2,2,4-Trimethyl-5-(4-tolyl-sulfon-yl)-2,3,4,5-tetra-hydro-1H-1,5-benzo-diazepine.

In the title compound, C(19)H(24)N(2)O(2)S, the benzodiazepine ring adopts a distorted boat conformation. The S atom shows a distorted tetra-hedral geometry, with the O-S-O [119.16 (14)°] and N-S-C [107.48 (10)°] angles deviating significantly from ideal values. The crystal packing is controlled by C-H⋯O, N-H⋯O and C-H⋯π inter-actions.

Related literature

For the use of benzodiazepines in the treatment of gastrointestinal and central nervous system disorders, see: Rahbaek et al. (1999 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For puckering and asymmetry parameters, see: Cremer & Pople (1975 ▶);) ; Nardelli (1983 ▶). For the Thorpe-Ingold effect, see: Bassindale (1984 ▶). For details of the preparation, see: Ponnuswamy et al. (2006 ▶).

Experimental

Crystal data

C19H24N2O2S

M = 344.46

Orthorhombic,

a = 7.3658 (3) Å

b = 14.8013 (8) Å

c = 17.4556 (10) Å

V = 1903.07 (17) Å3

Z = 4

Mo Kα radiation

μ = 0.18 mm−1

T = 293 K

0.25 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T min = 0.957, T max = 0.964

13544 measured reflections

5154 independent reflections

3278 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.145

S = 1.04

5154 reflections

224 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.18 e Å−3

Δρmin = −0.19 e Å−3

Absolute structure: Flack (1983 ▶), 2171 Friedel pairs

Flack parameter: −0.12 (9)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034837/bt5042sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034837/bt5042Isup2.hkl

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

C19H24N2O2S	F(000) = 736
Mr = 344.46	Dx = 1.202 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2546 reflections
a = 7.3658 (3) Å	θ = 1.8–29.4°
b = 14.8013 (8) Å	µ = 0.18 mm−1
c = 17.4556 (10) Å	T = 293 K
V = 1903.07 (17) Å3	Block, colourless
Z = 4	0.25 × 0.20 × 0.20 mm

Bruker Kappa APEXII area-detector diffractometer	5154 independent reflections
Radiation source: fine-focus sealed tube	3278 reflections with I > 2σ(I)
graphite	Rint = 0.034
ω and φ scans	θmax = 29.4°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −5→10
Tmin = 0.957, Tmax = 0.964	k = −20→18
13544 measured reflections	l = −23→23

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)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.145	w = 1/[σ2(Fo2) + (0.0742P)2] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.009
5154 reflections	Δρmax = 0.18 e Å−3
224 parameters	Δρmin = −0.19 e Å−3
0 restraints	Absolute structure: Flack (1983), 2171 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.12 (9)

