Potassium N-bromo-2,4-dichloro­benzene­sulfonamidate sesquihydrate

B Thimme Gowda; Sabine Foro; H S Spandana

doi:10.1107/S1600536812042456

. 2012 Oct 20;68(Pt 11):m1368. doi: 10.1107/S1600536812042456

Potassium N-bromo-2,4-dichlorobenzenesulfonamidate sesquihydrate

B Thimme Gowda ^a,^*, Sabine Foro ^b, H S Spandana ^a

PMCID: PMC3515121 PMID: 23284348

Abstract

The asymmetric unit of the title salt, K⁺·C₆H₃BrCl₂NO₂S⁻·1.5H₂O, contains one K⁺ cation, one N-bromo-2,4-dichlorobenzenesulfonamidate anion, one water molecule in general position and one water molecule located on a twofold rotation axis. The K⁺ cation is hepta-coordinated by three water O atoms and four sulfonyl O atoms from three symmetry-related N-bromo-2,4-dichlorobenzenesulfonamide anions. The S=N distance of 1.575 (3) Å is consistent with that of a double bond. In the crystal, the anions are linked by O—H⋯Br and O—H⋯N hydrogen bonds into layers parallel to the ac plane.

Related literature

For preparation of N-haloarylsulfonamides, see: Gowda & Mahadevappa (1983 ▶). For studies of the effect of substituents on the structures of N-haloarylsulfonamides, see: George et al. (2000 ▶); Gowda et al. (2007 ▶, 2011a ▶,b ▶); Olmstead & Power (1986 ▶).

Experimental

Crystal data

K⁺·C₆H₃BrCl₂NO₂S⁻·1.5H₂O
M _r = 740.18
Monoclinic,
a = 12.5263 (7) Å
b = 6.7638 (4) Å
c = 29.703 (2) Å
β = 98.352 (5)°
V = 2489.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.22 mm⁻¹
T = 293 K
0.32 × 0.32 × 0.28 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.345, T _max = 0.384
4960 measured reflections
2535 independent reflections
2204 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.093
S = 1.09
2535 reflections
150 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.76 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2009 ▶); 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

Click here for additional data file.^{(23KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812042456/nc2295sup1.cif

e-68-m1368-sup1.cif^{(23KB, cif)}

Click here for additional data file.^{(124.6KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812042456/nc2295Isup2.hkl

e-68-m1368-Isup2.hkl^{(124.6KB, 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	0.80 (2)	2.78 (2)	3.550 (3)	160 (4)
O3—H32⋯N1	0.81 (2)	2.15 (3)	2.917 (4)	158 (5)
O4—H41⋯N1ⁱⁱ	0.82 (2)	2.16 (2)	2.957 (3)	165 (5)

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

Acknowledgments

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

supplementary crystallographic information

Comment

The present work was undertaken in order to explore the effect of replacing sodium ion by potassium ion on the solid state structures of metal salts of N-haloarylsulfonamidates (Gowda et al., 2007, 2011a,b). As part of this work, the structure of potassium N-bromo-2,4-dichlorobenzenesulfonamidate sesquihydrate (I) has been determined (Fig. 1). The structure of (I) resembles those of potassium N-bromo-2-chlorobenzenesulfonamidate sesquihydrate (II) (Gowda et al., 2011a), potassium N-bromo-4-chlorobenzenesulfonamidate sesquihydrate (III) (Gowda et al., 2011b), sodium N-bromo-2,4-dichlorobenzenesulfonamidate sesquihydrate (IV) (Gowda et al., 2007) and other sodium N-chloro-arylsulfonamidates (George et al., 2000; Olmstead & Power, 1986).

In the title compound, K⁺ ion is hepta coordinated by three O atoms from water molecules and four sulfonyl O atoms of three different N-bromo-2,4-dichlorobenzenesulfonamide anions. The replacement of Na⁺ by K⁺ changes co-ordination from hexa to hepta in the structure (Gowda et al., 2007) and other parameters.

The S—N distance of 1.575 (3) Å is consistent with a S—N double bond and is in agreement with the observed values of 1.582 (4) Å in (II), 1.584 (6) Å in (III) and 1.590 (6) Å in (IV).

The asymmetric unit of (I) consists of one potassium cation, one N-bromo-2,4-dichlorobenzenesulfonamidate anion and one water molecule in general position and and one water molecule located on a twofold rotation axis.

In the crystal structure the anions are linked by intermolecular O—H···Br and O—H···N hydrogen bonding into layers, that are parallel to the ac plane (Fig. 2 and Table 1).

Experimental

The title compound was prepared by a method similar to the one described by Gowda & Mahadevappa (Gowda & Mahadevappa, 1983). 2 g of 2,4-dichlorobenzenesulfonamide was dissolved with stirring in 40 ml of 5M KOH at room temperature. The resultant solution was cooled in ice and 4 ml of liquid bromine was added drop wise with constant stirring. The resultant potassium salt of N-bromo-2,4-dichlorobenzenesulfonamide was filtered under suction, washed quickly with a minimum quantity of ice cold water. The purity of the compound was checked by determining its melting point (203–205° C) and estimating, iodometrically, the amount of active bromine present in it. It was further characterized from its infrared spectrum.

Prism like yellow single crystals of the title compound used in the X-ray diffraction studies were obtained from its aqueous solution at room temperature.