinone (free base) (17)
6.473.774.891007560
Codeine (anhydrous free base)(8)
6.393.537.0510010060
Cotarnine (free base) (12)
6.223.497.645010075
Narcotine (free base) (57)

Numerical Index

72. 5.99 to 5.75

5.8810.73.091009075
Cocaine Hydrochloride (7)
5.7710.65.025010090
Propylketobemidone (free base) (77)
5.878.135.107010070
dl-&beta-Prodine Hydrochloride (76)
5.807.584.11100100100
Benzylmorphine (free base) (4)
5.987.426.611006060
Morphine Monohydrate (free base) (49)
5.837.255.287510050
dl-Isomethadone Hydrochloride Monohydrate (28)
5.967.146.698010070
dl-&alpha-Prodine Hydrochloride (75)
5.956.794.168010060
Morphine Hydrochloride (anhydrous) (47)
5.885.217.701005040
Oxycodone (free base) (66)
5.764.906.331009085
Acetoxyketobemidone Hydrochloride (2)
5.824.803.361006060
Methylketobemidone Hydrochloride (42)
5.964.474.369010080
Protopine (free base) (78)
5.984.287.699010080
Methylketobemidone (free base) (41)
5.844.156.221007560
dl-Orphan (free base) (63)
5.793.733.871009085
Papaverine (free base) (68)

Numerical Index

71. 5.74 to 5.50

5.5910.19.139510075
Metopon (Dihydrate?) (free base) (43)
5.698.234.135010075
d-, and l-Orphan Tartrate Dihydrate (65)
5.646.044.208010090
Neopine Hydrobromide (61)
5.635.203.836010090
d-, and l-Methorphan Hydrobromide Monohydrate (39)
5.715.183.721005050
Morphine-N-oxide (free base) (50)
5.535.003.757010075
Hydroxypethidine Hydrochloride (27)
5.533.943.311009075
dl-Orphan Hydrobromide (64)
5.693.928.108010080
Ethylmorphine Hydrochloride (22)
5.562.834.011008060
Cryptopine (free base) (13)

Numerical Index

70. 5.49 to 5.25

5.4410.67.287510090
Oxycodone Hydrochloride (67)
5.359.783.638010090
Benzylmorphine Hydrochloride (5)
5.469.494.798010060
Pethidine (free base) (70)
5.287.255.835010075
dl-Isomethadone Hydrochloride Monohydrate (28)
5.297.005.081007550
Diamorphine (free base) (14)
5.354.687.791005040
Morphine Tartrate Monohydrate (53)
5.354.557.507510075
Hydroxypethidine (free base) (26)

Numerical Index

69. 5.24 to 5.00

5.0813.84.144510050
Narceine (free base) (56)
5.0210.65.779010050
Propylketobemidone (free base) (77)
5.179.037.269010080
Diamorphine Hydrochloride Monohydrate (15)
5.128.444.289010080
Dihydrocodeinone Bitartrate (Dihydrate?) (18)
5.108.135.877010070
dl-&beta-Prodine Hydrochloride (76)
5.117.763.739010090
Thebaine (free base) (81)
5.067.336.911008080
Nalorphine Hydrochloride (55)
5.066.553.514010060
Codeine Phosphate Dihydrate (11)
5.206.393.8410010090
Phenadoxone Hydrochloride (73)
5.215.887.705010040
Oxycodone (free base) (66)
5.185.713.725010050
Morphine-N-oxide (free base) (50)
5.085.297.005010075
Diamorphine (free base) (14)
5.124.563.577510075
Papaverine Hydrochloride (69)
5.084.498.444010060
Ketobemidone (free base) (29)
5.143.906.649010090
dl-Methorphan (free base) (38)
5.203.835.631009060
d-, and l-Methorphan Hydrobromide Monohydrate (39)
5.003.755.531007570
Hydroxypethidine Hydrochloride (27)
5.093.673.811007560
Ketobemidone Hydrochloride (30)
5.173.468.098010060
Hydrastinine Hydrochloride Monohydrate (25)

Numerical Index

68. 4.99 to 4.90

4.907.084.198010050
Pipidone Hydrochloride (74)
4.905.766.339010085
Acetoxyketobemidone Hydrochloride (2)

Numerical Index

67. 4.89 to 4.80

4.8110.44.228010075
Acedicon® Hydrochloride (1)
4.858.766.731009050
Codeine Monohydrate (free base) (9)
4.887.443.475010060
Thebaine Hydrochloride (82)
4.816.723.299010085
Mescaline Sulphate Dihydrate (33).
4.836.493.784010075
Dihydrocodeinone (free base) (17)
4.896.473.776010075
Codeine (anhydrous free base) (8)
4.805.823.366010060
Methylketobemidone Hydrochloride (42)

Numerical Index

66. 4.79 to 4.70

4.799.495.466010080
Pethidine (free base) (70)
4.708.366.747510090
d-, l-, and dl-Methadone (free base) (34)
4.756.557.077510070
&alpha-Monoacetylmorphine (free base) (45)
4.734.427.433010040
d-, and l-Methadone Hydrochloride (36)
4.723.896.037010060
Morphine Hydriodide Dihydrate (46)

Numerical Index

65. 4.69 to 4.60

4.678.043.617510090
Pethidine Hydrochloride (71)
4.607.586.521009080
dl-Methadone Hydrobromide (35)
4.685.357.795010040
Morphine Tartrate Monohydrate (53)
4.653.866.941005040
dl-Methorphan Hydrobromide Dihydrate (40)

Numerical Index

64. 4.59 to 4.50

4.577.506.481009070
all-Methadone Hydrochloride (37)
4.557.505.351007575
Hydroxypethidine (free base) (26)
4.576.656.0680100100
Dihydromorphinone Hydrochloride (20)
4.506.207.629010045
Phenadoxone (free base) (72)
4.565.123.571007575
Papaverine Hydrochloride (69)

Numerical Index

63. 4.49 to 4.40

4.498.445.081006040
Ketobemidone (free base) (29)
4.408.084.039010080
Apomorphine Hydrochloride (3)
4.427.434.731004030
d-, and l-Methadone Hydrochloride (36)
4.417.389.721006050
Cocaine (free base) (6)
4.466.9313.38010090
Ethylpethidine Hydrochloride (24)
4.446.548.767510075
Pseudomorphine Trihydrate (free base) (79)
4.475.964.361009080
Protopine (free base) (78)
4.453.4710.71007560
Thebenine Hydrochloride Monohydrate (83)

Numerical Index

62. 4.39 to 4.30

4.306.794.086010060
dl-Laudanine (free base) (31)
4.376.3412.61009075
Ethylnarceine Hydrochloride (23)
4.376.203.689010080
Morphine Sulphate Pentahydrate (52)
4.364.475.968010090
Protopine (free base) (78)

Numerical Index

61 4.29 to 4.20

4.2210.44.817510080
Acedicon® Hydrochloride (1)
4.288.445.128010090
Dihydrocodeinone Bitartrate (Dihydrate?) (18)
4.226.966.491008080
Metopon Hydrochloride (44)
4.246.913.594010050
Dioxyline Phosphate (21)
4.236.407.978010075
Narcotine Hydrochloride (I) (58)
4.286.267.184010040
Morphine Sulphate Dihydrate (51)
4.206.045.649010080
Neopine Hydrobromide (61)
4.285.987.691009080
Methylketobemidone (free base) (41)