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
S1	0.08799 (9)	0.63541 (4)	0.80960 (4)	0.0620 (2)
O1	0.2717 (3)	0.63113 (17)	0.78264 (12)	0.0849 (6)
O2	0.0096 (3)	0.55749 (13)	0.84498 (12)	0.0870 (7)
N1	−0.0887 (3)	0.84795 (14)	0.70370 (13)	0.0566 (5)
H1	−0.072 (4)	0.897 (2)	0.6945 (18)	0.073 (9)*
C2	−0.2833 (3)	0.83013 (16)	0.71790 (15)	0.0520 (6)
C3	−0.3323 (3)	0.73221 (16)	0.70025 (16)	0.0577 (6)
H3A	−0.4623	0.7257	0.7074	0.069*
H3B	−0.3078	0.7218	0.6464	0.069*
C4	−0.2402 (3)	0.65759 (15)	0.74511 (17)	0.0589 (7)
H4	−0.2719	0.6642	0.7993	0.071*
N5	−0.0387 (3)	0.66325 (13)	0.73728 (11)	0.0524 (5)
C6	0.0396 (3)	0.70241 (16)	0.66986 (13)	0.0497 (6)
C7	0.1455 (3)	0.6493 (2)	0.62250 (16)	0.0659 (7)
H7	0.1565	0.5877	0.6320	0.079*
C8	0.2354 (4)	0.6879 (3)	0.56082 (18)	0.0855 (10)
H8	0.3070	0.6524	0.5289	0.103*
C9	0.2182 (4)	0.7779 (3)	0.54737 (17)	0.0862 (11)
H9	0.2819	0.8041	0.5071	0.103*
C10	0.1077 (4)	0.8310 (2)	0.59246 (15)	0.0676 (7)
H10	0.0954	0.8922	0.5814	0.081*
C11	0.0141 (3)	0.79417 (17)	0.65442 (13)	0.0501 (6)
C12	−0.3967 (5)	0.8894 (2)	0.6654 (2)	0.0813 (9)
H12A	−0.3735	0.9518	0.6767	0.122*
H12B	−0.5231	0.8766	0.6732	0.122*
H12C	−0.3652	0.8773	0.6130	0.122*
C13	−0.3238 (4)	0.8554 (2)	0.80092 (17)	0.0704 (7)
H13A	−0.2526	0.8182	0.8345	0.106*
H13B	−0.4504	0.8460	0.8113	0.106*
H13C	−0.2939	0.9177	0.8092	0.106*
C14	−0.3082 (5)	0.5663 (2)	0.7171 (3)	0.0999 (13)
H14A	−0.2821	0.5600	0.6635	0.150*
H14B	−0.4369	0.5623	0.7251	0.150*
H14C	−0.2485	0.5190	0.7451	0.150*
C15	0.0750 (3)	0.72366 (16)	0.87704 (14)	0.0516 (5)
C16	0.1482 (4)	0.80712 (19)	0.85876 (15)	0.0640 (7)
H16	0.2035	0.8165	0.8115	0.077*
C17	0.1378 (4)	0.8753 (2)	0.91126 (17)	0.0759 (8)
H17	0.1873	0.9313	0.8988	0.091*
C18	0.0569 (4)	0.8647 (2)	0.98198 (17)	0.0722 (7)
C19	−0.0125 (4)	0.7808 (2)	0.99895 (18)	0.0796 (9)
H19	−0.0666	0.7712	1.0464	0.095*
C20	−0.0035 (4)	0.7106 (2)	0.94719 (17)	0.0700 (8)
H20	−0.0508	0.6543	0.9600	0.084*
C21	0.0455 (7)	0.9425 (3)	1.0377 (2)	0.1170 (14)
H21A	−0.0147	0.9229	1.0836	0.176*
H21B	−0.0217	0.9911	1.0150	0.176*
H21C	0.1657	0.9628	1.0501	0.176*

	U11	U22	U33	U12	U13	U23
S1	0.0663 (4)	0.0509 (3)	0.0687 (4)	0.0183 (3)	0.0157 (3)	0.0095 (3)
O1	0.0646 (11)	0.1087 (16)	0.0812 (13)	0.0422 (12)	0.0166 (10)	0.0088 (13)
O2	0.1298 (19)	0.0453 (10)	0.0858 (13)	0.0116 (11)	0.0213 (13)	0.0147 (10)
N1	0.0579 (12)	0.0403 (11)	0.0715 (13)	−0.0081 (9)	0.0017 (11)	−0.0036 (10)
C2	0.0474 (12)	0.0439 (12)	0.0648 (15)	0.0013 (9)	−0.0032 (11)	−0.0035 (11)
C3	0.0432 (11)	0.0530 (13)	0.0770 (17)	−0.0057 (10)	0.0066 (12)	−0.0146 (13)
C4	0.0530 (13)	0.0434 (13)	0.0803 (17)	−0.0027 (11)	0.0239 (13)	−0.0049 (12)
N5	0.0497 (11)	0.0486 (11)	0.0591 (11)	0.0025 (8)	0.0130 (9)	−0.0015 (9)
C6	0.0443 (12)	0.0558 (13)	0.0491 (12)	−0.0020 (10)	0.0070 (10)	−0.0089 (10)
C7	0.0542 (14)	0.0773 (19)	0.0663 (15)	0.0042 (13)	0.0106 (12)	−0.0189 (15)
C8	0.0705 (19)	0.128 (3)	0.0583 (18)	−0.001 (2)	0.0171 (16)	−0.0234 (19)
C9	0.0677 (19)	0.140 (4)	0.0504 (16)	−0.031 (2)	0.0072 (14)	0.005 (2)
C10	0.0623 (16)	0.087 (2)	0.0541 (14)	−0.0195 (15)	−0.0074 (13)	0.0098 (14)
C11	0.0442 (11)	0.0583 (14)	0.0478 (12)	−0.0100 (10)	−0.0031 (10)	−0.0029 (11)
C12	0.081 (2)	0.0666 (17)	0.097 (2)	0.0052 (16)	−0.0252 (18)	0.0046 (16)
C13	0.0620 (15)	0.0673 (17)	0.0819 (18)	0.0051 (13)	0.0077 (14)	−0.0183 (16)
C14	0.077 (2)	0.0482 (15)	0.174 (4)	−0.0146 (14)	0.024 (2)	−0.018 (2)
C15	0.0412 (11)	0.0547 (13)	0.0590 (13)	0.0080 (10)	0.0036 (11)	0.0126 (11)
C16	0.0731 (17)	0.0651 (17)	0.0538 (14)	−0.0065 (14)	−0.0021 (13)	0.0170 (13)
C17	0.091 (2)	0.0607 (17)	0.0764 (19)	−0.0149 (15)	−0.0173 (16)	0.0148 (15)
C18	0.0755 (18)	0.0681 (18)	0.0730 (17)	0.0079 (16)	−0.0034 (15)	−0.0024 (16)
C19	0.079 (2)	0.092 (2)	0.0674 (17)	0.0025 (17)	0.0194 (16)	−0.0025 (17)
C20	0.0712 (17)	0.0671 (18)	0.0717 (17)	−0.0057 (14)	0.0213 (15)	0.0072 (14)
C21	0.144 (4)	0.103 (3)	0.104 (3)	0.019 (3)	−0.017 (3)	−0.032 (2)

