(S)-(+)-Ketamine hydro-chloride.

The crystal structure of the title compound {systematic name: (S)-(+)-N-[1-(2-chloro-phen-yl)-2-oxocyclo-hexyl]meth-anam-in-ium chloride}, C(13)H(17)ClNO(+)·Cl(-), was determined at 90 (2) K. The (S)-(+)-ketamine hydro-chloride salt is a well known anesthetic compound and is dramatically more potent than its R isomer. In the title compound, the cyclo-hexa-none ring adopts a chair conformation with the oxo group in the equatorial orientation. The methyl-amino and 2-chloro-phenyl groups at the 2-position have an equatorial and an axial orientation, respectively. The packing of ions is stabilized by an infinite one-dimensional ⋯Cl⋯H-N-H⋯Cl⋯ hydrogen-bonding network, involving NH(2) (+) groups as donors and chloride anions as acceptors.

Related literature

For related literature, see: Chankvetadze et al. (2002 ▶); Domino et al. (1965 ▶); Marhofer et al. (2001 ▶); Mathisen et al. (1995 ▶); Pees et al. (2003 ▶); Reich & Silvay (1989 ▶); Smirnova et al. (1989 ▶); White et al. (1985 ▶); Wolff & Winstock (2006 ▶).

Experimental

Crystal data

C13H17ClNO+·Cl−

M = 274.18

Monoclinic,

a = 8.4338 (4) Å

b = 7.0715 (4) Å

c = 11.3524 (6) Å

β = 101.875 (1)°

V = 662.56 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.47 mm−1

T = 90 (2) K

0.50 × 0.12 × 0.10 mm

Data collection

Bruker APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ▶) T min = 0.798, T max = 0.954

6985 measured reflections

3251 independent reflections

3146 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.066

S = 1.07

3251 reflections

223 parameters

1 restraint

All H-atom parameters refined

Δρmax = 0.30 e Å−3

Δρmin = −0.17 e Å−3

Absolute structure: Flack (1983 ▶), 1472 Friedel pairs

Flack parameter: 0.00 (5)

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalMaker (Palmer, 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808021053/bh2181sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021053/bh2181Isup2.hkl

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

C13H17ClNO·Cl	F000 = 288
Mr = 274.18	Dx = 1.374 Mg m−3
Monoclinic, P21	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3471 reflections
a = 8.4338 (4) Å	θ = 2.5–28.2º
b = 7.0715 (4) Å	µ = 0.47 mm−1
c = 11.3524 (6) Å	T = 90 (2) K
β = 101.875 (1)º	Rod, colourless
V = 662.56 (6) Å3	0.50 × 0.12 × 0.10 mm
Z = 2

Bruker APEX CCD area-detector diffractometer	3251 independent reflections
Monochromator: graphite	3146 reflections with I > 2σ(I)
Detector resolution: 512 pixels mm-1	Rint = 0.020
T = 90(2) K	θmax = 28.3º
φ and ω scans	θmin = 1.8º
Absorption correction: multi-scan(SADABS; Sheldrick, 2008)	h = −11→11
Tmin = 0.798, Tmax = 0.954	k = −9→9
6985 measured reflections	l = −15→15

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	All H-atom parameters refined
R[F2 > 2σ(F2)] = 0.027	w = 1/[σ2(Fo2) + (0.0378P)2 + 0.0273P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.066	(Δ/σ)max = 0.001
S = 1.07	Δρmax = 0.31 e Å−3
3251 reflections	Δρmin = −0.17 e Å−3
223 parameters	Extinction correction: none
1 restraint	Absolute structure: Flack (1983), 1472 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.00 (5)
Secondary atom site location: difference Fourier map