Numerical Index

60 4.19 to 4.10

4.1413.85.085010045
Narceine (free base) (56)
4.138.235.697510050
d-, and l-Orphan Tartrate Dihydrate (65)
4.117.585.80100100100
Benzylmorphine (free base) (4)
4.197.084.945010080
Pipidone Hydrochloride (74)
4.166.795.956010080
Morphine Hydrochloride (anhydrous) (47)
4.186.017.416010075
Dihydromorphine Monohydrate (free base) (19)
4.155.846.227510060
dl-Orphan (free base) (63)

Numerical Index

59 4.09 to 4.00

4.038.084.408010090
Apomorphine Hydrochloride (3)
4.086.794.306010060
dl-Laudanine (free base) (31)
4.015.562.836010080
Cryptopine (free base) (13)

Numerical Index

58. 3.99 to 3.90

3.928.105.691008080
Ethylmorphine Hydrochloride (22)
3.906.645.141009090
dl-Methorphan (free base) (38)
3.956.1110.410010085
Morphine Hydrochloride Trihydrate (48)
3.945.533.319010075
dl-Orphan Hydrobromide (64)

Numerical Index

57. 3.89 to 3.80

3.846.395.2090100100
Phenadoxone Hydrochloride (73)
3.866.306.748010065
Codeine Phosphate (anhydrous) (10)
3.875.793.738510090
Papaverine (free base) (68)
3.835.205.639010060
d-, and l-Methorphan Hydrobromide Monohydrate (39)
3.815.093.676010075
Ketobemidone Hydrochloride (30)
3.894.726.031007060
Morphine Hydriodide Dihydrate (46)
3.864.656.945010040
dl-Methorphan Hydrobromide Dihydrate (40)

Numerical Index

56. 3.79 to 3.70

3.7510.63.54100100100
Morphothebaine Hydrochloride (54)
3.737.765.119010090
Thebaine (free base) (81)
3.786.494.837510040
Dihydrocodeinone (free base) (17)
3.776.474.897510060
Codeine (anhydrous free base) (8)
3.735.793.879010085
Papaverine (free base) (68)
3.725.715.185010050
Morphine-N-oxide (free base) (50)
3.755.005.537510070
Hydroxypethidine Hydrochloride (27)

Numerical Index

55. 3.69 to 3.60

3.639.785.359010080
Benzylmorphine Hydrochloride (5)
3.618.044.679010075
Pethidine Hydrochloride (71)
3.686.204.378010090
Morphine Sulphate Pentahydrate (52)
3.675.093.817510060
Ketobemidone Hydrochloride (30)

Numerical Index

54. 3.59 to 3.50

3.5410.63.75100100100
Morphothebaine Hydrochloride (54)
3.596.914.245010040
Dioxyline Phosphate (21)
3.516.555.0660100
.40
Codeine Phosphate Dihydrate (11)
3.536.397.0510010060
Cotarnine (free base) (12)
3.574.565.127510075
Papaverine Hydrochloride (69)

Numerical Index

53. 3.49 to 3.45

3.497.646.221007550
Narcotine (free base) (57)
3.477.444.886010050
Thebaine Hydrochloride (82)
3.465.178.091008060
Hydrastinine Hydrochloride Monohydrate (25)
3.474.4510.77510060
Thebaine Hydrochloride Monohydrate (83)

Numerical Index

51. 3.39 to 3.35

3.397.3911.16010060
Opianic Acid (62)
3.365.824.806010060
Methylketobemidone Hydrochloride (42)

Numerical Index

50. 3.34 to 3.30

3.315.533.957510090
all-Orphan Hydrobromide (64)

Numerical Index

49. 3.29 to 3.25

3.296.724.818510090
Mescaline Sulphate Dihydrate (33)

Numerical Index

48. 3.24 to 3.20

3.249.862.481006050
Meconic Acid Trihydrate (32)

Numerical Index

45. 3.09 to 3.05

3.095.8810.77510090
Cocaine Hydrochloride (7)

Numerical Index

40. 2.84 to 2.80

2.835.564.018010060
Cryptopine (free base) (13)

Numerical Index

33. 2.49 to 2.45

2.483.249.865010060
Meconic Acid Trihydrate (32)

Tabulated (d, I/I1) Data

1.Acedicon® Hydrochloride

d (A)I/I 1d (A)I/I 1
11.6152.762
10.41002.6712
8.20602.563 B
6.86302.463
6.46402.4020
6.16152.361
5.86602.322
5.56152.2625
5.338 B2.232
4.81802.1923
4.59602.152
4.52102.115
4.40302.0615
4.22751.983
3.91201.945
3.70701.8410
3.57601.812
3.44101.784
3.27501.704
3.04201.651
2.97601.632
2.8451.602

Tabulated (d, I/I1) Data

2. Acetoxyketobemidone Hydrochloride

d (A)I/I 1d (A)I/I 1
11.1603.1215
9.3753.0415
8.6422.951
6.33852.8970 B
5.761002.7610
4.90902.534
4.7112.4815
4.51602.3420
4.3252.2515
4.15152.124
4.0222.082
3.87752.041
3.68501.991
3.5640B1.8915 B
3.34501.752
3.19
I
1.661

Tabulated (d, I/I1) Data

3. Apomorphine Hydrochloride

d (A)I/I 1d (A)I/I 1
11.2105.851
10.1105.578
8.71205.3620
8.081005.013
7.6954.7170
6.65204.4090
6.0814.275
4.03803.005
3.82202.683 B
3.68252.525
3.5232.362
3.46202.193
3.33302.095
3.2451.922 B
3.14201.851 B

Tabulated (d, I/I1) Data

4. Benzylmorphine (free base)

d (A)I/I 1d (A)I/I 1
8.58903.3510
7.581003.245
7.27403.023
5.801002.9330
5.65902.872
5.31202.662
4.85802.622
4.6512.582
4.37302.3910
4.29102.2010
4.111002.162
3.87902.042
3.7252.0110
3.6311.913
3.56751.832
3.462

Tabulated (d, I/I1) Data

5. Benzylmorphine Hydrochloride

d (A)I/I 1d (A)I/I 1
9.781002.9810
9.3112.901
8.70602.842
7.58102.7630
7.2022.715
6.74302.6310
5.78452.543
5.35802.4710
5.16702.3925
4.85402.345
4.68802.282
4.47402.2025
4.06702.121
3.81452.0810
3.63902.0215 B
3.37351.9610
3.2951.9110 B
3.15451.8210
3.0651.72
I

Tabulated (d, I/I1) Data

6. Cocaine (free base)

d (A)I/I 1d (A)I/I 1
9.72502.951
8.08202.835
7.7212.7335
7.38602.613
6.94252.5510
6.25152.4620
5.92402.3710 B
5.6912.301
5.50202.265
4.95402.241
4.84402.213
4.411002.1810
4.3332.115 B
4.23402.075
4.11152.042
3.75401.993
3.68151.9415
3.47401.915
3.3911.885
3.20351.853 BB
3.13101.771
3.0711.745 B
3.0120

