3-(4-Methoxybenzyl)-1,5-benzo­thiazepin-4(5H)-one

R Selvakumar; M Bakthadoss; S Vijayakumar; S Murugavel

doi:10.1107/S1600536813009215

. 2013 Apr 10;69(Pt 5):o693. doi: 10.1107/S1600536813009215

3-(4-Methoxybenzyl)-1,5-benzothiazepin-4(5H)-one

R Selvakumar ^a, M Bakthadoss ^a,^b,^‡, S Vijayakumar ^c, S Murugavel ^d,^*

PMCID: PMC3648230 PMID: 23723850

Abstract

In the title compound, C₁₇H₁₅NO₂S, the thiazepine ring adopts a slightly distorted twist-boat conformation. The dihedral angle between the mean plane of the benzothiazepin ring system and the benzene ring is 65.7 (1)°. In the crystal, pairs of N—H⋯O hydrogen bonds link inversion-related molecules into dimers, generating R₂²(8) ring motifs. These dimers are further linked by C—H⋯π and π–π interactions [inter-centroid distance between the benzene rings of the benzothiazepine unit = 3.656 (3) Å] into a three-dimensional supramolecular network.

Related literature

For background to the biology of thiazepin derivatives and for a related structure, see: Bakthadoss et al. (2013 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶). graphic file with name e-69-0o693-scheme1.jpg

Experimental

Crystal data

C₁₇H₁₅NO₂S
M _r = 297.36
Triclinic,
a = 7.678 (5) Å
b = 9.612 (5) Å
c = 10.860 (5) Å
α = 77.208 (5)°
β = 74.117 (4)°
γ = 81.522 (5)°
V = 748.5 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.22 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 = 0.951, T _max = 0.968
18449 measured reflections
5363 independent reflections
3676 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.134
S = 1.05
5363 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.33 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 for Windows (Farrugia, 2012) ▶; software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(24.4KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813009215/sj5315sup1.cif

e-69-0o693-sup1.cif^{(24.4KB, cif)}

Click here for additional data file.^{(257.3KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009215/sj5315Isup2.hkl

e-69-0o693-Isup2.hkl^{(257.3KB, hkl)}

Click here for additional data file.^{(5.6KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813009215/sj5315Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg is the centroid of the C3–C7 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.86	2.02	2.860 (2)	167
C17—H17B⋯Cg ⁱⁱ	0.96	2.96	3.561 (3)	122

Open in a new tab

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

Acknowledgments

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

supplementary crystallographic information

Comment

The background to the biology of thiazepin derivatives and a related structure have been described recently (Bakthadoss et al., 2013). 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 a displacement ellipsoid plot of (I), with the atom numbering scheme. The seven membered thiazepine ring (N1/S1/C1/C2/C7/C8/C9) adopts slightly distorted twist-boat conformation as indicated by puckering parameters (Cremer & Pople, 1975) QT = 0.9884 (11) Å, φ₂ = 357.9 (1)° and φ₃ = 355.6 (3)°. The dihedral angle between the benzothiazepin ring system and the benzene ring is 65.7 (1) (1)°. The atom O1 deviates by -0.458 (1) Å from the least-squares plane of the thiazepin ring. The sum of angles at N1 atom of the thiazepin ring (359.9⁰) is in accordance with sp² hybridization. The geometric parameters of the title molecule agree well with those reported for a similar structure (Bakthadoss et al., 2013).

In the crystal, molecules are linked by N1—H1A···O1 hydrogen bonds into cylic centrosymmetric R₂²(8) dimers (Fig. 2 and Table 1). These dimers are further linked by C17—H17B···Cgⁱⁱ (Table 1; Symmetry code:(ii) = 1 + x, 1 + y, z) hydrogen bonds and π—π interactions between benzothiazepine benzene rings with Cg···Cgⁱⁱⁱ = 3.656 (3) Å (Symmetry code:(iii) = -x, 1 - y, 1 - z) forming a three-dimensional supramolecular network (Fig. 3; Cg is the centroid of the C2–C7 benzene ring).

Experimental

A mixture of (Z)-methyl 2-(bromomethyl)-3-(4-methoxyphenyl)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 x 20 ml). The organic layer was washed with brine (2 x 20 ml) and dried over anhydrous sodium sulfate. It was then concentrated to successfully provide the crude final product ((Z)-3-(4-methoxybenzyl)benzo[b][1,4]thiazepin-4(5H)-one). This was purified by column chromatography on silica gel with ethylacetate/hexane 1:19 as eluent to afford the title compound in good yield (45%). Single crystals suitable for X-ray diffraction were obtained by slow evaporation of an ethylacetate solution at room temperature.