A hydrogen sulfate salt of chlordiazepoxide.

CRYSTALS OF THE HYDROGEN SULFATE SALT OF CHLORDIAZEPOXIDE (SYSTEMATIC NAME: 7-chloro-N-methyl-5-phenyl-2,3-dihydro-1H-1,4-benzodiazepin-2-iminium 4-oxide hydrogen sulfate), C(16)H(15)ClN(3)O(+)·HSO(4) (-), were obtained from a solution of chlordiazepoxide and sulfuric acid in methanol. The structure features chlordiazepoxide mol-ecules that are protonated at the imine N atom. The seven-membered ring adopts a boat conformation with the CH(2) group as the prow and the two aryl C atoms as the stern. The dihedral angle between the benzene rings is 72.41 (6)°. In the crystal, the HSO(4) (-) anion acts as a bridging group between two chlordiazepoxide cations. The H atom of the protonated imino N forms an N-H⋯O hydrogen bond with a hydrogen sulfate ion. The anion in turn forms two hydrogen bonds, O-H⋯O with the anion as donor and N-H⋯O with the anion as acceptor, to generate an R(2) (2)(10) loop. Each HSO(4) (-) anion connects two chlordiazepoxide moieties of the same chirality.

Related literature

For general background to benzodiazepines, the structures of two polymorphs of chlordiazepoxide and a chlordiazepoxide dichloro­methane solvate, see: Fischer (2012 ▶) and references therein. For the structure of chlordiazepoxide hydro­chloride, see: Herrnstadt et al. (1979 ▶). For the synthesis of chlordiazepoxide, see: Sternbach et al. (1961 ▶). For acid–base equlibria of chlordiazepoxide and related compounds, see: Yang (1995 ▶). For the graph-set motifs, see: Etter et al. (1990 ▶).

Experimental

Crystal data

C16H15ClN3O+·HSO4 −

M = 397.84

Monoclinic,

a = 13.9899 (6) Å

b = 8.7579 (10) Å

c = 13.9084 (6) Å

β = 99.657 (9)°

V = 1679.9 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.39 mm−1

T = 173 K

0.58 × 0.54 × 0.14 mm

Data collection

Bruker–Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.806, T max = 0.947

23827 measured reflections

3835 independent reflections

2802 reflections with I > 2σ(I)

R int = 0.052

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.088

S = 1.03

3835 reflections

245 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.39 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/S1600536812024920/hb6784sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024920/hb6784Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812024920/hb6784Isup3.cml

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

C16H15ClN3O+·HSO4−	F(000) = 824
Mr = 397.84	Dx = 1.573 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 84 reflections
a = 13.9899 (6) Å	θ = 4.2–20.7°
b = 8.7579 (10) Å	µ = 0.39 mm−1
c = 13.9084 (6) Å	T = 173 K
β = 99.657 (9)°	Plate, yellow
V = 1679.9 (2) Å3	0.58 × 0.54 × 0.14 mm
Z = 4

Bruker–Nonius KappaCCD diffractometer	2802 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.052
φ and ω scans	θmax = 27.5°, θmin = 4.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −18→17
Tmin = 0.806, Tmax = 0.947	k = −11→11
23827 measured reflections	l = −18→18
3835 independent reflections

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0365P)2 + 1.1198P] where P = (Fo2 + 2Fc2)/3
3835 reflections	(Δ/σ)max < 0.001
245 parameters	Δρmax = 0.33 e Å−3
1 restraint	Δρmin = −0.39 e Å−3
13 constraints