Tabulated (d, I/I1) Data

7. Cocaine Hydrochloride

d (A)I/I 1d (A)I/I 1
10.7903.0975
9.8723.0210
9.23502.9515
7.4452.82
I0
7.15252.7425
6.1622.681
5.881002.5425
5.5712.4912
5.35252.421
5.17152.3325 B
4.9512.282
4.78502.2030 B
4.65502.0320 B
4.38251.9730
4.28251.9225
4.1851.8510
4.0551.815
3.97301.762
3.7711.722
3.6811.673
3.58351.652
3.51351.6020
3.41101.5610
3.34101.535
3.2520

Tabulated (d, I/I1) Data

8. Codeine (anhydrous free base)

d (A)I/I 1d (A)I/I 1
10.1153.2325 B
7.3433.10
l
6.85303.0520
6.6310 B3.0015
6.471002.915
6.20202.8425
6.00152.6920
5.23402.573
5.04402.5415
4.89602.492
4.77302.4510
4.125 B2.3912
3.88452.355
3.77752.283
3.67102.248
3.5215 B2.196
3.44152.1610
3.3452.1020
2.06101.791
2.0211.773 B
1.99101.732
1.9611.682
1.9381.6710
1.9111.634
1.88101.601
1.85151.581
1.8111.563

Tabulated (d, I/I1) Data

9. Codeine Monohydrate (free base)

d (A)I/I 1d (A)I/I 1
8.76902.9715
8.11202.882
6.73502.8112
6.32202.723 B
5.59252.6412
5.25402.444 B
4.851002.382
4.5212.335
4.3782.2510 B
4.05202.202
3.96102.1410
3.85152.1010
3.72302.001 B
3.4411.905
3.36301.871
3.30151.802 B
3.052 B

Tabulated (d, I/I1) Data

10. Codeine Phosphate (anhydrous)

d (A)I/I 1d (A)I/I 1
16.1203.048
12.652.952
8.04252.895
7.45102.758 B
7.0582.611
6.74652.5715
6.301002.515
6.0042.465
5.79602.358
5.496 B2.303 B
5.1730 B2.245
4.9052.178
4.72102.1112 B
4.51102.053
4.29102.004 B
4.1731.934 B
4.06201.871
3.9751.841
3.86801.721
3.6421.681
3.5611.631
3.5011.571
3.41501.511
3.2951.471
3.1425

Tabulated (d, I/I1) Data

11. Codeine Phosphate Dihydrate

d (A)I/I 1d (A)I/I 1
17.0204.2325
8.6714.0920
7.89203.9215 B
7.26103.761
6.8813.6310
6.551003.5160
5.87303.4610 B
5.51203.2210
5.26253.115
5.06403.0225
4.82352.9215
4.53102.821
4.40352.7212
2.63151.953
2.48101.8910
2.4141.843
2.3341.823
2.27101.791
2.2251.752
2.1911.712
2.1411.661
2.11151.603
2.0711.571
1.9821.521

Tabulated (d, I/I1) Data

12. Cotarnine (free base)

d (A)I/I 1d (A)I/I 1
7.05602.5610
6.391002.453
5.31602.3620
5.03402.3120
4.82302.253 B
4.431 B2.168
4.20202.0815
4.04602.015
3.92401.981
3.7731.958
3.531001.902
3.443 B1.888
3.271 B1.842
3.20101.7715
3.06451.713
2.99151.631
2.79101.601
2.69101.575
2.6111.531

Tabulated (d, I/I1) Data

13. Cryptopine (free base)

d (A)I/I 1d (A)I/I 1
7.6340 B24.95
6.57402.3330
5.561002.301
5.18202.1810
4.56252.145
4.3352.0520
4.17501.975
4.01601.9315
3.71601.881
3.58151.852
3.4651.8210
3.29401.775
3.2111.7415 B
3.14101.681
3.0351.6625
2.9821.6210
2.90151.575
2.83801.525
2.7621.432
2.6921.412
2.6030

Tabulated (d, I/I1) Data

14. Diamorphine (free base)

d (A)I/I 1d (A)I/I 1
10.7103.6620
9.2513.5050
8.10303.2125
7.0075 B3.085
6.5445 B2.931
5.6612.818
5.291002.6730
5.08502.525
4.46152.482
4.2812.402
4.13502.372
4.02502.3120
3.88202.252
3.7522.203
2.13101.792
2.0721.745
1.9951.691
1.9311.642
1.8931.571
1.832

Tabulated (d, I/I1) Data

15. Diamorphine Hydrochloride Monohydrate

d (A)I/I 1d (A)I/I 1
17.6103.2320
9.031003.0235
7.5552.9120
7.26802.853
6.97102.801
6.73102.668
6.44752.618
5.83302.541
5.35352.491
5.272 B2.3935 B
5.17902.3110
4.96352.211
4.77202.1515 B
4.61102.011 B
4.4921.981
4.28401.941
4.0735 B1.921
3.7680 B1.853
3.58401.785
3.3960

Tabulated (d, I/I1) Data

16. Dihydrocodeine (free base)

d (A)I/I 1d (A)I/I 1
9.63102.6120
7.10802.5710
6.825 B2.5210
6.331002.471
6.16802.4120
5.31502.348
5.1312.2715
4.95402.252
4.36502.183
4.18752.1530
4.0025 B2.113
3.82502.083
3.5412.061
3.46502.0020
3.35301.962
3.3021.9410
3.2321.924
3.1621.882 B
3.08501.822 B
3.0011.775
2.8521.704
2.80101.652 B
2.7411.618 B
2.66251.561 B

Tabulated (d, I/I1) Data

17. Dihydrocodeinone (free base)

d (A)I/I 1d (A)I/I 1
10.1153.5310
7.3333.4020
7.02253.251
6.491003.1618
6.3833.0710
5.87102.955
5.14252.891
5.02252.8020
4.83402.6615
4.7632.621
4.1532.581
4.0452.5310
3.90152.483
3.78752.423
3.645 B2.382
2.3211.971
2.3211.971
2.232 B1.933
2.1911.903
2.1721.858
2.1281.802
2.0681.743
2.0331.622

Tabulated (d, I/I1) Data

18. Dihydrocodeinone Bitartrate (Dihydrate?)

d (A)I/I 1d (A)I/I 1
16.6103.4040
12.8403.2760
9.82103.195 B
9.35203.0712 B
8.441002.954 B
7.40502.834
6.9432.724
6.40602.6215
6.18602.433
5.688 B2.3410
5.4352.2925
5.12902.262
4.92152.224
4.73402.182 B
4.4412.071
4.28801.991
3.90801.911
3.6851.851
3.6051.781

Tabulated (d, I/I1) Data

19. Dihydromorphine Monohydrate (free base)

d (A)I/I 1d (A)I/I 1
10.1202.9310
7.41752.8510
6.70402.748
6.51152.7015
6.22202.644
6.011002.481
5.27102.442
5.06502.3910
4.80152.331
4.18602.293
3.995 B2.251
3.8922.222
3.77252.172
3.6312.118
3.53202.082
3.46452.011 B
3.3511.951
3.23151.932
3.0751.812
3.025

Tabulated (d, I/I1) Data

20. Dihydromorphinone Hydrochloride

d (A)I/I 1d (A)I/I 1
9.62503.0640
6.651002.975
6.06100 B2.895
5.64602.8110 B
5.09502.7475
4.76152.6610
4.57802.602
4.44602.5520
4.3012.4820
4.15802.448
3.95152.3715 B
3.8422.2925
3.7522.218
3.66102.182
3.57802.152
3.43752.128
3.3212.062
3.23102.032
1.9931.671
1.9315 B1.622
1.8951.563
1.8651.522
1.8315 B1.491
1.7911.391
1.7821.351
1.7421.241
1.6810

