Racemic 9,10-dimeth­oxy-3-methyl-6-phenyl-7,7a-dihydro­benzo[b]benzo[4,5]isothia­zolo[2,3-d][1,4]diazepine 12,12-dioxide

Jatinder P Bassin; Virender P Shah; Lee Martin; Peter N Horton

doi:10.1107/S1600536811004983

. 2011 Feb 23;67(Pt 3):o684–o685. doi: 10.1107/S1600536811004983

Racemic 9,10-dimethoxy-3-methyl-6-phenyl-7,7a-dihydrobenzo[b]benzo[4,5]isothiazolo[2,3-d][1,4]diazepine 12,12-dioxide

Jatinder P Bassin ^a,^*, Virender P Shah ^a, Lee Martin ^a, Peter N Horton ^b

PMCID: PMC3052004 PMID: 21522430

Abstract

There are two molecules in the asymmetric unit of the title compound, C₂₄H₂₂N₂O₄S. The conformation of the seven-membered ring is twisted boat for both molecules. The molecule is chiral, but crystal symmetry generates a recemate. The crystal packing is stabilized by weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For related structures, see: Zia-ul-Haq et al. (2007 ▶); Boudina et al. (2007 ▶); Doubia et al. (2007 ▶); Sanudo et al. (2009 ▶); Spencer et al. (2009 ▶); Swamy et al. (2008 ▶). For the psychotropic properties of aptazapine [systematic name: 2-methyl-1,3,4,14b-tetrahydro-2H,10H-pyrazino[1,2-a]pyrrolo[2,1-c][1,4]benzodiazepine] and bretazenil [systematic name: t-butyl-8-bromo-11,12,13,13a-tetrahydro-9-oxo-9H-imidazo(1,5-a)pyrrolo(2,1-c)(1,4)benzodiazepine-1-carboxylate], see: Silvestri et al. (1994 ▶); Landquist (1984 ▶); Insuasty et al. (2008 ▶); Bennamane et al. (2008 ▶); Schutz (1982 ▶). For the bioactivity of benzodiazepines, see: Constanzo et al. (1990 ▶); Kelly et al. (1997 ▶). For the effect on the bioactivity of fusing different heterocyclic rings to the 1,4- and 1,5-benzodiazepine system, see: Chimirri et al. (1993a ▶,b ▶). For the synthesis of the title compound, see: Bassin et al. (2000 ▶).

Experimental

Crystal data

C₂₄H₂₂N₂O₄S
M _r = 434.51
Triclinic,
a = 11.9007 (4) Å
b = 12.8521 (4) Å
c = 14.6202 (5) Å
α = 109.852 (2)°
β = 90.743 (2)°
γ = 92.775 (2)°
V = 2099.76 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 120 K
0.50 × 0.30 × 0.10 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1997 ▶) T _min = 0.912, T _max = 0.981
31054 measured reflections
7393 independent reflections
5463 reflections with I > 2σ(I)
R _int = 0.060

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.106
S = 1.01
7393 reflections
566 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶); data reduction: DENZO, COLLECT and maXus (Mackay et al., 1999 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CAMERON (Watkin, et al., 1993 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811004983/rk2256sup1.cif

e-67-0o684-sup1.cif^{(30.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811004983/rk2256Isup2.hkl

e-67-0o684-Isup2.hkl^{(354.4KB, 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
N1—H1A⋯Cl1	0.89	2.44	3.303 (3)	162
N1—H1B⋯Cl1ⁱ	0.89	2.36	3.236 (2)	170
N1—H1C⋯O1ⁱⁱ	0.89	2.05	2.901 (4)	159
O1—H1H⋯Cl1	0.85	2.45	3.290 (3)	170
O1—H1I⋯Cl1ⁱⁱⁱ	0.85	2.39	3.228 (2)	170

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

We thank the EPSRC for funding the National Crystallography Service, and the STFC (formerly CCLRC) for access to synchrotron facilities.

supplementary crystallographic information

Comment

In recent years tetracyclic benzodiazepines have received a great deal of attention due to the psychotropic properties of such compounds as aptazapine and bretazenil (Silvestri et al., 1994; Landquist, 1984; Insuasty et al., 2008; Bennamane et al., 2008; Schutz, 1982). A number of structures of benzodiazepines have been reported: Zia-ul-Haq et al., (2007); Boudina et al., (2007); Doubia et al., (2007); Sanudo et al., (2009); Spencer et al., (2009); Swamy et al., (2008). Benzodiazepines containing heterocycles fused to the seven-membered ring have shown important and varied bioactivities (Constanzo et al., 1990; Kelly et al., 1997). It has been demonstrated that by fusing different heterocyclic rings to the 1,4- and 1,5-benzodiazepine system enhances the biological activity of these compounds (Chimirri et al., 1993a,b). We previously reported the synthesis of a new heterocyclic ring system dihydrobenzo[b]benzo[4,5]isothiazolo[2,3-d][1,4]diazepine 12,12-dioxide (Bassin et al., 2000). As, an extension of this work we report the crystal structure of the enantiomeric mixture of 9,10-dimethoxy-3-methyl-6-phenyl-7,7a-dihydrobenzo[b] benzo[4,5]isothiazolo [2,3-d][1,4]diazepine 12,12-dioxide.

Experimental

The title compound was synthesised following a modified procedure (Bassin et al., 2000) by refluxing (E)-4,5-dimethoxy-2-(3-oxo-3-phenylprop-1-en-1-yl)benzene-1-sulfonyl chloride with 3,4-diaminotoluene in ethanol for 1 hour. The reaction mixture was allowed to cool to room temperature the resulting precipitated product was filtered under suction and thoroughly washed with aqueous ethanol. The air dried product was re-crystallised from ethanol. A yellow crystalline product (yield: 82%, m.p.: 498 K) was obtained.