Stable polymorph of morphine.

In the stable polymorph of the title compound, C17H19NO3 [systematic name: (5α,6α)-7,8-didehydro-4,5-ep-oxy-17-methyl-morphinan-3,6-diol], the mol-ecular 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. Inter-molecular O-H⋯O hydrogen bonds link the mol-ecules into helical chains parallel to the b axis. Intra-molecular O-H⋯O 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 = 285.33

Orthorhombic,

a = 7.6989 (10) Å

b = 12.737 (4) Å

c = 13.740 (4) Å

V = 1347.4 (6) Å3

Z = 4

Cu Kα radiation

μ = 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 ▶) T min = 0.624, T max = 1.000

13009 measured reflections

1408 independent reflections

977 reflections with I > 2σ(I)

R int = 0.118

Refinement

R[F 2 > 2σ(F 2)] = 0.068

wR(F 2) = 0.141

S = 1.01

1408 reflections

192 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.26 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2003 ▶); 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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812048945/im2413sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812048945/im2413Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C17H19NO3	F(000) = 608
Mr = 285.33	Dx = 1.407 Mg m−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1360 reflections
a = 7.6989 (10) Å	θ = 3.2–68.2°
b = 12.737 (4) Å	µ = 0.78 mm−1
c = 13.740 (4) Å	T = 173 K
V = 1347.4 (6) Å3	Plate, colourless
Z = 4	0.15 × 0.10 × 0.03 mm

Oxford Diffraction Xcalibur (Ruby, Gemini ultra) diffractometer	1408 independent reflections
Radiation source: Enhance (Mo) X-ray Source	977 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.118
Detector resolution: 10.3575 pixels mm-1	θmax = 68.2°, θmin = 4.7°
ω scans	h = −9→8
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2003)	k = −14→15
Tmin = 0.624, Tmax = 1.000	l = −16→16
13009 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.068	H-atom parameters constrained
wR(F2) = 0.141	w = 1/[σ2(Fo2) + (0.0112P)2 + 2.P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
1408 reflections	Δρmax = 0.27 e Å−3
192 parameters	Δρmin = −0.26 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0043 (4)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.The Flack x parameter (Flack, 1983) and the Hooft y parameter (Hooft et al., 2008) were both indeterminate due to a lack of significant resonant scattering. Accordingly, Friedel opposites were merged prior to the final refinement. [Flack, H. D. (1983). Acta Cryst. A39, 876–881; Hooft, R. W. W., Straver, L. H. & Spek, A. L. (2008). J. Appl. Cryst.41, 96–103.]

	x	y	z	Uiso*/Ueq
O1	0.0998 (5)	0.6564 (3)	0.7856 (3)	0.0520 (12)
H1	0.0431	0.7103	0.7705	0.062*
O2	0.3165 (5)	0.4742 (3)	0.7958 (3)	0.0466 (11)
O3	0.1429 (6)	0.2969 (3)	0.7838 (3)	0.0546 (12)
H3	0.1096	0.3587	0.7941	0.066*
N1	0.8422 (6)	0.4378 (4)	0.5555 (4)	0.0492 (14)
C1	0.3549 (8)	0.6662 (5)	0.5563 (5)	0.0458 (15)
H1A	0.3611	0.7068	0.4984	0.055*
C2	0.2382 (8)	0.6935 (5)	0.6290 (5)	0.0466 (16)
H2	0.1665	0.7534	0.6198	0.056*
C3	0.2223 (7)	0.6362 (5)	0.7147 (5)	0.0429 (15)
C4	0.3281 (7)	0.5499 (4)	0.7238 (5)	0.0408 (14)
C5	0.2959 (8)	0.2985 (5)	0.7233 (5)	0.0494 (17)
H5	0.3554	0.2293	0.7320	0.059*
C6	0.4208 (7)	0.3836 (5)	0.7615 (5)	0.0462 (16)
H6	0.4902	0.3548	0.8168	0.055*
C7	0.2554 (9)	0.3091 (5)	0.6180 (5)	0.0499 (17)
H7	0.1398	0.2980	0.5961	0.060*
C8	0.3781 (9)	0.3338 (5)	0.5537 (5)	0.0506 (17)
H8	0.3524	0.3340	0.4861	0.061*
C9	0.6652 (8)	0.4267 (5)	0.5160 (5)	0.0450 (15)
H9	0.6748	0.3841	0.4551	0.054*
C10	0.5732 (8)	0.5321 (5)	0.4878 (5)	0.0491 (17)
H10A	0.6630	0.5838	0.4686	0.059*
H10B	0.4984	0.5194	0.4304	0.059*
C11	0.4634 (7)	0.5792 (5)	0.5682 (4)	0.0410 (14)
C12	0.4530 (7)	0.5257 (5)	0.6546 (4)	0.0386 (14)
C13	0.5465 (8)	0.4258 (5)	0.6810 (4)	0.0415 (15)
C14	0.5584 (8)	0.3617 (5)	0.5888 (5)	0.0466 (16)
H14	0.6227	0.2953	0.6033	0.056*
C15	0.7290 (7)	0.4477 (5)	0.7212 (5)	0.0443 (15)
H15A	0.7199	0.4948	0.7783	0.053*
H15B	0.7818	0.3809	0.7432	0.053*
C16	0.8453 (8)	0.4978 (5)	0.6457 (5)	0.0521 (17)
H16A	0.8056	0.5704	0.6329	0.062*
H16B	0.9657	0.5012	0.6708	0.062*
C17	0.9652 (8)	0.4788 (6)	0.4841 (5)	0.060 (2)
H17A	0.9335	0.5510	0.4672	0.090*
H17B	0.9621	0.4350	0.4254	0.090*
H17C	1.0826	0.4778	0.5117	0.090*