Tabulated (d, I/I1) Data

21. Dioxyline Phosphate

d (A)I/I 1d (A)I/I 1
12.4304.3515
10.9104.2440
10.2104.118 B
9.58253.8935
8.6813.671
8.2123.5950
6.911003.4835
6.23153.4330
5.62253.281
5.42153.201
5.1853.063 B
4.79102.924 B
4.571

Tabulated (d, I/I1) Data

22. Ethylmorphine Hydrochloride

d (A)I/I 1d (A)I/I 1
11.2202.4215
10.3502.381
8.10802.3310
6.3222.243 B
6.09702.171 B
5.69802.1240
5.4612.068
5.23402.0320
5.11101.9930
4.78751.9615
4.56101.8835
4.31101.8310
4.08101.7925
3.921001.751
3.67151.733
3.51401.682 B
3.39401.642
3.28401.622
3.17401.594
3.11501.564
3.0511.534
2.98601.508
2.9231.463 B
2.8531.403
2.78751.372
2.71151.333
2.63251.225
2.5831.203
2.5221.172
2.45151.154 B

Tabulated (d, I/I1) Data

23. Ethylnarceine Hydrochloride

d (A)I/I 1d (A)I/I 1
12.6754.2220
10.9204.1220
10.1754.0375
9.3733.9270
7.0230 B3.7160
6.72353.5250 B
6.34903.4310
6.02403.3520
5.7513.2120 B
5.03403.0315
4.82152.9120
4.66152.825
4.371002.772 B
2.67102.402
2.58102.092
2.5110

Tabulated (d, I/I1) Data

24. Ethylpethidine Hydrochloride

d (A)I/I 1d (A)I/I 1
13.3903.2340
8.95303.1560
7.84253.045 B
6.931002.9712 B
6.61102.834 B
6.04402.774
5.79152.704
5.51402.5715
5.3252.493
5.15102.4110
4.9332.3325
4.71602.282
4.46802.224
4.38502.162 B
4.2612.111
4.1351.971
4.0481.941
3.92601.911
3.83101.821
3.7521.791
3.65151.711
3.47751.581
3.3115

Tabulated (d, I/I1) Data

25. Hydrastinine Hydrochloride Monohydrate

d (A)I/I 1d (A)I/I 1
9.50402.77151
8.97402.681
8.09602.592
5.5832.533
5.17802.481
5.00102.401
4.52302.351
4.36152.302
4.1822.2410
4.0232.165
3.70152.115
3.461002.055
3.3952.001
3.3321.971
3.25201.921
3.1951.885
3.06301.831
2.9821.783
2.9111.736 B
2.84151.701

Tabulated (d, I/I1) Data

26. Hydroxypetidine (free base)

d (A)I/I 1d (A)I/I 1
14.8602.734
7.50752.6620
6.79302.555
5.72202.4910
5.35752.4020
4.80202.263
4.551002.222
4.18252.151
4.0532.108
3.90102.028
3.78121.9912 B
3.68151.951 B
3.46201.895
3.37601.871
3.16201.851
3.0911.833
3.0251.792
2.96351.731
2.8631.695
2.8115

Tabulated (d, I/I1) Data

27. Hydroxypethidine Hydrochloride

d (A)I/I 1d (A)I/I 1
13.9502.751
6.3452.668
6.97602.628
6.7822.5620
6.42102.505
5.53702.461 B
5.28152.4220
5.001002.385 B
4.36502.2820
4.07502.245
3.942 B2.164
3.75752.128
3.6451.984
3.51601.9515
3.34601.8810
3.18101.815
3.11101.772
3.0151.745
2.90401.702
2.8421.665
2.812

Tabulated (d, I/I1) Data

28. dl-Isomethadone Hydrochloride Monohydrate

d (A)I/I 1d (A)I/I 1
13.1152.8435
9.30402.785
8.7152.6610
7.251002.6212
6.53252.572
5.38752.475
5.28502.398
4.9252.3510
4.65102.2820
4.33502.185 B
4.14502.112
3.90152.0710
3.7352.031
3.64501.9515 B
3.49301.873 B
3.34401.823
3.22251.775 B
3.1531.651
3.08301.633
2.99251.563

Tabulated (d, I/I1) Data

29. Ketobemidone (free base)

d (A)I/I 1d (A)I/I 1
8.7733.492
8.44603.4230
7.59103.295
6.6653.192
6.47203.101
6.30252.936
5.80302.873
5.3912.821
5.20252.781
5.08402.734
4.612 B2.6915
4.491002.594
4.39152.544
3.25152.514
3.05102.391 B
3.9212.3210 B
3.79402.2210
3.7012.165
3.583

Tabulated (d, I/I1) Data

30. Ketobemidone Hydrochloride

d (A)I/I 1d (A)I/I 1
9.46506.0640
7.01405.385
6.56255.09100
6.31254.8750
4.71502.492
4.28252.461
4.14502.403
4.0432.355
3.81602.3110
3.67752.2312
3.5032.148
3.40252.075
3.35102.033
3.31101.991
3.1431.975
3.09151.932
3.03101.895
2.97151.848
2.9251.781
2.8741.751
2.7921.711
2.74201.681
2.6441.613
2.6011.571 B
2.56401.521

Tabulated (d, I/I1) Data

31. dl-Laudanine (free base)

d (A)I/I 1d (A)I/I 1
9.69402.945
8.0932.8815
6.791002.791
6.4712.7110
6.07452.631
5.7352.565
5.44452.4610 B
5.1622.352
4.86402.213
4.4840 BB2.1620
4.30602.105
4.08602.042
3.871 B2.0010
3.76201.945
3.66101.885
3.49151.8210
3.38501.772
3.0530 B

Tabulated (d, I/I1) Data

32. Meconic Acid Trihydrate

d (A)I/I 1d (A)I/I 1
9.86602.393
9.122 B2.3510
8.37302.2912
7.9212.2210 B
6.20302.1612
5.7812.1115
5.0630 B2.075
4.70352.005
4.4730 B1.9715
4.19201918
4.0031.8710
3.80201.8410 B
3.5251.788 B
3.3811.74
l B
3.241001.682 B
3.1240 B1.653
3.048 B1.622
2.87301.6112
2.74151.562 BB
2.6651.512 BB
2.57401.452 BB
2.48501.415
2.431

Tabulated (d, I/I1) Data

33. Mescaline Sulphate Dihydrate

d (A)I/I 1d (A)I/I 1
19.6156.72100
10.136.2560
7.7216.021
5.69302.622
5.25152.571
4.9630 B2.5110
4.81902.433 B
4.4052.3415
4.22252.282
4.06202.2310
3.96802.193 B
3.8722.1515
3.7722.053
3.60802.025
3.46701.9510
3.35101.8810
3.29851.845 B
3.15601.753
3.0151.708
2.90151.612
2.692 B

Tabulated (d, I/I1) Data

34. d-,l-, and dl-Methadone (free base)

d (A)I/I 1d (A)I/I 1
9.4113.181
8.361003.0825
7.8912.981
7.33602.895
6.74902.7820
6.3012.698
5.69102.634
5.50152.482
5.35402.4420
5.0012.381
4.8622.3320
4.70752.285
4.44752.242
4.2335 B2.152
3.93702.1215
3.65702.071
3.5711.9810
3.48601.941
3.3731.8510
3.253

