Chlordiazepoxide dichloro-methane monosolvate.

IN THE TITLE COMPOUND (SYSTEMATIC NAME: 7-chloro-2-methyl-amino-5-phenyl-3H-1,4-benzodiazepine 4-oxide dichloro-meth-ane monosolvate), C(16)H(14)ClN(3)O·CH(2)Cl(2), the seven-membered ring adopts a boat conformation with the CH(2) group as the prow and the two aromatic C atoms as the stern. The dihedral angle between the benzene rings is 75.25 (6)°. The crystal structure features centrosymmetric pairs of chlordiazepoxide mol-ecules linked by pairs of N-H⋯O hydrogen bonds, which generate R(2) (2)(12) loops.

Related literature

For the synthesis of chlordiazepoxide, see: Sternbach et al. (1961 ▶). For the structure of chlordiazepoxide, see: Bertolasi et al. (1982 ▶). For the structure of a second polymorph of chlordiazepoxide, see: Singh et al. (1998 ▶). For the structure of chlordiazepoxide hydro­chloride, see: Herrnstadt et al. (1979 ▶). For the early history of benzopdiazepines, see: Sternbach (1979 ▶).

Experimental

Crystal data

C16H14ClN3O·CH2Cl2

M = 384.69

Triclinic,

a = 7.8310 (12) Å

b = 9.461 (2) Å

c = 12.6947 (5) Å

α = 94.284 (11)°

β = 93.821 (9)°

γ = 108.499 (13)°

V = 885.4 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.53 mm−1

T = 173 K

0.60 × 0.33 × 0.04 mm

Data collection

Bruker–Nonius KappaCCD diffractometer

Absorption correction: multi-scan SADABS (Sheldrick, 2003 ▶) T min = 0.763, T max = 0.979

20348 measured reflections

4040 independent reflections

3124 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.104

S = 1.03

4040 reflections

221 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.76 e Å−3

Δρmin = −0.52 e Å−3

Data collection: COLLECT (Nonius, 1999 ▶); cell refinement: DIRAX (Duisenberg, 1992 ▶); data reduction: EVALCCD (Duisenberg et al., 2003 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2007 ▶).; software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812009695/hb6668sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812009695/hb6668Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812009695/hb6668Isup3.cml

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

C16H14ClN3O·CH2Cl2	Z = 2
Mr = 384.69	F(000) = 396
Triclinic, P1	Dx = 1.443 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8310 (12) Å	Cell parameters from 38 reflections
b = 9.461 (2) Å	θ = 8.7–19.5°
c = 12.6947 (5) Å	µ = 0.53 mm−1
α = 94.284 (11)°	T = 173 K
β = 93.821 (9)°	Plate, colourless
γ = 108.499 (13)°	0.60 × 0.33 × 0.04 mm
V = 885.4 (2) Å3

Bruker–Nonius KappaCCD diffractometer	4040 independent reflections
Radiation source: fine-focus sealed tube	3124 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
φ&ω scans	θmax = 27.5°, θmin = 4.5°
Absorption correction: multi-scan SADABS (Sheldrick, 2003)	h = −10→10
Tmin = 0.763, Tmax = 0.979	k = −12→12
20348 measured reflections	l = −15→16

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.104	w = 1/[σ2(Fo2) + (0.0409P)2 + 0.7625P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
4040 reflections	Δρmax = 0.76 e Å−3
221 parameters	Δρmin = −0.52 e Å−3
1 restraint

