Morphine hydro-chloride anhydrate.

In the title mol-ecular salt [systematic name: (5α,6α)-7,8-didehydro-4,5-ep-oxy-17-methyl-morphinan-3,6-diol hydro-chloride], 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-H⋯Cl and O-H⋯Cl 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 = 321.79

Orthorhombic,

a = 7.3504 (2) Å

b = 12.8524 (5) Å

c = 16.0372 (5) Å

V = 1515.04 (9) Å3

Z = 4

Mo Kα radiation

μ = 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 ▶) T min = 0.982, T max = 1.000

7406 measured reflections

2971 independent reflections

2803 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.069

S = 1.04

2971 reflections

229 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.18 e Å−3

Δρmin = −0.15 e Å−3

Absolute structure: Flack (1983 ▶), 1245 Friedel pairs

Flack parameter: 0.02 (5)

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

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812046405/lx2271sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812046405/lx2271Isup2.hkl

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

C17H20NO3+·Cl−	F(000) = 680
Mr = 321.79	Dx = 1.411 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4272 reflections
a = 7.3504 (2) Å	θ = 3.0–29.2°
b = 12.8524 (5) Å	µ = 0.27 mm−1
c = 16.0372 (5) Å	T = 173 K
V = 1515.04 (9) Å3	Block, colourless
Z = 4	0.20 × 0.20 × 0.20 mm

Oxford Diffraction Xcalibur (Ruby, Gemini ultra) diffractometer	2971 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2803 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 10.3575 pixels mm-1	θmax = 26.0°, θmin = 3.0°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2003)	k = −12→15
Tmin = 0.982, Tmax = 1.000	l = −19→19
7406 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.069	w = 1/[σ2(Fo2) + (0.0324P)2 + 0.2844P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
2971 reflections	Δρmax = 0.18 e Å−3
229 parameters	Δρmin = −0.15 e Å−3
3 restraints	Absolute structure: Flack (1983), 1245 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.02 (5)

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.