Tabulated (d, I/I1) Data

35. dl-Methadone Hydrobromide

d (A)I/I 1d (A)I/I 1
12.6302.9720 B
8.27252.885
7.7522.821
7.53902.7715
6.48802.713
6.2512.621
5.90102.5215 B
5.80202.385
5.47202.311
4.76502.281
4.601002.241
4.34452.211
4.17202.1115 B
3.9840 B2.0410 B
3.7751.972
3.6751.921 B
3.5130 B1.871 B
3.3911.835
3.26451.743
3.2031.681
3.13501.632
3.055

Tabulated (d, I/I1) Data

36. d-, and l-Methadone Hydrochloride

d (A)I/I 1d (A)I/I 1
12.4156.0815
8.0920 B5.621
7.6725.411
7.43404.7330
6.3724.611
4.421003.0820
4.14202.901
3.953 B2.851
3.7615 B2.772
3.5512.691
3.3522.583
3.1820

Tabulated (d, I/I1) Data

37. dl-Methadone Hydrochloride

d (A)I/I 1d (A)I/I 1
12.4253.1030
8.25103.033
7.8752.9710
7.50902.923
6.48702.845
6.2012.7520
5.92202.6815
5.7052.603 B
4.72302.5320
4.571002.482
4.34402.305
4.2032.231
4.14202.162
4.00202.118
3.87202.083
3.715 BB2.0415
3.4920 B1.992
3.3351.923
3.20251.672
3.141 B

Tabulated (d, I/I1) Data

38. dl. Methorphan (free base)

d (A)I/I 1d (A)I/I 1
10.3203.478 B
7.54403.3725
7.00303.1150 B
6.64902.921 B
6.43752.8415
5.87752.7920
5.14902.5720
5.00302.4715
4.86252.395
4.75502.252 B
4.47302.162
4.17452.1215
3.901002.0612 B
3.78501.975 B
3.6311.903 B
3.5630

Tabulated (d, I/I1) Data

39. d-, and l-Methorphan Hydrobromide Monohydrate

d (A)I/I 1d (A)I/I 1
13.7403.173
8.6613.116
7.68252.9850
6.9112.934
6.51202.8140
5.6602.7630
5.49302.6945
5.201002.6115
4.94402.5530
4.79252.511
4.73252.471
4.54402.4040
4.35252.2915
4.12352.251
3.94402.198 B
3.83902.128 B
3.7332.061 B
3.55501.975 B
3.4351.9210
3.3741.8515
3.28501.821
3.22301.775

Tabulated (d, I/I1) Data

40. dl-Methorphan Hydrobromide Dihydrate

d (A)I/I 1d (A)I/I 1
18.3123.0110 B
9.35302.903 B
6.94402.865
6.2732.813 B
6.0622.764
5.40202.7125
5.2882.638
5.07202.6020
4.651002.541
4.36252.4710
4.14102.361
4.0012.324
3.86502.284
3.7442.231
3.66202.1915
3.53252.154 B
3.48252.0810
3.4222.052 B
3.36201.953 B
3.242 B1.913
3.1310 B1.795
3.073

Tabulated (d, I/I1) Data

41. Methylketobemidone (free base)

d (A)I/I 1d (A)I/I 1
8.56753.0615
8.1353.0110
7.69802.9420
7.33802.8910
6.81752.8140
6.6022.7310 BB
5.98902.593 BB
5.72202.472
5.30202.4450
4.97202.391
4.79752.3410
4.67502.295
4.54502.248
4.48752.132
4.3942.083 B
4.281002.022
4.13251.964 B
4.01251.914
3.8331.873
3.74601.794
3.653 B1.713
3.49201.641
3.41201.612
3.2010 BB

Tabulated (d, I/I1) Data

42. Methylketobemidone Hydrochloride

d (A)I/I 1d (A)I/I 1
9.63253.014
5.821002.9215
5.17452.748 B
5.06502.691
4.80602.591
4.2412.452
4.1032.4010
3.98352.2710
3.57202.171
3.36602.125
3.23502.0610
3.1440

Tabulated (d, I/I1) Data

43. Metopon (Dihydrate?) (free base)

d (A)I/I 1d (A)I/I 1
10.11004.8740
9.13754.5330
7.37604.1350
5.8840 B4.004 B
5.59953.805
5.0323.7375 B
3.57652.411
3.5022.3410
3.4322.2910
3.35202.253
3.2942.1925
3.1912.123
3.1142.035
2.87402.011
2.8111.955
2.75201.902
2.69251.825
2.6511.715
2.487

Tabulated (d, I/I1) Data

44. Metopon Hydrochloride

d (A)I/I 1d (A)I/I 1
8.28152.4210
6.96802.3512 B
6.49802.2810
6.12702.2420
5.59502.175
5.13602.1230
4.92252.085
4.72752.013
4.48251.9820
4.221001.951
3.9211.931
3.80301.876
3.678 B1.813 BB
3.5711.755
3.50701.716
3.3511.672
3.17401.642
2.9515 B1.615
2.8711.562
2.80151.512
2.74601.482 B
2.7021.442
2.583 BB1.363
2.4620

Tabulated (d, I/I1) Data

45. &alpha-Monoacetylmorphine (free base)

d (A)I/I 1d (A)I/I 1
10.4252.993
8.3522.8130
7.07702.771
6.8112.731
6.551002.692
6.07602.663
5.5652.571
5.14302.515
4.9312.4515
4.75752.342 B
4.4712.252 B
4.25502.153 BB
3.9912.031
3.70601.994
3.60201.972
3.52101.922
3.45101.891
3.30121.852
3.2521.813
3.19151.772
3.1241.661
3.0315

Tabulated (d, I/I1) Data

46. Morphine Hydriodide Dihydrate

d (A)I/I 1d (A)I/I 1
11.0505.2160
8.0414.7270
6.49354.573
6.03604.2710
5.7520 B4.101
5.4713.89100
3.60202.2320 B
3.45402.191
3.38302.1415
3.2710 B2.112
3.1552.045 BB
3.09401.985
3.005 B1.9225
2.9420 B1.873
2.8381.822
2.7831.791
2.7321.761
2.6751.741
2.61151.693
2.5111.631
2.41201.611
2.3715

Tabulated (d, I/I1) Data

47. Morphine Hydrochloride (anhydrous)

d (A)I/I 1d (A)I/I 1
8.1252.698 BB
6.791002.583
5.95802.502 B
5.02102.4015
4.85202.3210
4.63502.295
4.16602.222
3.8682.182
3.61452.125
3.49102.0820
3.405 B2.042
3.38301.995
3.2211.933
3.131 B1.884
2.96201.782 B
2.915 B1.691 B
2.7525 B

Tabulated (d, I/I1) Data

48. Morphine Hydrochloride Trihydrate

d (A)I/I 1d (A)I/I 1
11.112.8120
10.4852.763
8.11752.683
6.111002.621
5.80852.5225
5.22502.4615
4.87402.395 BB
4.76502.311 B
4.5912.255 BB
4.32202.1625
4.15202.0725
3.951002.031
3.6310 B2.0025
3.50601.961
3.4230 B1.9310
3.33101.901
3.19101.8715
3.11701.841
3.01501.731
2.94251.703
2.881

