Potassium N-bromo-4-chloro-2-methyl­benzene­sulfonamidate monohydrate

Spandana, H.S.; Foro, S.; Gowda, B.T.

doi:10.1107/S1600536813014979

metal-organic compounds

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Volume 69| Part 7| July 2013| Page m370

https://doi.org/10.1107/S1600536813014979

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Potassium N-bromo-4-chloro-2-methylbenzenesulfonamidate monohydrate

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

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, ^bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany, and ^cJnanabharathi Campus, Bangalore University, Bangalore 560 056, India
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 26 May 2013; accepted 30 May 2013; online 8 June 2013)

In the title compound, K⁺·C₇H₆BrClNO₂S⁻·H₂O, the K⁺ cation is heptacoordinated by two water O atoms, four sulfonyl O atoms of four different N-bromo-4-chloro-2-methylbenzenesulfonamidate anions, and one Br atom of one of the anions. The S—N distance of 1.584 (3) Å is consistent with an S=N double bond. In the crystal, the anions are linked into layers by O—H⋯Br and O—H⋯N hydrogen bonds.

Related literature

For preparation of N-haloarylsulfonamides, see: Gowda & Mahadevappa (1983 ). For studies of the effect of substituents on the structures of N-haloarylsulfonamidates, see: George et al. (2000 ); Gowda et al. (2011a ,b , 2012 ); Olmstead & Power (1986 ). For restrained geometry, see: Nardelli (1999 )

Experimental

Crystal data

K⁺·C₇H₆BrClNO₂S·H₂O
M_r = 340.66
Monoclinic, P 2₁ /c
a = 15.265 (1) Å
b = 11.4817 (8) Å
c = 6.7552 (5) Å
β = 101.617 (7)°
V = 1159.72 (14) Å³
Z = 4
Mo Kα radiation
μ = 4.30 mm⁻¹
T = 293 K
0.42 × 0.30 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.265, T_max = 0.627
4387 measured reflections
2367 independent reflections
1971 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.129
S = 1.10
2367 reflections
143 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.97 e Å⁻³
Δρ_min = −1.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H31⋯N1ⁱ	0.84 (2)	2.00 (2)	2.835 (5)	173 (5)
O3—H32⋯Br1ⁱⁱ	0.82 (2)	2.93 (2)	3.744 (3)	173 (4)
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{5\over 2}}]$ ; (ii) -x, -y+1, -z+3.

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813014979/rz5069sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813014979/rz5069Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813014979/rz5069Isup3.cml

checkCIF report

Comment top

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., 2011a,b, 2012), the structure of potassium N-bromo-2-methyl-4-chlorobenzenesulfonamidate monohydrate (I) has been determined (Fig. 1). The structure of (I) resembles those of potassium N-bromo-2,4-dichlorobenzenesulfonamidate sesquihydrate (II) (Gowda et al., 2012), potassium N-bromo-4-chlorobenzenesulfonamidate monohydrate (III) (Gowda et al., 2011a), potassium N-bromo-2-methyl-benzenesulfonamidate sesquihydrate (IV) (Gowda et al., 2011b) and other sodium N-chloroarylsulfonamidates (George et al., 2000; Olmstead & Power, 1986).

In the title compound, the K⁺ ion is hepta coordinated by two O atoms from two different water molecules, four sulfonyl O atoms of four different N-bromo-2-methyl-4-chlorobenzenesulfonamide anions and one Br atom of N-bromo-2-methyl-4-chlorobenzenesulfonamide anion, similarly to that observed in III. But this is in contrast to the hepta coordination of K⁺ ion by three O atoms from three different water molecules, four sulfonyl O atoms of three different N-bromo-2-methyl-4-chlorobenzenesulfonamide anions in II and IV.

The S—N distance of 1.584 (3) Å is consistent with a S—N double bond and is in agreement with the observed values of 1.575 (3) Å in (II), 1.584 (6) Å in (III) and 1.577 (5) Å in (IV).

