3-[(3-Benzoyl-4-hy­droxy-1,1-dioxo-2H-1λ6,2-benzothia­zin-2-yl)meth­yl]benzo­nitrile

Nazia Sattar; Hamid Latif Siddiqui; Tanvir Hussain; Sana Aslam; Masood Parvez

doi:10.1107/S1600536811052706

. 2011 Dec 10;68(Pt 1):o91. doi: 10.1107/S1600536811052706

3-[(3-Benzoyl-4-hydroxy-1,1-dioxo-2H-1λ⁶,2-benzothiazin-2-yl)methyl]benzonitrile

Nazia Sattar ^a, Hamid Latif Siddiqui ^a,^*, Tanvir Hussain ^a, Sana Aslam ^a, Masood Parvez ^b

PMCID: PMC3254442 PMID: 22259590

Abstract

There are two independent molecules in the asymmetric unit of the title compound, C₂₃H₁₇N₂O₄S, with significant differences in their conformations, e.g. the benzene rings of the benzothiazine and benzonitrile units are inclined at 28.19 (10) and 17.89 (7)° in the two molecules, with the centroids of the rings separated by 3.975 (2) and 3.637 (2) Å, respectively. Moreover, the N—C—C—C torsion angles involving the benzoyl group are 14.3 (5) and 8.2 (5)° in the two molecules, showing different degrees of rotation of this group. In both molecules, the heterocyclic thiazine rings adopt half-chair conformations, with the S and N atoms displaced by 0.427 (6) and 0.365 (6) Å, respectively, in one molecule and by 0.356 (6) and 0.432 (6) Å, respectively, in the other, on opposite sides of the mean planes formed by the remaining ring atoms. The crystal structure is stabilized by intermolecular C—H⋯O hydrogen bonds and further consolidated by intramolecular O—H⋯O hydrogen bonds.

Related literature

For the biological activity of benzothiazine derivatives, see: Ahmad et al. (2010 ▶). For related structures, see: Siddiqui et al. (2008 ▶).

Experimental

Crystal data

C₂₃H₁₆N₂O₄S
M _r = 416.44
Orthorhombic,
a = 12.2900 (2) Å
b = 24.7970 (6) Å
c = 25.6080 (6) Å
V = 7804.2 (3) Å³
Z = 16
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 173 K
0.20 × 0.12 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1997 ▶) T _min = 0.961, T _max = 0.976
16724 measured reflections
8869 independent reflections
6212 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.079
wR(F ²) = 0.164
S = 1.13
8869 reflections
543 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶); data reduction: SCALEPACK (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶) and ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811052706/zl2435sup1.cif

e-68-00o91-sup1.cif^{(32.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811052706/zl2435Isup2.hkl

e-68-00o91-Isup2.hkl^{(425.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811052706/zl2435Isup3.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
C16—H16A⋯O3ⁱ	0.99	2.57	3.382 (4)	139
C16—H16B⋯O1ⁱ	0.99	2.60	3.456 (4)	145
C28—H28⋯O2ⁱⁱ	0.95	2.45	3.188 (4)	135
O3—H3O⋯O4	0.84	1.76	2.503 (4)	146
O7—H7O⋯O8	0.84	1.73	2.484 (4)	148

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

Acknowledgments

HLS is grateful to the Institute of Chemistry, University of the Punjab, Lahore, Pakistan, for financial support.

supplementary crystallographic information

Comment

In continuation of our research on the synthesis of biologically active benzothiazine derivatives (Ahmad et al., 2010), we now report the synthesis and crystal structure of the title compound in this article.

There are two independent molecules in an asymmetric unit of the title compound, labeled as molecules A (Fig. 1) and B (Fig. 2) containing the S1 and S2 atoms, respectively. There are significant differences in the conformations of the two molecules, e.g., the benzene rings of the benzothiazine and benzonitrile moieties are inclined at 28.19 (10) and 17.89 (7)° in the molecules A and B with centroids of the rings separated by 3.975 (2) and 3.637 (2) Å, respectively. Moreover, the torsion angles N1–C8–C9–C10 and N3–C31–C32–C33 in molecules A and B are 14.3 (5) and 8.2 (5)°, respectively, showing different degrees of rotation of these groups (Fig. 3). In both molecules, the heterocyclic thiazine rings adopt half chair conformations with atoms S and N displaced by 0.427 (6) and 0.365 (6) Å, in molecule A and 0.356 (6) and 0.432 (6) Å, in molecule B, respectively, on the opposite sides from the mean planes formed by the remaining ring atoms. The bond distances and angles in both molecules agree very well with the corresponding bond distances and angles reported in closely related compounds (Siddiqui et al., 2008).

The methylene H-atoms bonded to C16 in molecule A are hydrogen bonded to O1 and O3 of two symmetry related molecules A (Tab. 1 and Fig. 4). On the other hand, an aryl H-atom, H28 of molecule B, is hydrogen bonded to O2 of molecule A. The structure is consolidated by intramolecular interactions of the types O—H···O, C—H···N and C—H···O.

Experimental

An aqueous solution of sodium hydroxide (0.4 g, 9.96 mmol) was added to a solution of 3-benzoyl-4-hydroxy-2H-1,2-benzothiazine 1,1-dioxide (1.5 g, 4.9 mmol) in acetone (15 ml). 3-(Bromomethyl)benzonitrile (1.17 g, 5.98 mmol) was added with stirring and the reaction mixture was ultrasonicated for 15 minutes at 318 K. The completion of reaction was monitored with the help of thin layer chromatography (TLC). The contents of the flask were acidified to pH 3.0 by HCl (5%). Yellow precipitates of the title compound were filtered off and washed with excess of distilled water. Crystals suitable for crystallographic study were grown from methanol at room temperature. Yield = 1.93 g, 93.23%; m.p. = 444 - 446 K.