Morphine hydro­chloride anhydrateCAS number: 52–26–6.

Gelbrich, T.; Braun, D.E.; Griesser, U.J.

doi:10.1107/S1600536812046405

Volume 68
Part 12
Pages o3358-o3359
December 2012

Received 15 October 2012
Accepted 9 November 2012
Online 17 November 2012

Key indicators
Single-crystal X-ray study
T = 173 K
Mean (C-C) = 0.002 Å
R = 0.027
wR = 0.069
Data-to-parameter ratio = 13.0
Details

Morphine hydrochloride anhydrate¹

Thomas Gelbrich,^a ^* Doris E. Braun ^a and Ulrich J. Griesser ^a

^aInstitute of Pharmacy, University of Innsbruck, Innrain 52c, 6020 Innsbruck, Austria
Correspondence e-mail: thomas.gelbrich@uibk.ac.at

In the title molecular salt [systematic name: (5 [alpha] ,6 [alpha] )-7,8-didehydro-4,5-epoxy-17-methylmorphinan-3,6-diol hydrochloride], C₁₇H₂₀NO₃⁺·Cl^-, the conformation of the morphinium ion is in agreement with the characteristics of the previously reported morphine forms [for example, Gylbert (1973). Acta Cryst. B29, 1630-1635]. In the crystal, the cations and chloride anions are linked into a helical chain propagating parallel to the b-axis direction by N-HCl and O-HCl hydrogen bonds. The title salt and the morphine monohydrate [Bye (1976) Acta Chem. Scand. 30, 549-554] display very similar one-dimensional packing modes of their morphine components.

Related literature

For related structures, see: Guguta et al. (2008); Gylbert (1973); Mackay & Hodgkin (1955); Bye (1976); Wongweichintana et al. (1984); Lutz & Spek (1998); Scheins et al. (2005). For hysdrogen-bond motifs, see: Bernstein et al. (1995); Etter et al. (1990). For a description of the Cambridge Structural Database, see: Allen (2002). For the program XPac, see: Gelbrich & Hursthouse (2005) and for the corresponding XPac dissimilarity index, see: Gelbrich et al. (2012).

Experimental

Crystal data

C₁₇H₂₀NO₃⁺·Cl^-
M_r = 321.79
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.3504 (2) Å
b = 12.8524 (5) Å
c = 16.0372 (5) Å
V = 1515.04 (9) Å³
Z = 4
Mo K radiation
= 0.27 mm^-1
T = 173 K
0.20 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur (Ruby, Gemini ultra) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2003 $[Oxford Diffraction (2003). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.982, T_max = 1.000
7406 measured reflections
2971 independent reflections
2803 reflections with I > 2(I)
R_int = 0.024

Refinement

R[F² > 2(F²)] = 0.027
wR(F²) = 0.069
S = 1.04
2971 reflections
229 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
_max = 0.18 e Å^-3
_min = -0.15 e Å^-3
Absolute structure: Flack (1983), 1245 Friedel pairs
Flack parameter: 0.02 (5)

Table 1
Hydrogen-bond and short-contact geometry (Å, °)

Cg1 is the centroid of the C1-C4/C12/C11 benzene ring.

D-HA	D-H	HA	DA	D-HA
O1-H1OCl1	0.82 (1)	2.35 (1)	3.1585 (14)	173 (2)
O3-H3OCl1	0.83 (1)	2.32 (1)	3.1416 (13)	168 (2)
N1-H1NCl1ⁱ	0.93 (1)	2.15 (1)	3.0626 (15)	169 (2)
C17-H17CO3ⁱⁱ	0.98	2.38	3.278 (2)	153
C14-H14O2ⁱ	1.00	2.60	3.2149 (19)	120
C2-H2Cg1ⁱⁱⁱ	0.95	2.71	3.638 (2)	165
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+2, z-{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2003 $[Oxford Diffraction (2003). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LX2271 ).

Acknowledgements

We thank Volker Kahlenberg for access to the X-ray instrument used in this study. DEB acknowledges financial support from the Hertha Firnberg Programme of the Austrian Science Fund (FWF, project T593-N19).

References

Allen, F. H. (2002). Acta Cryst. B58, 380-388.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.
Bye, E. (1976). Acta Chem. Scand. Ser. B, 30, 549-554.
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.
Flack, H. D. (1983). Acta Cryst. A39, 876-881.
Gelbrich, T. & Hursthouse, M. B. (2005). CrystEngComm, 7, 324-336.
Gelbrich, T., Threlfall, T. L. & Hursthouse, M. B. (2012). CrystEngComm, 14, 5454-5464.
Guguta, C., Peters, T. P. J. & de Gelder, R. (2008). Cryst. Growth Des. 8, 4150-4158.
Gylbert, L. (1973). Acta Cryst. B29, 1630-1635.
Lutz, M. & Spek, A. L. (1998). Acta Cryst. C54, 1477-1479.
Mackay, M. & Hodgkin, D. C. (1955). J. Chem. Soc. pp. 3261-3267.
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.
Oxford Diffraction (2003). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.
Scheins, S., Messerschmidt, M. & Luger, P. (2005). Acta Cryst. B61, 443-448.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.
Wongweichintana, C., Holt, E. M. & Purdie, N. (1984). Acta Cryst. C40, 1486-1490.

organic compounds

Morphine hydrochloride anhydrate1