In the crystal structure the anions are linked by intermolecular O3—H32···Br1 and O3—H31···N1 hydrogen bonding into layers (Fig. 2 and Table 1).

Related literature top

For preparation of N-haloarylsulfonamides, see: Gowda & Mahadevappa (1983). For studies of the effect of substituents on the structures of N-haloarylsulfonamidates, see: George et al. (2000); Gowda et al. (2011a,b, 2012); Olmstead & Power (1986). For restrained geometry, see: Nardelli (1999)

Experimental top

The title compound was prepared by a method similar to the one described by Gowda & Mahadevappa (Gowda & Mahadevappa, 1983). 2 g of 2-methyl-4-chlorobenzenesulfonamide 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-methyl-4-chlorobenzenesulfon-amidate 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 (208° 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.

Structure description top

The S—N distance of 1.584 (3) Å is consistent with a S—N double bond and is in agreement with the observed values of 1.575 (3) Å in (II), 1.584 (6) Å in (III) and 1.577 (5) Å in (IV).

In the crystal structure the anions are linked by intermolecular O3—H32···Br1 and O3—H31···N1 hydrogen bonding into layers (Fig. 2 and Table 1).

For preparation of N-haloarylsulfonamides, see: Gowda & Mahadevappa (1983). For studies of the effect of substituents on the structures of N-haloarylsulfonamidates, see: George et al. (2000); Gowda et al. (2011a,b, 2012); Olmstead & Power (1986). For restrained geometry, see: Nardelli (1999)

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis CCD (Oxford Diffraction, 2009); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom labelling extended to show the coordination geometry of the K⁺ cation. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines.

Potassium N-bromo-4-chloro-2-methylbenzenesulfonamidate monohydrate top

Crystal data top

K⁺·C₇H₆BrClNO₂S·H₂O	F(000) = 672
M_r = 340.66	D_x = 1.951 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2484 reflections
a = 15.265 (1) Å	θ = 3.1–27.8°
b = 11.4817 (8) Å	µ = 4.30 mm⁻¹
c = 6.7552 (5) Å	T = 293 K
β = 101.617 (7)°	Prism, yellow
V = 1159.72 (14) Å³	0.42 × 0.30 × 0.12 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector	2367 independent reflections
Radiation source: fine-focus sealed tube	1971 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Rotation method data acquisition using ω scans.	θ_max = 26.4°, θ_min = 3.3°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −19→14
T_min = 0.265, T_max = 0.627	k = −14→14
4387 measured reflections	l = −8→8

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0847P)² + 0.3516P] where P = (F_o² + 2F_c²)/3
2367 reflections	(Δ/σ)_max = 0.001
143 parameters	Δρ_max = 0.97 e Å⁻³
3 restraints	Δρ_min = −1.18 e Å⁻³

Crystal data top

K⁺·C₇H₆BrClNO₂S·H₂O	V = 1159.72 (14) Å³
M_r = 340.66	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.265 (1) Å	µ = 4.30 mm⁻¹
b = 11.4817 (8) Å	T = 293 K
c = 6.7552 (5) Å	0.42 × 0.30 × 0.12 mm
β = 101.617 (7)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector	2367 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	1971 reflections with I > 2σ(I)
T_min = 0.265, T_max = 0.627	R_int = 0.030
4387 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	3 restraints
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.97 e Å⁻³
2367 reflections	Δρ_min = −1.18 e Å⁻³
143 parameters