	x	y	z	Uiso*/Ueq
Cl2	0.05227 (4)	0.23769 (5)	0.35081 (3)	0.01627 (9)
Cl1	0.34238 (5)	−0.13679 (5)	0.87212 (4)	0.02248 (10)
O1	0.38001 (14)	−0.03746 (17)	0.60012 (10)	0.0205 (2)
N1	0.11098 (16)	0.1291 (2)	0.62148 (11)	0.0132 (3)
C1	0.27185 (19)	0.0822 (2)	0.90899 (14)	0.0157 (3)
C2	0.2437 (2)	0.0998 (3)	1.02456 (15)	0.0212 (3)
C3	0.1889 (2)	0.2691 (3)	1.06202 (16)	0.0239 (4)
C4	0.1635 (2)	0.4199 (3)	0.98344 (15)	0.0218 (4)
C5	0.19088 (19)	0.4012 (2)	0.86757 (15)	0.0175 (3)
C6	0.24628 (16)	0.2315 (3)	0.82673 (13)	0.0140 (3)
C7	0.26395 (16)	0.2136 (2)	0.69555 (12)	0.0124 (3)
C8	0.40443 (19)	0.0878 (2)	0.67428 (13)	0.0155 (3)
C9	0.57016 (19)	0.1543 (2)	0.73576 (15)	0.0176 (3)
C10	0.59821 (19)	0.3492 (3)	0.68330 (14)	0.0175 (3)
C11	0.46277 (19)	0.4860 (2)	0.69619 (15)	0.0166 (3)
C12	0.29711 (19)	0.4052 (2)	0.63815 (14)	0.0142 (3)
C13	−0.04410 (18)	0.2160 (3)	0.63712 (14)	0.0170 (3)
H11B	0.471 (2)	0.511 (3)	0.7848 (19)	0.024 (5)*
H12A	0.294 (2)	0.378 (3)	0.5499 (16)	0.014 (4)*
H13A	−0.060 (2)	0.181 (3)	0.7166 (17)	0.015 (5)*
H10B	0.603 (2)	0.334 (3)	0.6003 (17)	0.016 (5)*
H9A	0.649 (2)	0.055 (3)	0.7199 (18)	0.024 (5)*
H1B	0.116 (2)	0.140 (3)	0.5461 (17)	0.008 (4)*
H10A	0.703 (3)	0.397 (3)	0.7211 (17)	0.021 (5)*
H13B	−0.126 (2)	0.167 (3)	0.5775 (18)	0.021 (5)*
H9B	0.574 (2)	0.167 (3)	0.8215 (18)	0.018 (5)*
H5	0.174 (2)	0.503 (3)	0.8174 (19)	0.023 (5)*
H12B	0.209 (2)	0.490 (3)	0.6419 (16)	0.018 (5)*
H3	0.166 (2)	0.278 (3)	1.1373 (19)	0.026 (6)*
H2	0.259 (2)	−0.003 (3)	1.0735 (17)	0.015 (5)*
H4	0.128 (2)	0.542 (3)	1.0038 (18)	0.022 (5)*
H13C	−0.038 (2)	0.351 (3)	0.6318 (16)	0.018 (5)*
H1A	0.105 (3)	0.015 (4)	0.6352 (18)	0.024 (5)*
H11A	0.483 (3)	0.601 (4)	0.6570 (18)	0.029 (6)*