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	0.29397 (13)	0.9226 (2)	0.03883 (14)	0.0192 (4)
C2	0.23368 (14)	1.0175 (2)	0.08120 (14)	0.0196 (4)
C3	0.18881 (14)	0.9588 (2)	0.15418 (14)	0.0189 (4)
C4	0.20316 (13)	0.8080 (2)	0.18584 (13)	0.0154 (4)
C5	0.26573 (13)	0.7120 (2)	0.14382 (13)	0.0157 (4)
C6	0.31045 (13)	0.7742 (2)	0.06926 (14)	0.0185 (4)
C7	0.29408 (13)	0.5551 (2)	0.17423 (13)	0.0147 (4)
C8	0.39263 (13)	0.5004 (2)	0.16413 (13)	0.0163 (4)
C9	0.40329 (14)	0.3805 (2)	0.10173 (14)	0.0192 (4)
C10	0.49545 (14)	0.3410 (2)	0.08574 (15)	0.0233 (4)
C11	0.57571 (14)	0.4185 (3)	0.13293 (15)	0.0253 (5)
C12	0.56519 (15)	0.5383 (3)	0.19530 (16)	0.0288 (5)
C13	0.47339 (14)	0.5800 (3)	0.21034 (15)	0.0251 (5)
C14	0.13111 (13)	0.5056 (2)	0.20202 (13)	0.0161 (4)
C15	0.12400 (12)	0.6247 (2)	0.27772 (13)	0.0144 (4)
C16	0.06161 (16)	0.6949 (3)	0.42636 (15)	0.0252 (5)
Cl1	0.35131 (4)	0.99179 (6)	−0.05429 (4)	0.02899 (14)
N1	0.15794 (11)	0.76324 (19)	0.26510 (11)	0.0159 (3)
N2	0.23277 (11)	0.46083 (18)	0.20355 (11)	0.0149 (3)
N3	0.08275 (12)	0.5887 (2)	0.35181 (12)	0.0173 (3)
O1	0.25496 (9)	0.32031 (15)	0.23206 (10)	0.0211 (3)
O2	0.21788 (10)	0.2042 (2)	0.39254 (12)	0.0328 (4)
O3	0.08836 (10)	0.02501 (17)	0.33641 (11)	0.0304 (4)
O4	0.12080 (11)	0.1162 (2)	0.50292 (11)	0.0361 (4)
O5	0.04859 (11)	0.28024 (17)	0.37061 (12)	0.0309 (4)
S1	0.11383 (3)	0.15276 (5)	0.40179 (3)	0.01669 (12)
H2	0.2234	1.1204	0.0605	0.024*
H3	0.1471	1.0227	0.1837	0.023*
H6	0.3529	0.7123	0.0393	0.022*
H9	0.3481	0.3259	0.0702	0.023*
H10	0.5033	0.2602	0.0421	0.028*
H11	0.6386	0.3895	0.1225	0.030*
H12	0.6206	0.5915	0.2275	0.035*
H13	0.4656	0.6631	0.2523	0.030*
H14A	0.0928	0.4149	0.2145	0.019*
H14B	0.1037	0.5461	0.1368	0.019*
H16A	0.1194	0.7562	0.4500	0.038*
H16B	0.0429	0.6375	0.4808	0.038*
H16C	0.0083	0.7625	0.3983	0.038*
H1	0.1412 (14)	0.834 (2)	0.2988 (14)	0.019*
H3A	0.0662 (16)	0.499 (3)	0.3548 (16)	0.021*
H2A	0.2223 (18)	0.242 (3)	0.340 (2)	0.039*

