2,2,4-Trimethyl-5-(4-tolyl­sulfon­yl)-2,3,4,5-tetra­hydro-1H-1,5-benzo­diazepine

Ravichandran, K.; Sathiyaraj, K.; Ilango, S.S.; Ponnuswamy, S.; Ponnuswamy, M.N.

doi:10.1107/S1600536809034837

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Pages o2363-o2364

doi:10.1107/S1600536809034837

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2,2,4-Trimethyl-5-(4-tolylsulfonyl)-2,3,4,5-tetrahydro-1H-1,5-benzodiazepine

K. Ravichandran,^a K. Sathiyaraj,^b S. S. Ilango,^b S. Ponnuswamy ^b and M. N. Ponnuswamy ^a ^*

^aCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, and ^bDepartment of Chemistry, Government Arts College (Autonomous), Coimbatore 641 018, India
^*Correspondence e-mail: mnpsy2004@yahoo.com

(Received 20 August 2009; accepted 30 August 2009; online 5 September 2009)

In the title compound, C₁₉H₂₄N₂O₂S, the benzodiazepine ring adopts a distorted boat conformation. The S atom shows a distorted tetrahedral 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 interactions.

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_r = 344.46
Orthorhombic, P 2₁ 2₁ 2₁
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[F² > 2σ(F²)] = 0.047
wR(F²) = 0.145
S = 1.04
5154 reflections
224 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.19 e Å⁻³
Absolute structure: Flack (1983 ), 2171 Friedel pairs
Flack parameter: −0.12 (9)

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) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x-1, y, z. Cg2 is the centroid of the = C15–C20 ring.

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 ).

Supporting information

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

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

checkCIF report

Comment top

Benzodiazepines are known for their natural occurrence in filamentous fungi and actinomycetes of the genera pencillium, aspergillus and streptomyces. Benzodiazepines from aspergillus include asperlicin, which is used for treatment of gastrointestinal and central nervous system (CNS) disorders (Rahbaek et al., 1999). In view of these importance and to ascertain the molecular conformation, a crystallographic study of the title compound has been carried out.

The ORTEP diagram of the title compound is shown in Fig.1. The benzodiazepine ring adopts a distorted boat conformation. The puckering parameters (Cremer & Pople, 1975) and the asymmetry parameters (Nardelli, 1983) for this ring are q₂ = 0.976 (3) Å, q₃ = 0.068 (3) Å, ϕ₂ = 152.5 (2)°, ϕ₃ = 30.0 (1)° and Δ2(C4)=7.8 (1)°. Atom S takes up a distorted tetrahedral geometry, with the O—S—O and N—S—C angles deviating significantly from ideal values, and this may be attributed to the Thorpe-Ingold effect (Bassindale, 1984). The sum of the bond angles at N1 (342.9°) of the benzodiazepine ring is in accordance with sp³ hybridization, whereas the one at N5(359.7°) is in sp² hybridization, respectively.

The crystal packing is controlled by C—H···O, N—H···O and C—H···π types of intra and intermolecular interactions. Atom N1 at (x, y, z) donates a proton to O1 (-x, y + 1/2, -z + 1/2 + 1), which forms a one-dimesional C7 chain (Bernstein et al., 1995) running along b–axis. The intermolecular hydrogen bond C14—H14B···O1 connects the molecule into a C6 one dimensional chain running along a–axis as shown in Fig 2. The methyl group H atom in the benzodiazepine ring interacts with the centroid atom of the toluenesulfonyl ring through an intramolecular C—H···π interaction involving atom C13, the separation between H13A and the centroid (Cg2) of the ring (C15/C16/C17/C18/C19/C20) being 2.899 Å.

Related literature top

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). Cg2 is the centroid of the = C15–C20 ring.