	U11	U22	U33	U12	U13	U23
Cl2	0.02035 (17)	0.01438 (16)	0.01376 (16)	0.00042 (14)	0.00279 (12)	−0.00059 (13)
Cl1	0.0302 (2)	0.01408 (17)	0.02266 (19)	0.00260 (16)	0.00414 (15)	0.00452 (14)
O1	0.0253 (6)	0.0180 (6)	0.0188 (6)	0.0042 (5)	0.0059 (5)	−0.0035 (5)
N1	0.0159 (6)	0.0117 (6)	0.0117 (6)	0.0003 (5)	0.0019 (5)	−0.0008 (5)
C1	0.0155 (7)	0.0150 (7)	0.0163 (7)	−0.0006 (6)	0.0020 (6)	0.0008 (6)
C2	0.0197 (8)	0.0285 (9)	0.0145 (7)	−0.0054 (7)	0.0016 (6)	0.0048 (7)
C3	0.0211 (8)	0.0358 (11)	0.0159 (8)	−0.0058 (7)	0.0064 (6)	−0.0049 (7)
C4	0.0192 (8)	0.0261 (9)	0.0203 (8)	−0.0013 (6)	0.0048 (6)	−0.0092 (7)
C5	0.0170 (7)	0.0169 (8)	0.0180 (7)	0.0013 (6)	0.0022 (6)	−0.0013 (6)
C6	0.0129 (6)	0.0164 (7)	0.0126 (6)	−0.0008 (6)	0.0026 (5)	−0.0003 (6)
C7	0.0130 (6)	0.0126 (7)	0.0113 (6)	0.0003 (6)	0.0015 (5)	0.0006 (6)
C8	0.0192 (8)	0.0145 (7)	0.0135 (7)	0.0044 (6)	0.0053 (6)	0.0035 (6)
C9	0.0148 (7)	0.0197 (8)	0.0183 (8)	0.0046 (6)	0.0038 (6)	0.0024 (6)
C10	0.0159 (7)	0.0200 (8)	0.0171 (7)	−0.0001 (6)	0.0044 (6)	0.0002 (6)
C11	0.0171 (7)	0.0143 (7)	0.0186 (8)	−0.0001 (6)	0.0042 (6)	0.0012 (6)
C12	0.0153 (7)	0.0127 (7)	0.0146 (7)	0.0003 (5)	0.0028 (5)	0.0013 (5)
C13	0.0149 (7)	0.0163 (8)	0.0197 (7)	−0.0001 (6)	0.0033 (5)	−0.0022 (7)