	U11	U22	U33	U12	U13	U23
C1	0.0178 (9)	0.0210 (11)	0.0193 (10)	−0.0002 (8)	0.0049 (7)	0.0032 (8)
C2	0.0213 (10)	0.0141 (10)	0.0233 (10)	0.0017 (8)	0.0030 (8)	0.0017 (8)
C3	0.0186 (10)	0.0169 (10)	0.0212 (10)	0.0034 (8)	0.0035 (7)	−0.0027 (8)
C4	0.0146 (9)	0.0157 (10)	0.0157 (9)	0.0002 (7)	0.0023 (7)	−0.0015 (8)
C5	0.0159 (9)	0.0139 (10)	0.0171 (9)	0.0013 (7)	0.0025 (7)	−0.0013 (8)
C6	0.0181 (9)	0.0186 (11)	0.0197 (10)	0.0026 (8)	0.0061 (7)	0.0007 (8)
C7	0.0167 (9)	0.0152 (10)	0.0124 (9)	0.0013 (7)	0.0029 (7)	−0.0020 (7)
C8	0.0157 (9)	0.0164 (10)	0.0178 (9)	0.0042 (8)	0.0056 (7)	0.0035 (8)
C9	0.0192 (10)	0.0170 (11)	0.0223 (10)	0.0011 (8)	0.0065 (8)	0.0017 (8)
C10	0.0261 (11)	0.0204 (11)	0.0258 (11)	0.0076 (9)	0.0109 (8)	0.0006 (9)
C11	0.0168 (10)	0.0330 (13)	0.0273 (11)	0.0091 (9)	0.0076 (8)	0.0065 (10)
C12	0.0162 (10)	0.0372 (14)	0.0318 (12)	−0.0031 (9)	0.0001 (8)	−0.0023 (10)
C13	0.0224 (11)	0.0259 (12)	0.0270 (11)	−0.0004 (9)	0.0044 (8)	−0.0089 (9)
C14	0.0136 (9)	0.0176 (10)	0.0178 (9)	0.0003 (7)	0.0052 (7)	−0.0031 (8)
C15	0.0110 (8)	0.0165 (10)	0.0159 (9)	0.0035 (7)	0.0023 (7)	−0.0004 (8)
C16	0.0315 (11)	0.0263 (12)	0.0201 (10)	0.0063 (9)	0.0113 (8)	0.0000 (9)
Cl1	0.0333 (3)	0.0255 (3)	0.0325 (3)	0.0051 (2)	0.0179 (2)	0.0108 (2)
N1	0.0191 (8)	0.0146 (9)	0.0156 (8)	0.0026 (7)	0.0073 (6)	−0.0036 (7)
N2	0.0178 (8)	0.0125 (8)	0.0151 (8)	0.0032 (6)	0.0048 (6)	−0.0009 (6)
N3	0.0202 (8)	0.0142 (9)	0.0191 (8)	0.0019 (7)	0.0082 (6)	−0.0007 (7)
O1	0.0272 (7)	0.0124 (7)	0.0265 (8)	0.0044 (6)	0.0123 (6)	0.0029 (6)
O2	0.0210 (8)	0.0484 (11)	0.0283 (8)	−0.0117 (7)	0.0018 (6)	0.0130 (8)
O3	0.0296 (8)	0.0227 (8)	0.0402 (9)	−0.0017 (6)	0.0100 (7)	−0.0145 (7)
O4	0.0409 (9)	0.0502 (11)	0.0195 (8)	0.0005 (8)	0.0113 (6)	0.0093 (7)
O5	0.0319 (8)	0.0177 (8)	0.0434 (9)	0.0045 (6)	0.0071 (7)	0.0043 (7)
S1	0.0206 (2)	0.0146 (2)	0.0162 (2)	−0.00200 (19)	0.00691 (17)	−0.00031 (19)

