Sodium N-bromo-2-chloro­benzene­sulfonamidate sesquihydrate

B Thimme Gowda; Sabine Foro; K Shakuntala

doi:10.1107/S160053681102071X

. 2011 Jun 11;67(Pt 7):m870. doi: 10.1107/S160053681102071X

Sodium N-bromo-2-chlorobenzenesulfonamidate sesquihydrate

B Thimme Gowda ^a,^*, Sabine Foro ^b, K Shakuntala ^a

PMCID: PMC3152083 PMID: 21836866

Abstract

In the title compound, Na⁺·C₆H₄BrClNO₂S⁻·1.5H₂O, one water molecule has crystallographically imposed twofold symmetry. The Na⁺ cation shows a pseudo-octahedral coordination provided by three O atoms of water molecules and three sulfonyl O atoms of different N-bromo-2-chlorobenzenesulfonamidate anions. The S—N distance of 1.579 (6) Å is consistent with an S=N double-bond character. The crystal structure is stabilized by O—H⋯Br, O—H⋯N and O—H⋯O hydrogen bonds.

Related literature

For background to the chemistry of N-haloarylsulfonamides, see: Gowda & Shetty (2004 ▶); Usha & Gowda (2006 ▶). For our study of the effect of substituents on the structures of N-haloarylsulfonamides, see: Gowda, Kožíšek et al. (2007 ▶); Gowda, Usha et al. (2007 ▶). For related structures, see: George et al. (2000 ▶); Olmstead & Power (1986 ▶). For an isostructural compound, see: Gowda et al. (2010 ▶).

Experimental

Crystal data

Na⁺·C₆H₄BrClNO₂S⁻·1.5H₂O
M _r = 319.53
Monoclinic,
a = 11.200 (2) Å
b = 6.728 (1) Å
c = 28.304 (3) Å
β = 100.94 (1)°
V = 2094.0 (5) Å³
Z = 8
Mo Kα radiation
μ = 4.41 mm⁻¹
T = 293 K
0.34 × 0.30 × 0.14 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD area detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.316, T _max = 0.578
7442 measured reflections
2147 independent reflections
1955 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.128
S = 1.25
2147 reflections
141 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.27 e Å⁻³
Δρ_min = −1.19 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681102071X/rz2602sup1.cif

e-67-0m870-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681102071X/rz2602Isup2.hkl

e-67-0m870-Isup2.hkl^{(105.7KB, 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
O3—H31⋯Br1ⁱ	0.82 (2)	2.70 (2)	3.518 (5)	171 (8)
O3—H32⋯N1	0.81 (2)	2.21 (5)	2.934 (7)	149 (8)
O3—H32⋯O2	0.81 (2)	2.51 (5)	3.232 (7)	148 (8)
O4—H41⋯N1ⁱⁱ	0.82 (2)	2.20 (3)	3.002 (7)	168 (8)

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

Acknowledgments

BTG thanks the University Grants Commission, Government of India, New Delhi, for the grant under theUGC-BSR one time grant to Faculty/Professors.

supplementary crystallographic information

Comment

The chemistry of N-halo arylsulfonamides are of interest in synthetic, mechanistic, analytical and biological chemistry (Gowda & Shetty, 2004; Usha & Gowda, 2006). In the present work, as a part of exploring the substituent effects on the crystal structures of N-haloarylsulfonamidates, the structure of sodium N-bromo-2-chlorobenzenesulfonamidate (I) has been determined (Fig. 1). The structure of (I) resembles those of sodium N-bromo-benzenesulfonamidate (II) (Gowda, Usha et al., 2007), sodium i>N-bromo-4-chlorobenzenesulfonamidate (III) (Gowda, Kožíšek et al., 2007) and other sodium N-chloro-arylsulfonamidates (George et al., 2000; Olmstead & Power, 1986), and is isostructural with the previously reported N-chloro-2-chloro-benzenesulfonamidate (Gowda et al., 2010) (IV).

In the title compound, one water molecule (O4) has crystallographically imposed twofold axis. The sodium ion shows octahedral coordination by three O atoms of water molecules and by three sulfonyl O atoms of three different N-bromo-2-chloro-benzenesulfonamide anions.

There is no interaction between the N and Na atoms in the molecule. The S—N distance of N1—S1, 1.579 (6)Å is consistent with a S—N double bond and is in agreement with the observed values of 1.578 (4)Å in (II), 1.588 (2) Å in (IV), and N1—S1, 1.574 (5)Å and N2—S2 1.579 (4)Å in (III).

The crystal packing consists of a two-dimensional polymeric layers running parallel to the ac plane (Fig. 2). The molecular packing is stabilized by O3—H31···Br1, O3—H32···N1, O3—H32···O2 and O4—H41···N1 hydrogen bonds (Table 1).

Experimental

The title compound was prepared according to the literature method (Usha & Gowda, 2006). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared and NMR spectra. Prism like yellow single crystals of the title compound used in X-ray diffraction studies were obtained from slow evaporation of its aqueous solution at room temperature.