Experimental top

To a solution of 2,2,4-Trimethyl-1H-tetrahydro-1,5-benzodiazepine (0.59 g) in anhydrous benzene (16 ml), triethylamine (0.7 ml) and 4-toluenesulfonyl chloride (1 gm) were added. The reaction mixture was allowed to reflux for 16 hrs. The benzene solution was washed with water, dried over anhydrous Na₂SO₄ and concentrated. The resulting mass was purified by crystallization from benzene (Ponnuswamy et al., 2006).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Perspective view of the molecule showing the displacement ellipsoids at 30% probability level. H atoms have been omitted for clarity.
	Fig. 2. The crystal packing of the molecules viewed down c–axis. H atoms not involved in hydrogen bonding have been omitted for clarity.

2,2,4-Trimethyl-5-(4-tolylsulfonyl)-2,3,4,5-tetrahydro-1H- 1,5-benzodiazepine top

Crystal data top

C₁₉H₂₄N₂O₂S	F(000) = 736
M_r = 344.46	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0742P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.009
5154 reflections	Δρ_max = 0.18 e Å⁻³
224 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 2171 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.12 (9)

Crystal data top

C₁₉H₂₄N₂O₂S	V = 1903.07 (17) Å³
M_r = 344.46	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.3658 (3) Å	µ = 0.18 mm⁻¹
b = 14.8013 (8) Å	T = 293 K
c = 17.4556 (10) Å	0.25 × 0.20 × 0.20 mm

Data collection top

Bruker Kappa APEXII area-detector diffractometer	5154 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	3278 reflections with I > 2σ(I)
T_min = 0.957, T_max = 0.964	R_int = 0.034
13544 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.145	Δρ_max = 0.18 e Å⁻³
S = 1.04	Δρ_min = −0.19 e Å⁻³
5154 reflections	Absolute structure: Flack (1983), 2171 Friedel pairs
224 parameters	Absolute structure parameter: −0.12 (9)
0 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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	3.759 (3)	150
C19—H19···Cg2ⁱ	0.93	2.90	3.519 (3)	126

Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₉H₂₄N₂O₂S
M_r	344.46
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	7.3658 (3), 14.8013 (8), 17.4556 (10)
V (Å³)	1903.07 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.957, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	13544, 5154, 3278
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.691

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.145, 1.04
No. of reflections	5154
No. of parameters	224
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19
Absolute structure	Flack (1983), 2171 Friedel pairs
Absolute structure parameter	−0.12 (9)

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20···O2	0.93	2.51	2.885 (4)	104.7
N1—H1···O2ⁱ	0.75 (3)	2.52 (3)	3.268 (3)	176 (3)
C14—H14B···O1ⁱⁱ	0.96	2.58	3.436 (4)	148.6
C13—H13A···Cg2	0.96	2.8987	3.7592 (31)	149.77
C19—H19···Cg2ⁱ	0.93	2.8965	3.5192 (34)	125.53

Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) x−1, y, z.

Acknowledgements

KR thanks Dr Babu Varghese, SAIF, IIT-Madras, India, for his help with the data collection and the management of Kandaswami Kandar's College, Velur, Namakkal, India, for their encouragement to pursue the programme.

References

Bassindale, A. (1984). The Third Dimension in Organic Chemistry, ch. 1, p. 11. New York: John Wiley and Sons. Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N. L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Nardelli, M. (1983). Acta Cryst. C39, 1141–1142. CrossRef CAS Web of Science IUCr Journals Google Scholar
Ponnuswamy, S., Murugadoss, R., Jeyaraman, R., Thiruvalluvar, A. & Parthasarathy, V. (2006). Indian J. Chem. Sect. B, 45, 2059–2070. Google Scholar
Rahbaek, L., Breinholt, J., Frisvad, J. C. & Christophersen, C. (1999). J. Org. Chem., 64, 1689–1692. Web of Science CrossRef PubMed Google Scholar
Sheldrick, G. M. (2001). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 65| Part 10| October 2009| Pages o2363-o2364

doi:10.1107/S1600536809034837

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2,2,4-Tri­methyl-5-(4-tolyl­sulfon­yl)-2,3,4,5-tetra­hydro-1H-1,5-benzo­diazepine

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2,2,4-Trimethyl-5-(4-tolylsulfonyl)-2,3,4,5-tetrahydro-1H-1,5-benzodiazepine