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
C1	0.4054 (3)	0.0142 (2)	0.68015 (14)	0.0228 (4)
C2	0.4147 (3)	−0.1283 (2)	0.67919 (15)	0.0233 (4)
C3	0.3620 (3)	−0.2137 (2)	0.76314 (15)	0.0229 (4)
C4	0.3110 (2)	−0.1489 (2)	0.85106 (14)	0.0219 (4)
C5	0.3146 (2)	0.00119 (19)	0.85985 (14)	0.0183 (3)
C6	0.3543 (2)	0.08072 (19)	0.76981 (14)	0.0188 (4)
C7	0.3392 (2)	0.23116 (19)	0.76213 (14)	0.0193 (4)
C8	0.2418 (3)	0.2605 (2)	0.66676 (14)	0.0213 (4)
C9	0.3090 (3)	0.3890 (2)	0.61483 (15)	0.0251 (4)
C10	0.2113 (3)	0.4097 (2)	0.52552 (16)	0.0335 (5)
C11	0.0461 (3)	0.3048 (3)	0.48835 (17)	0.0375 (5)
C12	−0.0217 (3)	0.1780 (3)	0.53961 (18)	0.0374 (5)
C13	0.0762 (3)	0.1547 (2)	0.62793 (16)	0.0300 (4)
C14	0.4974 (2)	0.2983 (2)	0.93612 (13)	0.0189 (4)
C15	0.3509 (2)	0.1940 (2)	0.99178 (13)	0.0186 (4)
C16	0.1763 (3)	0.1635 (2)	1.14472 (17)	0.0334 (5)
C17	0.0152 (4)	0.5580 (3)	0.1687 (3)	0.0561 (7)
Cl1	0.50033 (8)	−0.20239 (6)	0.57295 (4)	0.03756 (16)
Cl2	0.04988 (9)	0.72192 (8)	0.10404 (6)	0.0542 (2)
Cl3	0.19167 (10)	0.57040 (9)	0.26233 (6)	0.0620 (2)
O1	0.39853 (18)	0.47104 (13)	0.84472 (10)	0.0218 (3)
N1	0.4092 (2)	0.33547 (16)	0.84073 (11)	0.0176 (3)
N2	0.2700 (2)	0.05504 (17)	0.95575 (12)	0.0203 (3)
N3	0.3075 (2)	0.25397 (18)	1.08078 (12)	0.0227 (3)
H1	0.4336	0.0679	0.6199	0.027*
H3	0.3613	−0.3145	0.7599	0.027*
H4	0.2720	−0.2076	0.9078	0.026*
H9	0.4214	0.4621	0.6407	0.030*
H10	0.2581	0.4963	0.4896	0.040*
H11	−0.0206	0.3202	0.4275	0.045*
H12	−0.1357	0.1066	0.5144	0.045*
H13	0.0303	0.0662	0.6621	0.036*
H14A	0.5617	0.3906	0.9836	0.023*
H14B	0.5862	0.2490	0.9159	0.023*
H16A	0.0613	0.1156	1.1011	0.050*
H16B	0.1578	0.2274	1.2043	0.050*
H16C	0.2211	0.0863	1.1720	0.050*
H17A	−0.0980	0.5380	0.2038	0.067*
H17B	0.0001	0.4723	0.1151	0.067*
H3A	0.379 (3)	0.3395 (19)	1.1074 (17)	0.027*

	U11	U22	U33	U12	U13	U23
C1	0.0312 (10)	0.0182 (9)	0.0194 (9)	0.0079 (8)	0.0027 (7)	0.0051 (7)
C2	0.0296 (10)	0.0209 (9)	0.0205 (9)	0.0104 (8)	0.0026 (7)	0.0002 (7)
C3	0.0275 (10)	0.0175 (9)	0.0247 (9)	0.0094 (8)	−0.0012 (8)	0.0030 (7)
C4	0.0233 (9)	0.0206 (9)	0.0214 (9)	0.0059 (7)	0.0006 (7)	0.0067 (7)
C5	0.0156 (8)	0.0184 (8)	0.0192 (8)	0.0037 (7)	−0.0011 (7)	0.0015 (6)
C6	0.0206 (9)	0.0148 (8)	0.0200 (9)	0.0049 (7)	−0.0020 (7)	0.0013 (6)
C7	0.0209 (9)	0.0169 (8)	0.0197 (9)	0.0055 (7)	0.0009 (7)	0.0028 (6)
C8	0.0288 (10)	0.0192 (9)	0.0178 (9)	0.0117 (8)	−0.0014 (7)	−0.0008 (7)
C9	0.0343 (11)	0.0206 (9)	0.0209 (9)	0.0100 (8)	0.0001 (8)	0.0017 (7)
C10	0.0522 (14)	0.0285 (10)	0.0247 (10)	0.0199 (10)	−0.0009 (9)	0.0070 (8)
C11	0.0535 (15)	0.0380 (12)	0.0262 (11)	0.0260 (11)	−0.0128 (10)	0.0004 (9)
C12	0.0385 (13)	0.0344 (12)	0.0349 (12)	0.0114 (10)	−0.0164 (10)	−0.0044 (9)
C13	0.0361 (12)	0.0227 (10)	0.0292 (10)	0.0087 (9)	−0.0062 (9)	0.0024 (8)
C14	0.0175 (9)	0.0201 (9)	0.0175 (8)	0.0044 (7)	−0.0028 (7)	0.0023 (7)
C15	0.0166 (8)	0.0221 (9)	0.0165 (8)	0.0058 (7)	−0.0015 (7)	0.0038 (7)
C16	0.0309 (11)	0.0362 (11)	0.0273 (11)	0.0018 (9)	0.0105 (9)	−0.0007 (8)
C17	0.0338 (14)	0.0492 (15)	0.085 (2)	0.0101 (12)	0.0003 (13)	0.0207 (14)
Cl1	0.0618 (4)	0.0276 (3)	0.0305 (3)	0.0216 (2)	0.0185 (2)	0.00376 (19)
Cl2	0.0412 (3)	0.0717 (5)	0.0646 (4)	0.0315 (3)	0.0154 (3)	0.0322 (3)
Cl3	0.0553 (4)	0.0777 (5)	0.0559 (4)	0.0205 (4)	0.0033 (3)	0.0317 (4)
O1	0.0268 (7)	0.0131 (6)	0.0243 (7)	0.0060 (5)	−0.0019 (5)	−0.0003 (5)
N1	0.0189 (7)	0.0153 (7)	0.0183 (7)	0.0051 (6)	0.0001 (6)	0.0026 (5)
N2	0.0203 (8)	0.0206 (8)	0.0185 (7)	0.0048 (6)	0.0013 (6)	0.0018 (6)
N3	0.0214 (8)	0.0231 (8)	0.0203 (8)	0.0036 (7)	0.0013 (6)	−0.0015 (6)

