Potassium N-bromo-2-nitro­benzene­sulfonamidate monohydrate

B Thimme Gowda; Sabine Foro; H S Spandana

doi:10.1107/S1600536812042080

. 2012 Oct 13;68(Pt 11):m1358. doi: 10.1107/S1600536812042080

Potassium N-bromo-2-nitrobenzenesulfonamidate monohydrate

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

PMCID: PMC3515114 PMID: 23284341

Abstract

In the title compound, K⁺·C₆H₄BrN₂O₄S⁻·H₂O, the K⁺ ion is hepta-coordinated by two O atoms from two different water molecules, three sulfonyl O atoms from three N-bromo-2-nitro-benzenesulfonamidate anions and two nitro O atoms from two N-bromo-2-nitro-benzenesulfonamidate anions. The S—N distance of 1.576 (4) Å is consistent with an S=N double bond. The crystal structure is stabilized by intermolecular O—H⋯N and O—H⋯Br hydrogen bonds which link the molecules into polymeric layers running parallel to the bc plane.

Related literature

For the preparation of metal salts of N-haloarylsulfonamides, see: Gowda & Mahadevappa (1983 ▶); Usha & Gowda (2006 ▶). For studies on the effect of substituents and metal ions on the structures of N-haloarylsulfonamides, see: George et al. (2000 ▶); Gowda et al. (2011a ▶,b ▶); Olmstead & Power (1986 ▶). For positioning of water H atoms, see: Nardelli (1999 ▶).

Experimental

Crystal data

K⁺·C₆H₄BrN₂O₄S⁻·H₂O
M _r = 337.20
Monoclinic,
a = 13.034 (2) Å
b = 12.815 (2) Å
c = 6.7741 (9) Å
β = 100.65 (1)°
V = 1112.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.27 mm⁻¹
T = 293 K
0.48 × 0.48 × 0.24 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.234, T _max = 0.428
3896 measured reflections
2236 independent reflections
1847 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.145
S = 1.06
2236 reflections
152 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.79 e Å⁻³
Δρ_min = −1.21 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.^{(21.6KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812042080/zl2509sup1.cif

e-68-m1358-sup1.cif^{(21.6KB, cif)}

Click here for additional data file.^{(109.9KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812042080/zl2509Isup2.hkl

e-68-m1358-Isup2.hkl^{(109.9KB, hkl)}

Click here for additional data file.^{(3.7KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812042080/zl2509Isup3.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
O5—H51⋯N1ⁱ	0.84 (2)	2.13 (3)	2.926 (5)	157 (5)
O5—H52⋯Br1ⁱⁱ	0.84 (2)	2.85 (4)	3.509 (4)	137 (4)

Open in a new tab

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

In the present work, to explore the effect of substituents on the crystal structures of metal salts of N-haloarylsulfonamidates (George et al., 2000; Gowda et al., 2011a,b; Olmstead & Power, 1986), the crystal structure of potassium N-bromo-2-nitro-benzenesulfonamidate monohydrate (I) has been determined (Fig. 1). The structure of (I) resembles those of potassium N-bromo-2-chloro-benzenesulfonamidate sesquihydrate (II) (Gowda et al., 2011a), potassium N-bromo-2-methyl-benzenesulfonamidate sesquihydrate (III) (Gowda et al., 2011b), and sodium N-chloro-arylsulfonamidates (George et al., 2000; Olmstead & Power, 1986).

In the title compound (I), the K⁺ ion is hepta coordinated by two O atoms from two different water molecules, three sulfonyl O atoms from three N-bromo-2-nitro-benzenesulfonamidate anions and two nitro O atoms from two N-bromo-2-nitro-benzenesulfonamidate anions (Fig 2.). This is in contrast to K⁺ ion hepta coordination by three O atoms from water molecules and by four sulfonyl O atoms of three N-bromo-2-chloro-benzenesulfonamide anions in (II) and three N-bromo-2-methyl-benzenesulfonamide anions in (III).

The S—N distance of 1.576 (4) Å in (I) is consistent with an S—N double bond and is in agreement with the observed values of 1.582 (4) Å in (II) and 1.577 (5) Å in (III).

The packing diagram consists of a two-dimensional polymeric layer running parallel to the bc plane (Fig. 2). The molecular packing is stabilized by O5—H51···N1 and O5—H52···Br1 hydrogen bonds (Table 1).

Experimental

The title compound was prepared by a method similar to the one described by Gowda & Mahadevappa (Gowda & Mahadevappa, 1983) and Usha & Gowda (Usha & Gowda, 2006). 2 g of 2-nitrobenzenesulfonamide 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-nitro-benzenesulfonamidate monohydrate 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 (175–177°C) and estimating, iodometrically, the amount of active bromine present in it. It was further characterized from its infrared spectrum. The characteristic absorptions observed are 3624.3, 3333.0, 3192.2, 2978.1, 2922.2, 2075.4, 1626.0, 1602.9, 1477.5, 1452.4, 1242.2, 1122.6, 1060.9, 937.4, 817.8, 686.7, 640.4, 578.6, 549.6, 524.6 and 470.6 cm^-1.

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.