(Z)-3-(4-Chloro­benz­yl)-1,5-benzothia­zepin-4(5H)-one

D Lakshmanan; S Murugavel; R Selvakumar; M Bakthadoss

doi:10.1107/S1600536812026608

. 2012 Jun 16;68(Pt 7):o2130. doi: 10.1107/S1600536812026608

(Z)-3-(4-Chlorobenzyl)-1,5-benzothiazepin-4(5H)-one

D Lakshmanan ^a, S Murugavel ^b,^*, R Selvakumar ^c, M Bakthadoss ^c,^‡

PMCID: PMC3393941 PMID: 22798806

Abstract

In the title compound, C₁₆H₁₂ClNOS, the seven-membered thiazepine ring adopts a distorted twisted boat conformation. The dihedral angle between the least-squares planes of the 1,5-benzothiazepine ring system and the benzene ring is 50.2 (1)°. In the crystal, pairs of N—H⋯O hydrogen bonds link centrosymmetrically related molecules into dimers, generating R ₂ ²(8) ring motifs. The crystal packing is further stabilized by π–π interactions [centroid–centroid distance = 3.763 (2) Å].

Related literature

For the pharmaceutical properties of thiazepin derivatives, see: Tomascovic et al. (2000 ▶); Rajsner et al. (1971 ▶); Metys et al. (1965 ▶). For related structures, see: Sridevi et al. (2011 ▶); Sabari et al. (2011 ▶); Selvakumar et al. (2012 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₆H₁₂ClNOS
M _r = 301.78
Orthorhombic,
a = 9.0486 (3) Å
b = 9.4105 (3) Å
c = 33.4876 (10) Å
V = 2851.53 (16) Å³
Z = 8
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 293 K
0.23 × 0.21 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.910, T _max = 0.941
14850 measured reflections
3099 independent reflections
2382 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.118
S = 1.03
3099 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.45 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812026608/tk5111sup1.cif

e-68-o2130-sup1.cif^{(23.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812026608/tk5111Isup2.hkl

e-68-o2130-Isup2.hkl^{(149.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812026608/tk5111Isup3.cml

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—H1⋯O1ⁱ	0.86	2.07	2.854 (2)	151

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Dr Babu Vargheese, SAIF, IIT, Madras, India, for his help with the data collection.

supplementary crystallographic information

Comment

The title compound is used as an intermediate for the synthesis of dosulepin, which is an anti-depressant of the tricyclic family. Dosulepin prevents reabsorbing of serotonin and noradrenaline in the brain, helps to prolong the mood lightening effect of any released noradrenaline and serotonin, thus relieving depression. The dibenzo[c,e]thiazepin derivatives exhibit chiroptical properties (Tomascovic et al., 2000). Dibenzo[b,e]thiazepin-5,5-dioxide derivatives possess anti-histaminic and anti-allergenic activities (Rajsner et al., 1971). Benzene thiazepin derivatives are identified as a new type of effective anti-histaminic compounds (Metys et al., 1965). In view of this biological importance, the crystal structure of the title compound has been carried out and the results are presented here.

Fig. 1. shows the seven membered thiazepine ring (N1/S1/C1/C2/C7/C8/C9) to adopt a twisted-boat conformation as indicated by puckering parameters (Cremer & Pople, 1975) QT = 1.0015 (16) Å, θ₂ = 74.1 (1)°, φ₂ = 177.3 (1)° and φ₃ = 177.6 (4)°. The dihedral angle between the benzothiazepin ring system and the benzene ring is 50.2 (1)°. The geometric parameters of the title molecule agree well with those reported for similar structures (Sridevi et al., 2011; Sabari et al., 2011).

In the crystal packing (Fig. 2), centrosymmetrically related molecules are linked by N1—H1···O1 hydrogen bonds into cyclic R₂²(8) dimers (Bernstein et al., 1995). The crystal packing (Fig. 3) is further stabilized by intermolecular π—π interactions with a Cg—Cgⁱ separation of 3.763 (1) Å [Cg is the centroid of the C2–C7 benzene ring, symmetry code as in Fig. 3].

Experimental

A mixture of (Z)-methyl 2-(bromomethyl)-3-(4-chlorophenyl)acrylate (2 mmol) and o-aminothiophenol (2 mmol) in the presence of potassium tert-butoxide (4.8 mmol) in dry THF (10 ml) was stirred at room temperature for 1 h. After the completion of the reaction as indicated by TLC, the reaction mixture was concentrated and the resulting crude mass was diluted with water (20 ml) and extracted with ethyl acetate (3 × 20 ml). The organic layer was washed with brine (2 × 20 ml) and dried over anhydrous sodium sulfate. The organic layer was concentrated, which successfully provided the crude final product. The final product was purified by column chromatography on silica gel to afford the title compound in good yield (43%).