Potassium N-chloro-o-toluene­sulfonamidate monohydrate

B Thimme Gowda; Sabine Foro; K Shakuntala

doi:10.1107/S1600536811023555

. 2011 Jun 22;67(Pt 7):m961. doi: 10.1107/S1600536811023555

Potassium N-chloro-o-toluenesulfonamidate monohydrate

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

PMCID: PMC3151940 PMID: 21836939

Abstract

In the crystal structure of the title compound, K⁺·C₇H₇ClNO₂S⁻·H₂O, the K⁺ ion is heptacoordinated by two O atoms from water molecules, four sulfonyl O atoms and the Cl atom of the anion. The S—N distance of 1.584 (3) Å is consistent with an S—N double bond. In the crystal, anions are connected by K⁺ cations into layers parallel to the ab plane. The water molecules are coordinated to the K⁺ cations and are additionally linked by intermolecular O—H⋯Cl and O—H⋯N hydrogen bonding.

Related literature

For our studies of the effect of substituents on the structures of N-haloarylsulfonamides, see: Gowda et al. (2009 ▶, 2011a ▶,b ▶); and on the oxidative strengths of N-halolarylsulfonamides, see: Gowda & Kumar (2003 ▶); Usha & Gowda (2006 ▶). For similar structures, see: George et al. (2000 ▶); Olmstead & Power (1986 ▶). For the preparation of the title compound, see: Jyothi & Gowda (2004 ▶).

Experimental

Crystal data

K⁺·C₇H₇ClNO₂S⁻·H₂O
M _r = 261.76
Orthorhombic,
a = 11.4968 (9) Å
b = 6.7990 (5) Å
c = 26.883 (2) Å
V = 2101.4 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.94 mm⁻¹
T = 293 K
0.42 × 0.40 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.694, T _max = 0.766
4396 measured reflections
2150 independent reflections
1992 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.123
S = 0.92
2150 reflections
134 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.59 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/S1600536811023555/nc2234sup1.cif

e-67-0m961-sup1.cif^{(19.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811023555/nc2234Isup2.hkl

e-67-0m961-Isup2.hkl^{(105.8KB, 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
O3—H31⋯Cl1ⁱ	0.85 (1)	2.74 (2)	3.568 (3)	166 (4)
O3—H32⋯N1ⁱⁱ	0.85 (1)	2.08 (1)	2.909 (4)	167 (3)

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

Acknowledgments

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

supplementary crystallographic information

Comment

The crystal structure of the title compound (I) was determined as a part of a project to explore the substituent effects and the effect of replacing sodium ions by potassium ions on the solid state structures of N-halo-arylsulfonamides (Gowda & Kumar, 2003; Usha & Gowda, 2006, Gowda et al., 2009, 2011a,b). The structure resembles those of potassium N, 2-dichloro-benzenesulfonamidate sesquihydrate (II)(Gowda et al., 2011a), potassium N-bromo, o-toluenesulfonamidate sesquihydrate (Gowda et al., 2011b) and sodium N-chloro, o-toluenesulfonamidate sesquihydrate (IV) (Gowda et al., 2009) and other sodium N-chloro-aryl- sulfonamidates (George et al., 2000; Olmstead & Power, 1986).

In the crystal structure of the title compound the K⁺ ion is hepta coordinated by two O atoms from water molecules, four sulfonyl O atoms and one Cl atom of the N-chloro,o-toluenesulfonamidate anions (Fig. 1). This coordination geometry is different from that in II and III, in which the potassium cations are hepta coordinated by three O atoms from water molecules and by four sulfonyl O atoms and and in III, in which the cations are octahedral coordinated.

The S—N distance of 1.584 (3)Å is consistent with an S—N double bond and is in agreement with the observed values of 1.582 (2)Å in II, 1.577 (5)Å in III and 1.590 (2) Å in IV.

The crystal structure comprises sheets parallel to the ab plane (Fig. 2). The molecular packing is additionally stabilized by O—H···Cl and O—H···N hydrogen bonds (Table 1).

Experimental

The title compound was prepared by the method similar to that reported in literature (Jyothi & Gowda, 2004). o-Toluenesulfonamide (2 g) was dissolved in hot aqueous solution (70° C) of 5 M KOH (40 ml). The resulting solution was filtered and Chlorine gas was passed through the clear solution of o-toluenesulfonamide in KOH to obtain the title compound. It was filtered under suction, quickly washed with a minimum quantity of ice cold water and dried. The purity of the compound was checked by determining its melting point (155° C). Colourless prisms of the compound were obtained from its aqueous solution at room temperature.