	U11	U22	U33	U12	U13	U23
O1	0.040 (2)	0.053 (2)	0.063 (3)	0.012 (2)	0.008 (2)	0.002 (2)
O2	0.031 (2)	0.048 (2)	0.060 (3)	0.0019 (19)	0.004 (2)	0.000 (2)
O3	0.040 (2)	0.050 (2)	0.074 (3)	−0.006 (2)	0.014 (3)	−0.002 (2)
N1	0.026 (2)	0.063 (3)	0.059 (3)	0.001 (3)	0.005 (2)	0.003 (3)
C1	0.040 (3)	0.043 (3)	0.055 (4)	0.003 (3)	0.002 (3)	0.006 (3)
C2	0.035 (3)	0.044 (3)	0.061 (5)	0.008 (3)	−0.004 (3)	0.000 (3)
C3	0.027 (3)	0.047 (3)	0.055 (4)	0.003 (3)	0.003 (3)	−0.003 (3)
C4	0.025 (3)	0.046 (3)	0.051 (4)	0.000 (3)	0.001 (3)	0.000 (3)
C5	0.034 (3)	0.048 (4)	0.066 (5)	−0.006 (3)	0.009 (3)	−0.001 (3)
C6	0.030 (3)	0.048 (4)	0.061 (4)	0.000 (3)	−0.001 (3)	0.003 (3)
C7	0.039 (3)	0.047 (4)	0.064 (5)	−0.005 (3)	0.006 (3)	−0.005 (3)
C8	0.044 (3)	0.052 (4)	0.056 (4)	−0.005 (3)	0.003 (3)	−0.008 (3)
C9	0.037 (3)	0.048 (4)	0.050 (4)	0.004 (3)	0.003 (3)	−0.003 (3)
C10	0.040 (3)	0.058 (4)	0.050 (4)	0.008 (3)	0.007 (3)	0.006 (3)
C11	0.030 (3)	0.047 (3)	0.045 (4)	0.004 (3)	0.003 (3)	−0.006 (3)
C12	0.024 (3)	0.044 (3)	0.048 (4)	0.002 (3)	−0.003 (3)	0.001 (3)
C13	0.030 (3)	0.046 (3)	0.048 (4)	0.000 (3)	−0.002 (3)	0.000 (3)
C14	0.038 (3)	0.038 (3)	0.065 (5)	−0.001 (3)	−0.001 (3)	0.002 (3)
C15	0.032 (3)	0.051 (4)	0.050 (4)	0.001 (3)	−0.005 (3)	0.000 (3)
C16	0.028 (3)	0.064 (4)	0.064 (4)	−0.003 (3)	0.000 (3)	0.000 (4)
C17	0.033 (3)	0.080 (5)	0.066 (5)	0.000 (4)	0.008 (3)	0.008 (4)