Tabulated (d, I/I1) Data

49. Morphine Monohydrate (free base)

d (A)I/I 1d (A)I/I 1
10.1304.045
7.42603.945
7.0513.772
6.61603.7210
6.23353.612
5.981003.555
5.25103.4660
5.05603.351
4.9213.1910
4.78153.0710
4.17602.995
2.91152.235
2.83122.174
2.73102.1115 B
2.70202.032
2.65101.931
2.5851.895
2.5411.872
2.5051.843
2.4511.792
2.40251.671
2.29201.641

Tabulated (d, I/I1) Data

50. Morphine-N-oxide (free base)

d (A)I/I 1d (A)I/I 1
9.7332.5215 B
7.70252.4012
6.34402.3610
6.0952.288
5.9312.253
5.711002.212
5.18502.1815
4.8810 BB2.141
4.50452.1010
4.15152.073
3.952 B2.0510
3.8312.0110
3.72501.978
3.5115 B1.921
3.402 B1.8730 B
3.27451.7910 B
3.0951.771
2.98301.715
2.8531.632
2.75101.618
2.71101.582
2.6421.553

Tabulated (d, I/I1) Data

51. Morphine Sulphate Dihydrate

d (A)I/I 1d (A)I/I 1
14.3153.205 B
8.41103.1315
8.05123.041
7.6212.985
7.18402.8810 B
6.75102.801
6.261002.738
5.6032.6810
5.46302.532
5.25202.505
5.01202.394
4.772 B2.274
4.67102.201 B
4.28402.188
4.1822.144
4.0422.111
3.93302.0910
3.8552.051
3.691 B2.022
3.5520 B1.991
3.44251.872
3.372

Tabulated (d, I/I1) Data

52. Morphine Sulphate Pentahydrate

d (A)I/I 1d (A)I/I 1
15.0705.0345
8.42354.7120
7.64504.3790
7.3414.211
6.50604.0340 B
6.201003.8715 B
5.9113.6880
5.67753.582
5.4213.5015
5.20353.3870
3.25302.193
3.1320 B2.1515
3.05102.098 B
2.94202.008 B
2.835 B1.965
2.7711.911 B
2.65601.841 B
2.56251.795 B
2.465 B1.751
2.3011.701
2.2731.674
2.2381.593

Tabulated (d, I/I1) Data

53. Morphine Tartrate Monohydrate

d (A)I/I 1d (A)I/I 1
15.3153.432
9.67203.2530
9.19203.103
7.7940
3.Ol
1O
6.53402.932
6.181O2.861
5.93202.762
5.351OO2.671
4.68502.6115
4.3352.481
4.20252.441
3.9312.331
3.8432.275
3.7032.203
3.6432.154
3.5432.044

Tabulated (d, I/I1) Data

54. Morphothebaine Hydrochloride

d (A)I/I 1d (A)I/I 1
10.61003.062
9.52252.9610 B
8.87252.8310 B
7.97502.693 B
7.17302.632
6.47152.582
6.2132.5110
5.9652.453
5.5152.393
5.31602.292
4.87202.251
4.57102.212
4.2552.135
4.1142.051
4.0082.002
3.751001.971
3.541001.912
3.44151.8515 B
3.3751.785
3.2420 B

Tabulated (d, I/I1) Data

55. Nalorphine Hydrochloride

d (A)I/I 1d (A)I/I 1
10.5203.2520
7.33803.1818
6.91803.0418
6.58303.001
6.23202.9525
5.36102.892
5.061002.832
4.32502.7630
4.0832.7125
4.00502.643
3.7852.5910
3.68152.5235
3.62752.4620
3.45452.415
3.36202.342 B
2.3181.941
2.2751.8810
2.2421.814 B
2.2031.742 B
2.1251.6810
2.071 B1.635
2.0151.502
1.9610

Tabulated (d, I/I1) Data

56. Narceine (free base)

d (A)I/I 1d (A)I/I 1
13.81003.8030 B
9.67153.5635
8.7553.441
6.86253.3340
6.17303.075
5.61402.972
5.241 BB2.862
5.08452.752 B
4.85452.652
4.7322.555 B
4.5352.491
4.36152.424
4.14502.374
3.9645

Tabulated (d, I/I1) Data

57. Narcotine (free base)

d (A)I/I 1d (A)I/I 1
16.2253.381
14.033.3220
11.2203.135
8.85103.022
8.1512.9610
7.64752.812
7.1030 B2.772
6.48352.672
6.22502.623
5.91352.535
5.70252.491
5.50152.443
5.33402.382
5.06202.342
4.93202.288
4.79252.223
4.533 B2.152 B
4.30252.081
4.07202.022
3.96151.972
3.81501.911 B
3.75301.861 B
3.5810 B1.823
3.49100

Tabulated (d, I/I1) Data

58. Narcotine Hydrochloride (I)

d (A)I/I 1d (A)I/I 1
14.8303.4615 B
9.22503.3010 B
7.97753.1850
7.5553.095
7.19453.0210 B
6.40100 B2.9230 B
5.79252.7820 B
5.18502.633
5.0252.535
4.83602.473
4.6022.413
4.23802.353
4.00502.295 B
3.8452.173 B
3.71602.135 B
3.60402.052

Tabulated (d, I/I1) Data

59. Narcotine Hydrochloride (II)

d (A)I/I 1d (A)I/I 1
15.9304.2425 B
12.43 B4.0650 BB
10.6753.7040
9.81153.5340
8.181003.2730
7.62503.1335
7.1432.995 B
6.76902.8615 B
6.48202.785 B
5.79152.6220
5.36152.475B
5.02302.1725
4.5425 B2.113

Tabulated (d, I/I1) Data

60. Narcotine Hydrochloride (III)

d (A)I/I 1d (A)I/I 1
16.4254.0350 B
14.853.8350 B
11.6603.725
10.6103.5445
9.2553.465 B
8.16653.2640
7.7083.1230
6.771003.0440 B
6.535 B2.8510 B
6.0752.718
5.7532.635
5.58202.5110 B
5.20502.418
4.6615 B2.1610
4.3252.092
4.18401.922

Tabulated (d, I/I1) Data

61. Neopine Hydrobromide

d (A)I/I 1d (A)I/I 1
12.2402.4225
7.56152.353
6.64202.321
6.041002.251
5.64802.215
5.22502.183
4.88152.141
4.70502.103
4.20902.023 BB
4.025 B1.961
3.72751.922
3.62801.893
3.45751.852
3.3831.832
3.32301.8115
3.18201.733
3.10401.694
2.9511.562
2.90101.525
2.84151.501
2.7811.472
2.68251.461
2.62201.382
2.5711.342
2.5351.322
2.4910

Tabulated (d, I/I1) Data

62. Opianic Acid

d (A)I/I 1d (A)I/I 1
11.1603.9120
8.25503.7750
7.391003.4820
6.80103.3960 B
5.1423.252
4.7413.1725
4.27103.0615
4.11203.025
2.8852.3330
2.84102.2710
2.7782.221
2.69102.1230
2.6412.075
2.5711.861

Tabulated (d, I/I1) Data

63. dl-Orphan (free base)

d (A)I/I 1d (A)I/I 1
8.28403.371
7.2913.291
6.93203.123
6.57203.025
6.22602.944
5.841002.8710
5.56252.8320
5.23202.7025
5.00102.5315
4.54152.4212
4.3582.315
4.15752.275
3.95252.1920
3.79102.128
3.6825 B2.025
3.5411.9925
3.4415

