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

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

doi:10.1107/S1600536809034837

. 2009 Sep 5;65(Pt 10):o2363–o2364. doi: 10.1107/S1600536809034837

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, M N Ponnuswamy ^a,^*

PMCID: PMC2970367 PMID: 21577831

Abstract

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,
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
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)

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 ▶).

Supplementary Material

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

e-65-o2363-sup1.cif^{(21.5KB, cif)}

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

e-65-o2363-Isup2.hkl^{(247.3KB, hkl)}

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

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

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

Acknowledgments

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.

supplementary crystallographic information

Comment

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.

Experimental

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).