S1—O2	1.430 (2)	C10—C11	1.394 (3)
S1—O1	1.434 (2)	C10—H10	0.9300
S1—N5	1.623 (2)	C12—H12A	0.9600
S1—C15	1.761 (3)	C12—H12B	0.9600
N1—C11	1.395 (3)	C12—H12C	0.9600
N1—C2	1.478 (3)	C13—H13A	0.9600
N1—H1	0.75 (3)	C13—H13B	0.9600
C2—C12	1.519 (4)	C13—H13C	0.9600
C2—C13	1.526 (4)	C14—H14A	0.9600
C2—C3	1.525 (3)	C14—H14B	0.9600
C3—C4	1.515 (4)	C14—H14C	0.9600
C3—H3A	0.9700	C15—C20	1.368 (4)
C3—H3B	0.9700	C15—C16	1.385 (4)
C4—N5	1.493 (3)	C16—C17	1.366 (4)
C4—C14	1.522 (4)	C16—H16	0.9300
C4—H4	0.9800	C17—C18	1.380 (4)
N5—C6	1.433 (3)	C17—H17	0.9300
C6—C7	1.382 (3)	C18—C19	1.375 (4)
C6—C11	1.397 (3)	C18—C21	1.510 (5)
C7—C8	1.387 (5)	C19—C20	1.379 (4)
C7—H7	0.9300	C19—H19	0.9300
C8—C9	1.359 (5)	C20—H20	0.9300
C8—H8	0.9300	C21—H21A	0.9600
C9—C10	1.378 (5)	C21—H21B	0.9600
C9—H9	0.9300	C21—H21C	0.9600
O2—S1—O1	119.16 (14)	N1—C11—C10	121.6 (2)
O2—S1—N5	107.96 (13)	N1—C11—C6	120.6 (2)
O1—S1—N5	107.36 (11)	C10—C11—C6	117.6 (2)
O2—S1—C15	106.71 (12)	C2—C12—H12A	109.5
O1—S1—C15	107.67 (14)	C2—C12—H12B	109.5
N5—S1—C15	107.48 (10)	H12A—C12—H12B	109.5
C11—N1—C2	121.86 (19)	C2—C12—H12C	109.5
C11—N1—H1	109 (2)	H12A—C12—H12C	109.5
C2—N1—H1	112 (3)	H12B—C12—H12C	109.5
N1—C2—C12	109.2 (2)	C2—C13—H13A	109.5
N1—C2—C13	107.8 (2)	C2—C13—H13B	109.5
C12—C2—C13	108.9 (2)	H13A—C13—H13B	109.5
N1—C2—C3	111.42 (19)	C2—C13—H13C	109.5
C12—C2—C3	107.3 (2)	H13A—C13—H13C	109.5
C13—C2—C3	112.2 (2)	H13B—C13—H13C	109.5
C4—C3—C2	118.8 (2)	C4—C14—H14A	109.5
C4—C3—H3A	107.6	C4—C14—H14B	109.5
C2—C3—H3A	107.6	H14A—C14—H14B	109.5
C4—C3—H3B	107.6	C4—C14—H14C	109.5
C2—C3—H3B	107.6	H14A—C14—H14C	109.5
H3A—C3—H3B	107.0	H14B—C14—H14C	109.5
N5—C4—C3	110.93 (19)	C20—C15—C16	119.8 (3)
N5—C4—C14	110.3 (2)	C20—C15—S1	121.1 (2)
C3—C4—C14	109.5 (3)	C16—C15—S1	119.09 (19)
N5—C4—H4	108.7	C17—C16—C15	118.9 (3)
C3—C4—H4	108.7	C17—C16—H16	120.6
C14—C4—H4	108.7	C15—C16—H16	120.6
C6—N5—C4	119.9 (2)	C16—C17—C18	122.7 (3)
C6—N5—S1	120.68 (16)	C16—C17—H17	118.7
C4—N5—S1	119.08 (17)	C18—C17—H17	118.7
C7—C6—C11	120.9 (2)	C19—C18—C17	117.2 (3)
C7—C6—N5	119.2 (2)	C19—C18—C21	121.9 (3)
C11—C6—N5	119.8 (2)	C17—C18—C21	120.9 (3)
C6—C7—C8	120.0 (3)	C18—C19—C20	121.5 (3)
C6—C7—H7	120.0	C18—C19—H19	119.3