Tabulated (d, I/I1) Data

64. dl-Orphan Hydrobromide

d (A)I/I 1d (A)I/I 1
14.7203.0420
10.5252.9640
7.3240 B2.9040
6.5540 B2.7740
5.97252.6110 B
5.531002.5515
5.18402.468 B
4.69602.391
4.43202.298 B
4.08402.221
3.94902.1418
3.80102.102
3.60802.053 B
3.48152.004
3.31751.9120
3.1410

Tabulated (d, I/I1) Data

65. d-, and l-Orphan Tartrate Dihydrate

d (A)I/I 1d (A)I/I 1
9.3933.272
8.231003.211
7.11153.0915
6.53402.9745
6.2132.832
6.0752.762
5.69502.655
5.40202.551
4.76302.501
4.53352.3520
4.36102.2815
4.13752.241
3.813 B2.182
3.595 B2.065
3.4822.031
3.4021.951
3.3421.921

Tabulated (d, I/I1) Data

66. Oxycodone (free base)

d (A)I/I 1d (A)I/I 1
10.5205.2150
7.70405.0310
7.14254.7710
6.8054.512
6.4544.1815
5.881004.0335
3.82102.501
3.731 B2.436 B
3.563 B2.352
3.50302.281
3.3912.258
3.29252.212
3.1852.155
3.1182.092 B
3.0531.9912
2.9841.952
2.9211.9110
2.775 B1.84
l
2.62151.802

Tabulated (d, I/I1) Data

67. Oxycodone Hydrochloride

d (A)I/I 1d (A)I/I 1
11.623.2915
10.61003.1540
9.5913.0610
8.75102.9740
8.21702.872
7.7452.771
7.28902.692
6.8432.5530
6.28602.505
6.0922.452
5.44752.401
5.1452.353
4.98402.292
4.82402.235
4.60502.182
4.37502.142
4.2822.103
4.08252.064
3.9212.014
3.78151.982
3.69201.918
3.52501.841
3.4121.715

Tabulated (d, I/I1) Data

68. Papaverine (free base)

d (A)I/I 1d (A)I/I 1
14.8102.633
8.90122.5720
7.8932.442
5.791002.3910
5.21252.338 B
4.93302.218
4.77302.183
4.61402.132
4.48202.108
4.3822.023 BB
4.26251.9529 B
3.87851.884 B
3.73901.845
3.6551.821
3.5751.811
3.51151.791
3.3521.744
3.28401.716
3.1325 B1.662B
3.01151.614
2.9011.571
2.7830 B1.542

Tabulated (d, I/I1) Data

69. Papaverine Hydrochloride

d (A)I/I 1d (A)I/I 1
10.1204.56100
7.87204.4470
6.85404.323
6.5954.203
5.93154.0825
5.35403.7920
5.12753.6860
3.57752.5520
3.42752.482
3.35252.402
3.1412.341
3.0412.235 B
2.97102.095 B
2.8951.963
2.8521.884
2.75201.711
2.675

Tabulated (d, I/I1) Data

70. Pethidine (free base)

d (A)I/I 1d (A)I/I 1
9.491003.238
7.6813.1410
7.2713.012
5.99102.9020
5.7212.825
5.46802.6025
5.2182.491
4.9312.351
4.79602.308
4.5010 B2.241
4.3612 B2.201
3.99302.1510
3.8732.112
3.78502.043
3.62121.9912
3.5651.931
3.47101.895
3.3610

Tabulated (d, I/I1) Data

71. Pethidine Hydrochloride

d (A)I/I 1d (A)I/I 1
8.041003.0625
7.7252.994
6.65202.941
5.73602.8625
5.24402.802
5.14502.7410
4.7532.684
4.67752.5910
4.5052.433
4.3152.331
4.1732.254
4.08502.225
3.96152.172 B
3.733 B2.053
3.61901.982 B
3.5551.945
3.4151.901
3.3431.841
3.2221.802
3.142

Tabulated (d, I/I1) Data

d (A)I/I 1d (A)I/I 1
8.79253.482
8.07353.3810
7.62453.253
6.43102.952
6.201002.7810
5.9712.735
5.6912.6415
5.4012.592
5.18402.4410
4.89252.387
4.6532.3015
4.50902.255
4.34152.113
4.0935 B2.083
3.88402.0215 B
3.76351.9210
3.6421.871
3.58401.833

Tabulated (d, I/I1) Data

73. Phenadoxone Hydrochloride

d (A)I/I 1d (A)I/I 1
12.8302.948
7.59252.8750
7.39402.793
6.391002.662
5.72602.5620
5.201002.4810
4.6725 B2.391
4.4050 B2.3120
4.16402.185
3.97202.155
3.84902.101
3.62502.043
3.4910 B1.981 B
3.1120 B1.921 B
3.0325 B1.803 B

Tabulated (d, I/I1) Data

74. Pipidone Hydrochloride

d (A)I/I 1d (A)I/I 1
10.8403.0120
9.88452.9225
8.4152.821
7.6222.762
7.081002.692
5.974 B2.605
5.60202.541
5.40252.483
5.10102.374
4.94802.325
4.33202.261
4.19502.222
3.9222.183
3.72252.121
3.54302.003
3.33201.965
3.1481.891

Tabulated (d, I/I1) Data

75. dl-&alpha-Prodine Hydrochloride

d (A)I/I 1d (A)I/I 1
15.1503.251
7.5053.0920 B
7.141003.0010
6.8712.873
6.69702.833
5.96802.675
5.52102.5910
5.16602.542
5.01102.492 B
4.74302.393 B
4.56302.321
4.3952.238
4.27252.162
4.06202.125
3.88202.043
3.78301.982 B
3.58601.891
3.45301.791
3.3451.672

Tabulated (d, I/I1) Data

76. dl-&beta-Prodine Hydrochloride

d (A)I/I 1d (A)I/I 1
11.2203.5225
8.131003.3120
6.08253.243
5.87703.183
5.39203.093 B
5.24152.9525
5.10702.8320
4.6352.791 B
4.41152.711
4.23402.661
4.08402.613
3.8240 B2.522 B
3.6940 B2.461 B
2.4052.033 B
2.3521.975
2.3151.945
2.2015 B1.911 B
2.1311.872 B

Tabulated (d, I/I1) Data

77. Propylketobemidone (free base)

d (A)I/I 1d (A)I/I 1
10.61002.8010
9.05102.6220
6.73152.505
6.0912.432
5.77502.352
5.3512.3010
5.02902.2420
4.54102.151
4.3712.1120
4.19302.071
4.01202.0025
3.91501.961
3.7811.931
3.65301.905
3.54101.872
3.30301.813
3.02101.745
2.9430 B

Tabulated (d, I/I1) Data

78. Protopine (free base)

d (A)I/I 1d (A)I/I 1
10.7202.6810
8.74352.6325
6.77252.591 B
6.5752.533 B
6.31302.435
5.96902.403
5.5152.363
5.3030 B2.2520 B
4.97352.202
4.471002.1820
4.36802.141
4.16252.092 B
4.01802.012
3.87201.965
3.65601.895 B
3.5321.813
3.46451.7910
3.3481.7715
3.28101.732
3.14251.703
3.09201.652 B
3.0051.621
2.95101.582
2.9151.562
2.8651.442 B
2.773 B