Special details top

Experimental. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic)treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.23345 (3)	0.48001 (4)	1.31553 (6)	0.03995 (19)
K1	0.04696 (6)	0.63387 (8)	1.34287 (13)	0.0345 (2)
Cl1	0.53340 (9)	0.62486 (17)	0.7141 (2)	0.0736 (5)
S1	0.15358 (6)	0.55763 (8)	0.91712 (13)	0.0261 (2)
O1	0.09358 (19)	0.5225 (3)	0.7316 (4)	0.0384 (7)
O2	0.1350 (2)	0.6710 (2)	0.9950 (4)	0.0373 (7)
O3	−0.0700 (2)	0.7364 (3)	1.5563 (6)	0.0487 (8)
H31	−0.091 (3)	0.801 (3)	1.511 (8)	0.058*
H32	−0.109 (3)	0.694 (3)	1.588 (8)	0.058*
N1	0.1502 (2)	0.4538 (3)	1.0698 (5)	0.0342 (8)
C1	0.2632 (2)	0.5708 (3)	0.8616 (5)	0.0252 (7)
C2	0.3104 (3)	0.4738 (3)	0.8140 (6)	0.0299 (8)
C3	0.3941 (3)	0.4935 (4)	0.7699 (7)	0.0381 (10)
H3	0.4277	0.4310	0.7389	0.046*
C4	0.4281 (3)	0.6058 (5)	0.7717 (6)	0.0412 (11)
C5	0.3810 (3)	0.7006 (4)	0.8170 (6)	0.0433 (11)
H5	0.4046	0.7753	0.8170	0.052*
C6	0.2980 (3)	0.6829 (4)	0.8625 (6)	0.0337 (8)
H6	0.2651	0.7460	0.8939	0.040*
C7	0.2770 (3)	0.3482 (3)	0.8127 (6)	0.0330 (9)
H7A	0.2162	0.3443	0.7399	0.050*
H7B	0.2801	0.3224	0.9491	0.050*
H7C	0.3137	0.2989	0.7483	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0480 (3)	0.0389 (3)	0.0321 (3)	0.00845 (18)	0.00612 (19)	0.00640 (16)
K1	0.0322 (5)	0.0317 (5)	0.0400 (5)	−0.0031 (3)	0.0087 (4)	−0.0016 (4)
Cl1	0.0330 (7)	0.1197 (13)	0.0715 (9)	−0.0165 (7)	0.0187 (6)	0.0105 (8)
S1	0.0229 (5)	0.0261 (5)	0.0291 (5)	0.0015 (4)	0.0047 (3)	0.0014 (4)
O1	0.0251 (15)	0.0519 (18)	0.0348 (16)	−0.0037 (13)	−0.0019 (12)	0.0013 (13)
O2	0.0389 (17)	0.0294 (14)	0.0460 (17)	0.0086 (13)	0.0139 (12)	0.0002 (12)
O3	0.042 (2)	0.0411 (18)	0.066 (2)	0.0001 (15)	0.0176 (15)	−0.0089 (17)
N1	0.0352 (19)	0.0316 (18)	0.0374 (19)	−0.0041 (14)	0.0111 (14)	0.0036 (14)
C1	0.0226 (18)	0.0256 (19)	0.0268 (17)	−0.0038 (15)	0.0039 (14)	0.0022 (14)
C2	0.031 (2)	0.032 (2)	0.0265 (19)	0.0019 (16)	0.0050 (15)	0.0015 (15)
C3	0.029 (2)	0.050 (3)	0.037 (2)	0.0066 (18)	0.0090 (17)	0.0018 (19)
C4	0.022 (2)	0.069 (3)	0.034 (2)	−0.010 (2)	0.0065 (16)	0.007 (2)
C5	0.041 (3)	0.048 (3)	0.041 (2)	−0.018 (2)	0.0081 (18)	0.000 (2)
C6	0.037 (2)	0.029 (2)	0.035 (2)	−0.0032 (17)	0.0048 (16)	0.0009 (16)
C7	0.033 (2)	0.029 (2)	0.038 (2)	0.0080 (16)	0.0091 (16)	−0.0041 (16)