	x	y	z	Uiso*/Ueq
Cl1	0.96273 (5)	0.72090 (4)	0.82895 (3)	0.03438 (12)
O1	0.83825 (19)	0.64336 (10)	0.65098 (8)	0.0367 (3)
H1O	0.877 (3)	0.6586 (18)	0.6972 (8)	0.051 (7)*
O2	0.55524 (15)	0.77200 (8)	0.73074 (6)	0.0242 (2)
O3	0.62377 (17)	0.85259 (10)	0.88464 (7)	0.0294 (3)
H3O	0.709 (2)	0.8207 (16)	0.8625 (13)	0.050 (7)*
N1	0.29227 (19)	1.08986 (11)	0.56252 (9)	0.0242 (3)
H1N	0.221 (2)	1.1239 (15)	0.6013 (10)	0.044 (6)*
C1	0.7896 (2)	0.86915 (13)	0.51135 (9)	0.0243 (4)
H1	0.8436	0.8943	0.4615	0.042 (6)*
C2	0.8430 (2)	0.77357 (14)	0.54336 (10)	0.0259 (4)
H2	0.9308	0.7338	0.5139	0.031 (5)*
C3	0.7717 (2)	0.73423 (12)	0.61752 (10)	0.0245 (3)
C4	0.6342 (2)	0.79226 (12)	0.65458 (9)	0.0202 (3)
C5	0.5554 (2)	0.92311 (12)	0.82414 (9)	0.0227 (3)
H5	0.4628	0.9669	0.8534	0.019 (4)*
C6	0.4532 (2)	0.86543 (12)	0.75454 (9)	0.0202 (3)
H6	0.3301	0.8446	0.7753	0.022 (4)*
C7	0.6973 (2)	0.99708 (13)	0.79168 (10)	0.0242 (4)
H7	0.8131	1.0002	0.8179	0.031 (5)*
C8	0.6628 (2)	1.05776 (13)	0.72718 (10)	0.0232 (4)
H8	0.7501	1.1073	0.7090	0.027 (5)*
C9	0.4862 (2)	1.09416 (13)	0.59477 (10)	0.0220 (3)
H9	0.5211	1.1691	0.5999	0.022 (4)*
C10	0.6209 (2)	1.04229 (14)	0.53414 (11)	0.0272 (4)
H10A	0.5727	1.0489	0.4767	0.029 (5)*
H10B	0.7377	1.0805	0.5364	0.048 (6)*
C11	0.6574 (2)	0.92863 (13)	0.55164 (9)	0.0207 (3)
C12	0.5743 (2)	0.88337 (12)	0.61978 (9)	0.0188 (3)
C13	0.43158 (19)	0.93188 (12)	0.67453 (9)	0.0181 (3)
C14	0.4832 (2)	1.04739 (12)	0.68285 (9)	0.0193 (3)
H14	0.3875	1.0836	0.7163	0.012 (4)*
C15	0.2383 (2)	0.92357 (13)	0.63760 (10)	0.0243 (4)
H15A	0.2078	0.8493	0.6290	0.033 (5)*
H15B	0.1498	0.9528	0.6778	0.017 (4)*
C16	0.2217 (2)	0.98094 (13)	0.55534 (11)	0.0283 (4)
H16A	0.2912	0.9433	0.5119	0.030 (5)*
H16B	0.0924	0.9827	0.5380	0.021 (4)*
C17	0.2666 (3)	1.14956 (15)	0.48358 (11)	0.0349 (4)
H17A	0.3241	1.1120	0.4374	0.035 (5)*
H17B	0.3225	1.2184	0.4892	0.046 (6)*
H17C	0.1363	1.1574	0.4723	0.041 (6)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0245 (2)	0.0376 (2)	0.0411 (2)	0.00496 (19)	0.00355 (18)	0.0024 (2)
O1	0.0476 (8)	0.0244 (7)	0.0383 (8)	0.0127 (6)	0.0048 (6)	−0.0009 (6)
O2	0.0310 (6)	0.0171 (5)	0.0246 (6)	0.0019 (5)	0.0063 (5)	0.0017 (4)
O3	0.0345 (7)	0.0337 (7)	0.0201 (6)	0.0081 (6)	0.0012 (5)	0.0051 (5)
N1	0.0265 (7)	0.0226 (7)	0.0236 (7)	0.0017 (6)	−0.0054 (6)	0.0008 (6)
C1	0.0234 (8)	0.0297 (9)	0.0199 (8)	−0.0052 (7)	0.0032 (7)	−0.0035 (7)
C2	0.0240 (8)	0.0281 (9)	0.0256 (8)	0.0007 (8)	0.0028 (7)	−0.0120 (8)
C3	0.0274 (8)	0.0180 (8)	0.0282 (8)	0.0014 (7)	−0.0008 (7)	−0.0051 (7)
C4	0.0222 (7)	0.0190 (8)	0.0195 (7)	−0.0047 (7)	0.0005 (6)	−0.0038 (6)
C5	0.0258 (8)	0.0242 (8)	0.0181 (7)	0.0037 (7)	0.0012 (7)	0.0008 (6)
C6	0.0201 (7)	0.0184 (8)	0.0221 (7)	0.0003 (7)	0.0049 (7)	0.0008 (6)
C7	0.0236 (8)	0.0250 (8)	0.0240 (8)	−0.0018 (7)	−0.0044 (7)	−0.0058 (7)
C8	0.0245 (8)	0.0185 (8)	0.0267 (8)	−0.0063 (7)	−0.0010 (7)	−0.0032 (7)
C9	0.0235 (8)	0.0168 (7)	0.0258 (8)	−0.0025 (7)	−0.0040 (6)	0.0029 (6)
C10	0.0279 (9)	0.0268 (9)	0.0269 (9)	0.0001 (8)	0.0029 (7)	0.0075 (7)
C11	0.0201 (8)	0.0243 (8)	0.0177 (7)	−0.0042 (7)	−0.0020 (6)	−0.0009 (6)
C12	0.0188 (7)	0.0179 (7)	0.0198 (7)	−0.0030 (6)	−0.0024 (6)	−0.0041 (6)
C13	0.0173 (7)	0.0177 (7)	0.0192 (7)	−0.0029 (6)	−0.0002 (6)	0.0002 (6)
C14	0.0204 (7)	0.0167 (7)	0.0209 (8)	−0.0008 (6)	−0.0001 (6)	−0.0016 (6)
C15	0.0200 (8)	0.0225 (8)	0.0303 (9)	−0.0033 (7)	−0.0022 (7)	−0.0012 (7)
C16	0.0256 (9)	0.0268 (9)	0.0325 (9)	−0.0009 (7)	−0.0096 (7)	−0.0051 (8)
C17	0.0449 (11)	0.0311 (10)	0.0288 (9)	0.0037 (9)	−0.0109 (8)	0.0055 (8)

