Stable polymorph of morphineCAS number: 57–27–2.

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

doi:10.1107/S1600536812048945

Volume 69
Part 1
Page o2
January 2013

Received 19 November 2012
Accepted 28 November 2012
Online 5 December 2012

Key indicators
Single-crystal X-ray study
T = 173 K
Mean (C-C) = 0.009 Å
R = 0.068
wR = 0.141
Data-to-parameter ratio = 7.3
Details

Stable polymorph of morphine¹

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 stable polymorph of the title compound, C₁₇H₁₉NO₃ [systematic name: (5 [alpha] ,6 [alpha] )-7,8-didehydro-4,5-epoxy-17-methylmorphinan-3,6-diol], the molecular conformation is in agreement with the characteristics of previously reported morphine forms. The molecule displays the typical T-shape and its piperidine ring adopts a slightly distorted chair conformation. Intermolecular O-HO hydrogen bonds link the molecules into helical chains parallel to the b axis. Intramolecular O-HO hydrogen bonds are also observed.

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); Gelbrich et al. (2012). For decriptions of morphine polymorphs, see: Kofler (1933); Kuhnert-Brandstätter et al. (1975). For a description of the Cambridge Structural Database, see: Allen (2002). For the program XPac, see: Gelbrich & Hursthouse (2005).

Experimental

Crystal data

C₁₇H₁₉NO₃
M_r = 285.33
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.6989 (10) Å
b = 12.737 (4) Å
c = 13.740 (4) Å
V = 1347.4 (6) Å³
Z = 4
Cu K radiation
= 0.78 mm^-1
T = 173 K
0.15 × 0.10 × 0.03 mm

Data collection

Oxford Diffraction Xcalibur (Ruby, Gemini ultra) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2003 $[Oxford Diffraction (2003). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd., Abingdon, Oxfordshire, England.]$ ) T_min = 0.624, T_max = 1.000
13009 measured reflections
1408 independent reflections
977 reflections with I > 2(I)
R_int = 0.118

Refinement

R[F² > 2(F²)] = 0.068
wR(F²) = 0.141
S = 1.01
1408 reflections
192 parameters
H-atom parameters constrained
_max = 0.27 e Å^-3
_min = -0.26 e Å^-3

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
O1-H1O3ⁱ	0.84	1.96	2.757 (6)	159
O3-H3O2	0.84	2.17	2.629 (6)	114
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2003 $[Oxford Diffraction (2003). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd., Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Bruker, 1998) and Mercury (Bruno et al., 2002); 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: IM2413 ).

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 No. T593-N19).

References

Allen, F. H. (2002). Acta Cryst. B58, 380-388.
Bruker (1998). XP. Bruker AXS Inc., Madison, Wisconsin, USA
Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389-397.
Bye, E. (1976). Acta Chem. Scand. Ser. B, 30, 549-554.
Gelbrich, T., Braun, D. E. & Griesser, U. J. (2012). Acta Cryst. E68, o3358-o3359.
Gelbrich, T. & Hursthouse, M. B. (2005). CrystEngComm, 7, 324-336.
Guguta, C., Peters, T. P. J. & de Gelder, R. (2008). Cryst. Growth Des. 8, 4150-4158.
Gylbert, L. (1973). Acta Cryst. B29, 1630-1635.
Kofler, L. (1933). Pharm. Monatsh. 14, 220-222.
Kuhnert-Brandstätter, M., Kofler, A. & Heindl, W. (1975). Pharm. Acta Helv. 50, 360-372.
Lutz, M. & Spek, A. L. (1998). Acta Cryst. C54, 1477-1479.
Mackay, M. & Hodgkin, D. C. (1955). J. Chem. Soc. 3261-3267.
Oxford Diffraction (2003). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd., Abingdon, Oxfordshire, 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

Stable polymorph of morphine1