C1—C2	1.372 (3)	C16—N3	1.451 (3)
C1—C6	1.402 (2)	C17—Cl3	1.730 (3)
C2—C3	1.391 (3)	C17—Cl2	1.762 (3)
C2—Cl1	1.7428 (19)	O1—N1	1.3090 (18)
C3—C4	1.376 (3)	C1—H1	0.9500
C4—C5	1.407 (2)	C3—H3	0.9500
C5—N2	1.393 (2)	C4—H4	0.9500
C5—C6	1.413 (2)	C9—H9	0.9500
C6—C7	1.475 (2)	C10—H10	0.9500
C7—N1	1.306 (2)	C11—H11	0.9500
C7—C8	1.478 (2)	C12—H12	0.9500
C8—C13	1.394 (3)	C13—H13	0.9500
C8—C9	1.396 (3)	C14—H14A	0.9900
C9—C10	1.386 (3)	C14—H14B	0.9900
C10—C11	1.384 (3)	C16—H16A	0.9800
C11—C12	1.380 (3)	C16—H16B	0.9800
C12—C13	1.387 (3)	C16—H16C	0.9800
C14—N1	1.474 (2)	C17—H17A	0.9900
C14—C15	1.511 (2)	C17—H17B	0.9900
C15—N2	1.297 (2)	N3—H3A	0.854 (16)
C15—N3	1.338 (2)
C2—C1—C6	120.20 (16)	C6—C1—H1	119.9
C1—C2—C3	121.22 (17)	C4—C3—H3	120.7
C1—C2—Cl1	119.68 (14)	C2—C3—H3	120.7
C3—C2—Cl1	119.07 (14)	C3—C4—H4	118.8
C4—C3—C2	118.55 (16)	C5—C4—H4	118.8
C3—C4—C5	122.33 (16)	C10—C9—H9	120.1
N2—C5—C4	116.32 (15)	C8—C9—H9	120.1
N2—C5—C6	126.13 (16)	C11—C10—H10	119.8
C4—C5—C6	117.48 (16)	C9—C10—H10	119.8
C1—C6—C5	119.75 (16)	C12—C11—H11	120.0
C1—C6—C7	116.61 (15)	C10—C11—H11	120.0
C5—C6—C7	123.60 (16)	C11—C12—H12	120.0
N1—C7—C6	119.34 (16)	C13—C12—H12	120.0
N1—C7—C8	121.14 (15)	C12—C13—H13	119.8
C6—C7—C8	119.51 (15)	C8—C13—H13	119.8
C13—C8—C9	119.24 (17)	N1—C14—H14A	110.2
C13—C8—C7	118.08 (16)	C15—C14—H14A	110.2
C9—C8—C7	122.68 (17)	N1—C14—H14B	110.2
C10—C9—C8	119.88 (19)	C15—C14—H14B	110.2
C11—C10—C9	120.4 (2)	H14A—C14—H14B	108.5
C12—C11—C10	120.04 (19)	N3—C16—H16A	109.5
C11—C12—C13	120.1 (2)	N3—C16—H16B	109.5
C12—C13—C8	120.31 (19)	H16A—C16—H16B	109.5
N1—C14—C15	107.42 (14)	N3—C16—H16C	109.5
N2—C15—N3	121.51 (16)	H16A—C16—H16C	109.5
N2—C15—C14	122.57 (16)	H16B—C16—H16C	109.5
N3—C15—C14	115.91 (16)	Cl3—C17—H17A	109.0
Cl3—C17—Cl2	112.88 (15)	Cl2—C17—H17A	109.0
C7—N1—O1	124.88 (15)	Cl3—C17—H17B	109.0
C7—N1—C14	118.94 (14)	Cl2—C17—H17B	109.0
O1—N1—C14	116.05 (13)	H17A—C17—H17B	107.8
C15—N2—C5	118.83 (15)	C15—N3—H3A	117.0 (15)
C15—N3—C16	121.24 (16)	C16—N3—H3A	119.7 (15)
C2—C1—H1	119.9

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1i	0.85 (2)	2.08 (2)	2.916 (2)	166 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1i	0.85 (2)	2.08 (2)	2.916 (2)	166 (2)

Symmetry code: (i) .