O1—C3	1.375 (2)	C7—H7	0.9500
O1—H1O	0.817 (9)	C8—C14	1.505 (2)
O2—C4	1.3770 (17)	C8—H8	0.9500
O2—C6	1.4665 (18)	C9—C14	1.535 (2)
O3—C5	1.4196 (19)	C9—C10	1.540 (2)
O3—H3O	0.831 (10)	C9—H9	1.0000
N1—C17	1.492 (2)	C10—C11	1.511 (2)
N1—C16	1.497 (2)	C10—H10A	0.9900
N1—C9	1.517 (2)	C10—H10B	0.9900
N1—H1N	0.925 (9)	C11—C12	1.380 (2)
C1—C2	1.388 (2)	C12—C13	1.503 (2)
C1—C11	1.395 (2)	C13—C14	1.538 (2)
C1—H1	0.9500	C13—C15	1.543 (2)
C2—C3	1.395 (2)	C14—H14	1.0000
C2—H2	0.9500	C15—C16	1.516 (2)
C3—C4	1.390 (2)	C15—H15A	0.9900
C4—C12	1.370 (2)	C15—H15B	0.9900
C5—C7	1.504 (2)	C16—H16A	0.9900
C5—C6	1.536 (2)	C16—H16B	0.9900
C5—H5	1.0000	C17—H17A	0.9800
C6—C13	1.549 (2)	C17—H17B	0.9800
C6—H6	1.0000	C17—H17C	0.9800
C7—C8	1.320 (2)
C3—O1—H1O	105.8 (17)	C10—C9—H9	107.7
C4—O2—C6	106.96 (11)	C11—C10—C9	114.53 (14)
C5—O3—H3O	106.9 (16)	C11—C10—H10A	108.6
C17—N1—C16	111.81 (13)	C9—C10—H10A	108.6
C17—N1—C9	112.91 (14)	C11—C10—H10B	108.6
C16—N1—C9	112.69 (13)	C9—C10—H10B	108.6
C17—N1—H1N	104.8 (14)	H10A—C10—H10B	107.6
C16—N1—H1N	107.3 (14)	C12—C11—C1	116.35 (15)
C9—N1—H1N	106.7 (13)	C12—C11—C10	118.42 (14)
C2—C1—C11	120.71 (15)	C1—C11—C10	124.55 (15)
C2—C1—H1	119.6	C4—C12—C11	122.73 (14)
C11—C1—H1	119.6	C4—C12—C13	109.92 (13)
C1—C2—C3	122.00 (15)	C11—C12—C13	126.61 (14)
C1—C2—H2	119.0	C12—C13—C14	106.19 (12)
C3—C2—H2	119.0	C12—C13—C15	112.92 (13)
O1—C3—C4	123.21 (14)	C14—C13—C15	109.10 (12)
O1—C3—C2	120.45 (15)	C12—C13—C6	100.58 (12)
C4—C3—C2	116.33 (15)	C14—C13—C6	115.78 (12)
C12—C4—O2	112.80 (13)	C15—C13—C6	111.97 (12)
C12—C4—C3	121.21 (14)	C8—C14—C9	112.77 (13)
O2—C4—C3	125.76 (14)	C8—C14—C13	110.04 (13)
O3—C5—C7	113.23 (13)	C9—C14—C13	107.56 (12)
O3—C5—C6	111.20 (13)	C8—C14—H14	108.8
C7—C5—C6	113.13 (12)	C9—C14—H14	108.8
O3—C5—H5	106.2	C13—C14—H14	108.8
C7—C5—H5	106.2	C16—C15—C13	112.00 (13)
C6—C5—H5	106.2	C16—C15—H15A	109.2
O2—C6—C5	109.51 (12)	C13—C15—H15A	109.2
O2—C6—C13	106.75 (11)	C16—C15—H15B	109.2
C5—C6—C13	112.69 (12)	C13—C15—H15B	109.2
O2—C6—H6	109.3	H15A—C15—H15B	107.9
C5—C6—H6	109.3	N1—C16—C15	111.09 (13)
C13—C6—H6	109.3	N1—C16—H16A	109.4
C8—C7—C5	120.73 (15)	C15—C16—H16A	109.4
C8—C7—H7	119.6	N1—C16—H16B	109.4
C5—C7—H7	119.6	C15—C16—H16B	109.4
C7—C8—C14	119.11 (15)	H16A—C16—H16B	108.0
C7—C8—H8	120.4	N1—C17—H17A	109.5
C14—C8—H8	120.4	N1—C17—H17B	109.5
N1—C9—C14	106.60 (12)	H17A—C17—H17B	109.5
N1—C9—C10	111.91 (13)	N1—C17—H17C	109.5
C14—C9—C10	114.89 (13)	H17A—C17—H17C	109.5
N1—C9—H9	107.7	H17B—C17—H17C	109.5
C14—C9—H9	107.7

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···Cl1	0.82 (1)	2.35 (1)	3.1585 (14)	173 (2)
O3—H3O···Cl1	0.83 (1)	2.32 (1)	3.1416 (13)	168 (2)
N1—H1N···Cl1i	0.93 (1)	2.15 (1)	3.0626 (15)	169 (2)
C17—H17C···O3ii	0.98	2.38	3.278 (2)	153
C14—H14···O2i	1.00	2.60	3.2149 (19)	120
C2—H2···Cg1iii	0.95	2.71	3.638 (2)	165

Table 1

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯Cl1	0.82 (1)	2.35 (1)	3.1585 (14)	173 (2)
O3—H3O⋯Cl1	0.83 (1)	2.32 (1)	3.1416 (13)	168 (2)
N1—H1N⋯Cl1i	0.93 (1)	2.15 (1)	3.0626 (15)	169 (2)
C17—H17C⋯O3ii	0.98	2.38	3.278 (2)	153
C14—H14⋯O2i	1.00	2.60	3.2149 (19)	120
C2—H2⋯Cg1iii	0.95	2.71	3.638 (2)	165

Symmetry codes: (i) ; (ii) ; (iii) .