C8—C7—H7	120.0	C20—C19—H19	119.3
C9—C8—C7	119.6 (3)	C15—C20—C19	120.0 (3)
C9—C8—H8	120.2	C15—C20—H20	120.0
C7—C8—H8	120.2	C19—C20—H20	120.0
C8—C9—C10	121.0 (3)	C18—C21—H21A	109.5
C8—C9—H9	119.5	C18—C21—H21B	109.5
C10—C9—H9	119.5	H21A—C21—H21B	109.5
C9—C10—C11	120.8 (3)	C18—C21—H21C	109.5
C9—C10—H10	119.6	H21A—C21—H21C	109.5
C11—C10—H10	119.6	H21B—C21—H21C	109.5
C11—N1—C2—C12	−95.9 (3)	C8—C9—C10—C11	1.7 (4)
C11—N1—C2—C13	145.9 (2)	C2—N1—C11—C10	123.8 (3)
C11—N1—C2—C3	22.4 (3)	C2—N1—C11—C6	−62.0 (3)
N1—C2—C3—C4	61.1 (3)	C9—C10—C11—N1	175.7 (2)
C12—C2—C3—C4	−179.4 (2)	C9—C10—C11—C6	1.3 (4)
C13—C2—C3—C4	−59.8 (3)	C7—C6—C11—N1	−178.1 (2)
C2—C3—C4—N5	−57.2 (3)	N5—C6—C11—N1	−0.7 (3)
C2—C3—C4—C14	−179.3 (2)	C7—C6—C11—C10	−3.7 (3)
C3—C4—N5—C6	−27.7 (3)	N5—C6—C11—C10	173.7 (2)
C14—C4—N5—C6	93.9 (3)	O2—S1—C15—C20	−1.4 (3)
C3—C4—N5—S1	145.32 (18)	O1—S1—C15—C20	−130.5 (2)
C14—C4—N5—S1	−93.1 (3)	N5—S1—C15—C20	114.2 (2)
O2—S1—N5—C6	−146.99 (18)	O2—S1—C15—C16	177.6 (2)
O1—S1—N5—C6	−17.3 (2)	O1—S1—C15—C16	48.5 (2)
C15—S1—N5—C6	98.24 (18)	N5—S1—C15—C16	−66.8 (2)
O2—S1—N5—C4	40.06 (19)	C20—C15—C16—C17	−1.0 (4)
O1—S1—N5—C4	169.70 (18)	S1—C15—C16—C17	−180.0 (2)
C15—S1—N5—C4	−74.71 (19)	C15—C16—C17—C18	−0.1 (4)
C4—N5—C6—C7	−116.8 (2)	C16—C17—C18—C19	1.0 (4)
S1—N5—C6—C7	70.3 (3)	C16—C17—C18—C21	−178.9 (3)
C4—N5—C6—C11	65.7 (3)	C17—C18—C19—C20	−0.8 (5)
S1—N5—C6—C11	−107.2 (2)	C21—C18—C19—C20	179.1 (3)
C11—C6—C7—C8	3.2 (4)	C16—C15—C20—C19	1.2 (4)
N5—C6—C7—C8	−174.3 (2)	S1—C15—C20—C19	−179.8 (2)
C6—C7—C8—C9	−0.1 (4)	C18—C19—C20—C15	−0.3 (5)
C7—C8—C9—C10	−2.3 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20···O2	0.93	2.51	2.885 (4)	105
N1—H1···O2i	0.75 (3)	2.52 (3)	3.268 (3)	176 (3)
C14—H14B···O1ii	0.96	2.58	3.436 (4)	149
C13—H13A···Cg2	0.96	2.90	3.7592 (31)	150
C19—H19···Cg2i	0.93	2.90	3.5192 (34)	126

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C20—H20⋯O2	0.93	2.51	2.885 (4)	105
N1—H1⋯O2i	0.75 (3)	2.52 (3)	3.268 (3)	176 (3)
C14—H14B⋯O1ii	0.96	2.58	3.436 (4)	149
C13—H13A⋯Cg2	0.96	2.90	3.7592 (31)	150
C19—H19⋯Cg2i	0.93	2.90	3.5192 (34)	126

Symmetry codes: (i) ; (ii) . Cg2 is the centroid of the = C15–C20 ring.