Cl1—C1	1.7403 (16)	C7—C8	1.540 (2)
O1—C8	1.210 (2)	C7—C12	1.553 (2)
N1—C13	1.488 (2)	C8—C9	1.503 (2)
N1—C7	1.5108 (19)	C9—C10	1.539 (2)
N1—H1B	0.869 (18)	C9—H9A	1.01 (2)
N1—H1A	0.83 (3)	C9—H9B	0.97 (2)
C1—C2	1.386 (2)	C10—C11	1.527 (2)
C1—C6	1.397 (2)	C10—H10B	0.957 (18)
C2—C3	1.382 (3)	C10—H10A	0.96 (2)
C2—H2	0.91 (2)	C11—C12	1.528 (2)
C3—C4	1.378 (3)	C11—H11B	1.01 (2)
C3—H3	0.92 (2)	C11—H11A	0.96 (2)
C4—C5	1.388 (2)	C12—H12A	1.014 (17)
C4—H4	0.96 (2)	C12—H12B	0.96 (2)
C5—C6	1.401 (2)	C13—H13A	0.971 (19)
C5—H5	0.91 (2)	C13—H13B	0.93 (2)
C6—C7	1.5321 (19)	C13—H13C	0.96 (2)
C13—N1—C7	116.17 (12)	C9—C8—C7	114.74 (13)
C13—N1—H1B	107.8 (12)	C8—C9—C10	107.60 (13)
C7—N1—H1B	107.7 (12)	C8—C9—H9A	106.5 (12)
C13—N1—H1A	106.8 (15)	C10—C9—H9A	113.3 (12)
C7—N1—H1A	111.3 (15)	C8—C9—H9B	109.6 (12)
H1B—N1—H1A	106.7 (19)	C10—C9—H9B	109.0 (12)
C2—C1—C6	122.11 (15)	H9A—C9—H9B	110.8 (16)
C2—C1—Cl1	116.19 (13)	C11—C10—C9	110.66 (13)
C6—C1—Cl1	121.69 (12)	C11—C10—H10B	110.3 (11)
C3—C2—C1	120.18 (16)	C9—C10—H10B	108.8 (12)
C3—C2—H2	121.6 (12)	C11—C10—H10A	111.8 (13)
C1—C2—H2	118.2 (12)	C9—C10—H10A	110.1 (13)
C4—C3—C2	119.23 (15)	H10B—C10—H10A	105.0 (16)
C4—C3—H3	121.0 (14)	C10—C11—C12	110.94 (14)
C2—C3—H3	119.7 (14)	C10—C11—H11B	108.0 (12)
C3—C4—C5	120.40 (16)	C12—C11—H11B	111.3 (12)
C3—C4—H4	123.7 (13)	C10—C11—H11A	106.8 (14)
C5—C4—H4	115.9 (13)	C12—C11—H11A	110.4 (13)
C4—C5—C6	121.81 (16)	H11B—C11—H11A	109.3 (17)
C4—C5—H5	118.8 (13)	C11—C12—C7	111.90 (12)
C6—C5—H5	119.4 (13)	C11—C12—H12A	109.5 (10)
C1—C6—C5	116.27 (13)	C7—C12—H12A	106.2 (12)
C1—C6—C7	123.69 (15)	C11—C12—H12B	113.2 (13)
C5—C6—C7	119.89 (14)	C7—C12—H12B	108.5 (12)
N1—C7—C6	109.33 (11)	H12A—C12—H12B	107.2 (15)
N1—C7—C8	106.29 (12)	N1—C13—H13A	107.3 (11)
C6—C7—C8	115.60 (12)	N1—C13—H13B	107.4 (12)
N1—C7—C12	108.57 (11)	H13A—C13—H13B	111.0 (17)
C6—C7—C12	113.44 (13)	N1—C13—H13C	110.3 (11)
C8—C7—C12	103.13 (11)	H13A—C13—H13C	109.3 (16)
O1—C8—C9	124.09 (15)	H13B—C13—H13C	111.5 (17)
O1—C8—C7	120.38 (14)
C6—C1—C2—C3	−0.2 (2)	C5—C6—C7—C8	146.41 (14)
Cl1—C1—C2—C3	179.44 (13)	C1—C6—C7—C12	−157.03 (14)
C1—C2—C3—C4	−0.3 (3)	C5—C6—C7—C12	27.58 (18)
C2—C3—C4—C5	0.7 (3)	N1—C7—C8—O1	6.73 (18)
C3—C4—C5—C6	−0.7 (3)	C6—C7—C8—O1	128.23 (15)
C2—C1—C6—C5	0.2 (2)	C12—C7—C8—O1	−107.40 (16)
Cl1—C1—C6—C5	−179.37 (11)	N1—C7—C8—C9	177.01 (12)
C2—C1—C6—C7	−175.34 (14)	C6—C7—C8—C9	−61.50 (17)
Cl1—C1—C6—C7	5.1 (2)	C12—C7—C8—C9	62.88 (15)
C4—C5—C6—C1	0.2 (2)	O1—C8—C9—C10	107.30 (17)
C4—C5—C6—C7	175.93 (14)	C7—C8—C9—C10	−62.57 (16)
C13—N1—C7—C6	48.63 (18)	C8—C9—C10—C11	55.38 (17)
C13—N1—C7—C8	174.05 (13)	C9—C10—C11—C12	−55.57 (17)
C13—N1—C7—C12	−75.59 (16)	C10—C11—C12—C7	59.27 (17)
C1—C6—C7—N1	81.64 (16)	N1—C7—C12—C11	−171.44 (12)
C5—C6—C7—N1	−93.75 (17)	C6—C7—C12—C11	66.81 (16)
C1—C6—C7—C8	−38.2 (2)	C8—C7—C12—C11	−58.97 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2i	0.83 (3)	2.39 (3)	3.1359 (15)	151 (2)
N1—H1B···Cl2	0.869 (19)	2.278 (19)	3.1065 (13)	159.4 (17)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl2i	0.83 (3)	2.39 (3)	3.1359 (15)	151 (2)
N1—H1B⋯Cl2	0.869 (19)	2.278 (19)	3.1065 (13)	159.4 (17)

Symmetry code: (i) .