Tabulated (d, I/I1) Data

79. Pseudomorphine Trihydrate (free base)

d (A)I/I 1d (A)I/I 1
9.23303.5660
8.76753.3710
8.15253.095
7.25153.024
6.541002.932
6.11252.802
5.82102.732
5.52202.581
4.8652.405
4.6052.263
4.44752.141
4.14152.101
4.02152.044
3.9031.992
3.73151.941
3.642

Tabulated (d, I/I1) Data

80. Sinomenine Hydrochloride Dihydrate

d (A)I/I 1d (A)I/I 1
11.5403.0740
9.62752.8940
7.1252.7225
6.75752.6412
6.45402.582
6.111002.532
5.75252.4715
5.36152.402
5.0912.315
4.91752.2615
4.7912.1940
4.56252.152
4.28602.092
4.01602.041
3.90501.998
3.71201.961
3.5841.931
3.51251.845
3.39501.702
3.30501.601
3.21251.561

Tabulated (d, I/I1) Data

81. Thebaine (free base)

d (A)I/I 1d (A)I/I 1
7.761003.3112
7.43303.1715
6.85303.071
6.35402.9525
5.65352.731
5.11902.502
4.90102.3710
4.66102.294
4.2852.193 B
4.18202.042
4.06351.992
3.8931.951
3.73901.882 B
3.4310

Tabulated (d, I/I1) Data

82. Thebaine Hydrochloride

d (A)I/I 1d (A)I/I 1
7.441002.562
6.99302.5125
6.75202.445 B
5.9752.3910
5.62102.3410
5.3235 B2.2730
4.88502.215
4.71452.1610
4.29452.0810
4.12402.002
3.79251.9220
3.63401.872
3.47601.852
3.37101.8225
3.2620 B1.803
3.16301.763
3.00201.733
2.94201.7115
2.83351.661 B
2.7851.621 B
2.7131.583 B
2.66101.541
2.61101.512

Tabulated (d, I/I1) Data

83. Thebenine Hydrochloride Monohydrate

d (A)I/I 1d (A)I/I 1
10.7603.365
6.04203.292
5.52403.0215
4.451002.852
4.25502.758
4.1032.535
3.99102.462
3.4775

FIGURES

Fig. 1. Acedicon® Hydrochloride

Fig. 2. Acetoxyketobemidone Hydrochloride

Fig. 3. Apomorphine Hydrochloride

Fig. 4. Benzylmorphine (free base)

Fig. 5. Benzylmorphine Hydrochloride

Fig. 6. Cocaine (free base)

Fig. 7. Cocaine Hydrochloride

Fig. 8. Codeine (anhydrous free base)

Fig. 9. Codeine Monohydrate (free base)

Fig. 10. Codeine Phosphate (anhydrous)

Fig. 11. Codeine Phosphate Dihydrate

Fig. 12. Cotarnine (free base)

Fig. 13. Cryptopine (free base)

Fig. 14. Diamorphine (free base)

Fig. 15. Diamorphine Hydrochloride Monohydrate

Fig. 16. Dihydrocodeine (free base)

Fig. 17. Dihydrocodeinone (free base)

Fig. 18. Dihydrocodeinone Bitartrate (Dihydrate ?)

Fig. 19. Dihydromorphine Monohydrate (free base)

Fig. 20. Dihydromorphinone Hydrochloride

Fig. 21. Dioxyline Phosphate

Fig. 22. Ethylmorphine Hydrochloride

Fig. 23. Ethylnarceine Hydrochloride

Fig. 24. Ethylpethidine Hydrochloride

Fig. 25. Hydrastinine Hydrochloride Monohydrate

Fig. 26. Hydroxypethidine (free base)

Fig. 27. Hydroxypethidine Hydrochloride

Fig. 28.dl-Isomethadone Hydrochloride Monohydrate

Fig. 29. Ketobemidone (free base)

Fig. 30. Ketobemidone Hydrochloride

Fig. 31.dl-Laudanine (free base)

Fig. 32. Meconic Acid Trihydrate

Fig. 33. Mescaline Sulphate Dihydrate

Fig. 34.d-, l-, and dl-Methadone (free base)

Fig. 35.dl-Methadone Hydrobromide

Fig. 36.d-, and l-Methadone Hydrochloride

Fig. 37.dl-Methadone Hydrochloride

Fig. 38.dl-Methorphan (free base)

Fig. 39.d-, and l-Methorphan Hydrobromide Mono- hydrate

Fig. 40.dl-Methorphan Hydrobromide Dihydrate

Fig. 41. Methylketobemidone (free base)

Fig. 42. Methylketobemidone Hydrochloride

Fig. 43. Metopon (Dihydrate ?) (free base)

Fig. 44. Metopon Hydrochloride

Fig. 45.&alpha-Monoacetylmorphine (free base)

Fig. 46. Morphine Hydriodide Dihydrate

Fig. 47. Morphine Hydrochloride (anhydrous)

Fig. 48. Morphine Hydrochloride Trihydrate

Fig. 49. Morphine Monohydrate (free base)

Fig. 50. Morphine-N-oxide (free base)

Fig. 51. Morphine Sulphate Dihydrate

Fig. 52. Morphine Sulphate Pentahydrate

Fig. 53. Morphine Tartrate Monohydrate

Fig. 54. Morphothebaine Hydrochloride

Fig. 55. Nalorphine Hydrochloride

Fig. 56. Narceine (free base)

Fig. 57. Narcotine (free base)

Fig. 58. Narcotine Hydrochloride (I)

Fig. 59. Narcotine Hydrochloride (II)

Fig. 60. Narcotine Hydrochloride (III)

Fig. 61. Neopine Hydrobromide

Fig. 62. Opianic Acid

Fig. 63.dl-Orphan (free base)

Fig. 64.dl-Orphan Hydrobromide

Fig. 65.d-, and l-Orphan Tartrate Dihydrate

Fig. 66. Oxycodone (free base)

Fig. 67. Oxycodone Hydrochloride

Fig. 68. Papaverine (free base)

Fig. 69. Papaverine Hydrochloride

Fig. 70. Pethidine (free base)

Fig. 71. Pethidine Hydrochloride

Fig. 72. Phenadoxone (free base)

Fig. 73. Phenadoxone Hydrochloride

Fig. 74. Pipidone Hydrochloride

Fig. 75.dl-&alpha-Prodine Hydrochloride

Fig. 76.dl-&beta-Prodine Hydrochloride

Fig. 77. Propylketobemidone (free base)

Fig. 78. Protopine (free base)

Fig. 79. Pseudomorphine Trihydrate (free base)

Fig. 80. Sinomenine Hydrochloride Dihydrate

Fig. 81. Thebaine (free base)

Fig. 82. Thebaine Hydrochloride

Fig. 83. Thebenine Hydrochloride Monohydrate

Fig. 84. Codeine (free base); anhydrous and mono- hydrate

Fig. 85. Codeine Phosphate; mixed phases, A

Fig. 86. Codeine Phosphate; mixed phases, B, C

Fig. 87. Metopon; polymorph (?)

Fig. 88. Morphine Sulphate; dihydrate and penta- hydrate

Fig. 89.dl-Prodine Hydrochloride; &alpha and &beta

Fig. 90. Protopine, with "unknown"

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