C1—C6	1.375 (3)	N2—O1	1.314 (2)
C1—C2	1.384 (3)	O2—S1	1.5495 (15)
C1—Cl1	1.7426 (19)	O3—S1	1.4481 (15)
C2—C3	1.379 (3)	O4—S1	1.4299 (15)
C3—C4	1.396 (3)	O5—S1	1.4611 (15)
C4—C5	1.409 (3)	C2—H2	0.9500
C4—N1	1.415 (2)	C3—H3	0.9500
C5—C6	1.407 (3)	C6—H6	0.9500
C5—C7	1.473 (3)	C9—H9	0.9500
C7—N2	1.304 (2)	C10—H10	0.9500
C7—C8	1.488 (2)	C11—H11	0.9500
C8—C9	1.386 (3)	C12—H12	0.9500
C8—C13	1.390 (3)	C13—H13	0.9500
C9—C10	1.388 (3)	C14—H14A	0.9900
C10—C11	1.381 (3)	C14—H14B	0.9900
C11—C12	1.385 (3)	C16—H16A	0.9800
C12—C13	1.384 (3)	C16—H16B	0.9800
C14—N2	1.472 (2)	C16—H16C	0.9800
C14—C15	1.497 (3)	N1—H1	0.837 (15)
C15—N3	1.301 (2)	N3—H3A	0.82 (2)
C15—N1	1.325 (2)	O2—H2A	0.81 (3)
C16—N3	1.460 (3)
C6—C1—C2	121.28 (18)	O4—S1—O2	103.70 (9)
C6—C1—Cl1	118.89 (15)	O3—S1—O2	107.94 (9)
C2—C1—Cl1	119.83 (16)	O5—S1—O2	107.58 (9)
C3—C2—C1	118.37 (18)	C3—C2—H2	120.8
C2—C3—C4	121.68 (18)	C1—C2—H2	120.8
C3—C4—C5	120.00 (17)	C2—C3—H3	119.2
C3—C4—N1	116.63 (16)	C4—C3—H3	119.2
C5—C4—N1	123.22 (17)	C1—C6—H6	119.3
C6—C5—C4	117.30 (17)	C5—C6—H6	119.3
C6—C5—C7	116.17 (16)	C8—C9—H9	120.4
C4—C5—C7	126.42 (17)	C10—C9—H9	120.4
C1—C6—C5	121.36 (18)	C11—C10—H10	119.9
N2—C7—C5	121.40 (16)	C9—C10—H10	119.9
N2—C7—C8	119.59 (17)	C10—C11—H11	119.8
C5—C7—C8	118.85 (16)	C12—C11—H11	119.8
C9—C8—C13	120.34 (17)	C13—C12—H12	120.2
C9—C8—C7	120.11 (17)	C11—C12—H12	120.2
C13—C8—C7	119.25 (17)	C12—C13—H13	120.0
C8—C9—C10	119.30 (18)	C8—C13—H13	120.0
C11—C10—C9	120.29 (19)	N2—C14—H14A	109.5
C10—C11—C12	120.47 (18)	C15—C14—H14A	109.5
C13—C12—C11	119.6 (2)	N2—C14—H14B	109.5
C12—C13—C8	120.01 (19)	C15—C14—H14B	109.5
N2—C14—C15	110.70 (15)	H14A—C14—H14B	108.1
N3—C15—N1	122.88 (17)	N3—C16—H16A	109.5
N3—C15—C14	118.61 (17)	N3—C16—H16B	109.5
N1—C15—C14	118.50 (16)	H16A—C16—H16B	109.5
C15—N1—C4	125.00 (16)	N3—C16—H16C	109.5
C7—N2—O1	123.56 (15)	H16A—C16—H16C	109.5
C7—N2—C14	120.75 (16)	H16B—C16—H16C	109.5
O1—N2—C14	115.63 (14)	C15—N1—H1	117.9 (15)
C15—N3—C16	125.30 (18)	C4—N1—H1	115.7 (15)
O4—S1—O3	114.42 (10)	C15—N3—H3A	116.0 (16)
O4—S1—O5	113.54 (10)	C16—N3—H3A	118.7 (16)
O3—S1—O5	109.17 (9)	S1—O2—H2A	114.0 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O5	0.82 (2)	1.95 (2)	2.764 (2)	171 (2)
N1—H1···O3i	0.84 (2)	1.93 (2)	2.741 (2)	162 (2)
O2—H2A···O1	0.81 (3)	1.78 (3)	2.583 (2)	170 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O5	0.82 (2)	1.95 (2)	2.764 (2)	171 (2)
N1—H1⋯O3i	0.84 (2)	1.93 (2)	2.741 (2)	162 (2)
O2—H2A⋯O1	0.81 (3)	1.78 (3)	2.583 (2)	170 (3)

Symmetry code: (i) .