2-[(Methyl­sulfan­yl)meth­yl]-1,2-benz­isothia­zol-3(2H)-one 1,1-dioxide

Waseeq Ahmad Siddiqui; Saeed Ahmad; Hamid Latif Siddiqui; Rana Altaf Hussain; Masood Parvez

doi:10.1107/S1600536808028109

. 2008 Sep 6;64(Pt 10):o1897. doi: 10.1107/S1600536808028109

2-[(Methylsulfanyl)methyl]-1,2-benzisothiazol-3(2H)-one 1,1-dioxide

Waseeq Ahmad Siddiqui ^a,^*, Saeed Ahmad ^b, Hamid Latif Siddiqui ^c, Rana Altaf Hussain ^c, Masood Parvez ^d

PMCID: PMC2959482 PMID: 21201108

Abstract

In the title molecule, C₉H₉NO₃S₂, the essentially planar benzisothiazole ring system and the C—S—C atoms of the methylsulfanyl side chain form an angle of 64.45 (7)°. The structure is devoid of any classical hydrogen bonding. However, weak non-classical inter- and intramolecular hydrogen bonds of the type C—H⋯O are present.

Related literature

For related literature, see: Bernstein et al. (1994 ▶); Masashi et al. (1999 ▶); Nagasawa et al. (1995 ▶); Siddiqui et al. (2007a ▶,b ▶, 2008a ▶,b ▶); Xu et al. (2006 ▶); Liang (2006 ▶).

Experimental

Crystal data

C₉H₉NO₃S₂
M _r = 243.29
Monoclinic,
a = 7.550 (3) Å
b = 17.332 (8) Å
c = 9.455 (3) Å
β = 124.26 (2)°
V = 1022.6 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 173 (2) K
0.18 × 0.16 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1997 ▶) T _min = 0.915, T _max = 0.970
3975 measured reflections
2322 independent reflections
2004 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.094
S = 1.05
2322 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: HKL 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: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808028109/lh2683sup1.cif

e-64-o1897-sup1.cif^{(16.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808028109/lh2683Isup2.hkl

e-64-o1897-Isup2.hkl^{(111.8KB, 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
C2—H2⋯O2ⁱ	0.95	2.49	3.390 (2)	158
C9—H9B⋯O3	0.98	2.56	3.383 (3)	142

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

1,2-benzisothiazole-3-one 1,1-dioxide (saccharin) has been identified as an important molecular component in various classes of 5-HTla antagonists, analgesics and human mast cell tryptase inhibitors (Liang et al., 2006). Particularly, the substituted derivatives with e.g. N-hydroxy and N-alkyl substutuents have shown important biological activities (Nagasawa et al., 1995). Various biologically important saccharin skeletons and their N-alkyl derivatives were efficiently prepared (Xu et al., 2006) by chromium oxide-catalyzed oxidation of N-alkyl(o-methyl)arenesulfonamides in acetonitrile besides the already developed methodology utilizing irradiation techniques (Masashi et al., 1999) for similar type of conversions. In continuation of our research program on the synthesis of benzisothiazole derivatives (Siddiqui et al., 2007a,b,2008a,b), we report the synthesis (see Fig. 3) and crystal structure of the title compound, in this paper.

In the molecular structure (Fig. 1) the benzisothiazole rings system is essentially planar, the maximum deviation of any atom from the mean plane through S1/N1/C1–C7 being 0.0224 (8) Å for atom S1. The side chain comprising of atoms S2/C8/C9 is inclined at an angle 64.45 (7)° with the mean-plane of the benzisothiazole rings system. The structure is devoid of any classical hydrogen bonding. However, non-classical intermolecular hydrogen bond of the type C—H···O are present resulting in dimeric units in an R₂²(8) motif (Bernstein et al., 1994). In addition, intramolecular hydrogen bonds of the type C—H···O are also present in the structure resulting in an S(7) pattern (Bernstein et al., 1994) (details are in Fig. 2 and Table 1).

Experimental

A suspension of saccharin (I) (1.0 g, 5.46 mmol), sodium sulfite (1.4 g, 10.93 mmol) and an excess of 2-chloro-5-methylaniline (5 ml) was first stirred at room temperature (30 min.) and then under reflux (1.5 hrs). The reaction mixture turned orange red after reflux. Cooled the reaction mixture to room temperature and extracted the product with chloroform (3 X 25 ml). Concentrated the organic layer under reduced pressure (11 torr) to get light yellow product (II) (0.6 g, 2.46 mmol), yield = 45%. Recrystallization Solvent: MeOH:CH₃CN (1:1). The solution was subjected to slow evaporation at 313 K to obtain colorless crystals.