O1—C3	1.380 (7)	C7—H7	0.9500
O1—H1	0.8400	C8—C14	1.512 (9)
O2—C4	1.385 (7)	C8—H8	0.9500
O2—C6	1.483 (7)	C9—C14	1.538 (9)
O3—C5	1.442 (8)	C9—C10	1.566 (9)
O3—H3	0.8400	C9—H9	1.0000
N1—C16	1.456 (8)	C10—C11	1.516 (8)
N1—C17	1.460 (8)	C10—H10A	0.9900
N1—C9	1.474 (8)	C10—H10B	0.9900
C1—C2	1.387 (9)	C11—C12	1.371 (8)
C1—C11	1.397 (8)	C12—C13	1.507 (8)
C1—H1A	0.9500	C13—C14	1.511 (9)
C2—C3	1.390 (9)	C13—C15	1.535 (8)
C2—H2	0.9500	C14—H14	1.0000
C3—C4	1.374 (8)	C15—C16	1.512 (8)
C4—C12	1.387 (8)	C15—H15A	0.9900
C5—C7	1.486 (9)	C15—H15B	0.9900
C5—C6	1.542 (8)	C16—H16A	0.9900
C5—H5	1.0000	C16—H16B	0.9900
C6—C13	1.563 (9)	C17—H17A	0.9800
C6—H6	1.0000	C17—H17B	0.9800
C7—C8	1.331 (9)	C17—H17C	0.9800
C3—O1—H1	109.5	C11—C10—C9	114.3 (5)
C4—O2—C6	106.2 (4)	C11—C10—H10A	108.7
C5—O3—H3	109.5	C9—C10—H10A	108.7
C16—N1—C17	112.0 (5)	C11—C10—H10B	108.7
C16—N1—C9	112.2 (5)	C9—C10—H10B	108.7
C17—N1—C9	112.7 (5)	H10A—C10—H10B	107.6
C2—C1—C11	120.1 (6)	C12—C11—C1	117.4 (6)
C2—C1—H1A	119.9	C12—C11—C10	117.9 (5)
C11—C1—H1A	119.9	C1—C11—C10	124.2 (6)
C1—C2—C3	122.3 (6)	C11—C12—C4	121.6 (5)
C1—C2—H2	118.8	C11—C12—C13	126.9 (5)
C3—C2—H2	118.8	C4—C12—C13	110.7 (5)
C4—C3—O1	119.3 (6)	C12—C13—C14	106.5 (5)
C4—C3—C2	116.4 (6)	C12—C13—C15	111.7 (5)
O1—C3—C2	124.1 (5)	C14—C13—C15	110.1 (5)
C3—C4—O2	125.7 (5)	C12—C13—C6	99.5 (5)
C3—C4—C12	121.7 (6)	C14—C13—C6	116.4 (5)
O2—C4—C12	112.4 (5)	C15—C13—C6	112.0 (5)
O3—C5—C7	113.0 (5)	C13—C14—C8	109.8 (5)
O3—C5—C6	108.9 (5)	C13—C14—C9	106.7 (5)
C7—C5—C6	113.5 (5)	C8—C14—C9	114.2 (6)
O3—C5—H5	107.0	C13—C14—H14	108.7
C7—C5—H5	107.0	C8—C14—H14	108.7
C6—C5—H5	107.0	C9—C14—H14	108.7
O2—C6—C5	108.5 (5)	C16—C15—C13	111.9 (5)
O2—C6—C13	107.1 (5)	C16—C15—H15A	109.2
C5—C6—C13	112.8 (5)	C13—C15—H15A	109.2
O2—C6—H6	109.5	C16—C15—H15B	109.2
C5—C6—H6	109.5	C13—C15—H15B	109.2
C13—C6—H6	109.5	H15A—C15—H15B	107.9
C8—C7—C5	121.3 (6)	N1—C16—C15	110.7 (5)
C8—C7—H7	119.4	N1—C16—H16A	109.5
C5—C7—H7	119.4	C15—C16—H16A	109.5
C7—C8—C14	119.7 (6)	N1—C16—H16B	109.5
C7—C8—H8	120.1	C15—C16—H16B	109.5
C14—C8—H8	120.1	H16A—C16—H16B	108.1
N1—C9—C14	107.8 (5)	N1—C17—H17A	109.5
N1—C9—C10	115.3 (5)	N1—C17—H17B	109.5
C14—C9—C10	112.4 (5)	H17A—C17—H17B	109.5
N1—C9—H9	107.0	N1—C17—H17C	109.5
C14—C9—H9	107.0	H17A—C17—H17C	109.5
C10—C9—H9	107.0	H17B—C17—H17C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3i	0.84	1.96	2.757 (6)	159
O3—H3···O2	0.84	2.17	2.629 (6)	114

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3i	0.84	1.96	2.757 (6)	159
O3—H3⋯O2	0.84	2.17	2.629 (6)	114

Symmetry code: (i) .