Geometric parameters (Å, º) top

Br1—N1	1.901 (4)	O3—K1ⁱ	2.786 (4)
Br1—K1	3.3868 (10)	O3—H31	0.842 (19)
K1—O2ⁱ	2.706 (3)	O3—H32	0.824 (19)
K1—O1ⁱⁱ	2.765 (3)	C1—C6	1.392 (5)
K1—O3	2.773 (3)	C1—C2	1.399 (5)
K1—O3ⁱⁱⁱ	2.786 (4)	C2—C3	1.387 (6)
K1—O1^iv	2.878 (3)	C2—C7	1.529 (5)
K1—O2	2.964 (3)	C3—C4	1.389 (7)
K1—N1	3.366 (4)	C3—H3	0.9300
Cl1—C4	1.743 (4)	C4—C5	1.373 (7)
S1—O1	1.453 (3)	C5—C6	1.377 (6)
S1—O2	1.453 (3)	C5—H5	0.9300
S1—N1	1.584 (3)	C6—H6	0.9300
S1—C1	1.794 (4)	C7—H7A	0.9600
O1—K1ⁱⁱ	2.765 (3)	C7—H7B	0.9600
O1—K1^v	2.878 (3)	C7—H7C	0.9600
O2—K1ⁱⁱⁱ	2.706 (3)

N1—Br1—K1	73.06 (11)	O3—K1—K1ⁱⁱⁱ	104.29 (8)
O2ⁱ—K1—O1ⁱⁱ	156.13 (10)	O3ⁱⁱⁱ—K1—K1ⁱⁱⁱ	39.16 (7)
O2ⁱ—K1—O3	76.93 (10)	O1^iv—K1—K1ⁱⁱⁱ	162.22 (6)
O1ⁱⁱ—K1—O3	79.22 (10)	O2—K1—K1ⁱⁱⁱ	38.44 (5)
O2ⁱ—K1—O3ⁱⁱⁱ	91.20 (10)	N1—K1—K1ⁱⁱⁱ	82.90 (6)
O1ⁱⁱ—K1—O3ⁱⁱⁱ	81.70 (9)	Br1—K1—K1ⁱⁱⁱ	98.488 (15)
O3—K1—O3ⁱⁱⁱ	75.20 (7)	S1—K1—K1ⁱⁱⁱ	57.636 (16)
O2ⁱ—K1—O1^iv	90.50 (9)	K1^vi—K1—K1ⁱⁱⁱ	156.16 (3)
O1ⁱⁱ—K1—O1^iv	85.28 (9)	K1ⁱ—K1—K1ⁱⁱⁱ	103.41 (4)
O3—K1—O1^iv	77.35 (10)	O1—S1—O2	115.20 (18)
O3ⁱⁱⁱ—K1—O1^iv	151.34 (10)	O1—S1—N1	104.79 (19)
O2ⁱ—K1—O2	84.95 (8)	O2—S1—N1	113.85 (17)
O1ⁱⁱ—K1—O2	114.10 (9)	O1—S1—C1	107.20 (17)
O3—K1—O2	142.52 (10)	O2—S1—C1	104.97 (18)
O3ⁱⁱⁱ—K1—O2	72.64 (9)	N1—S1—C1	110.72 (18)
O1^iv—K1—O2	135.98 (9)	O1—S1—K1	116.01 (13)
O2ⁱ—K1—N1	117.70 (9)	O2—S1—K1	49.88 (12)
O1ⁱⁱ—K1—N1	86.17 (9)	N1—S1—K1	65.99 (13)
O3—K1—N1	165.27 (10)	C1—S1—K1	136.12 (12)
O3ⁱⁱⁱ—K1—N1	104.65 (10)	S1—O1—K1ⁱⁱ	131.95 (17)
O1^iv—K1—N1	99.80 (9)	S1—O1—K1^v	131.38 (17)
O2—K1—N1	46.90 (8)	K1ⁱⁱ—O1—K1^v	94.72 (8)
O2ⁱ—K1—Br1	95.38 (7)	S1—O2—K1ⁱⁱⁱ	136.25 (17)
O1ⁱⁱ—K1—Br1	106.34 (7)	S1—O2—K1	108.10 (15)
O3—K1—Br1	152.38 (8)	K1ⁱⁱⁱ—O2—K1	98.64 (9)
O3ⁱⁱⁱ—K1—Br1	132.00 (8)	K1—O3—K1ⁱ	101.45 (11)
O1^iv—K1—Br1	76.23 (7)	K1—O3—H31	115 (4)
O2—K1—Br1	60.75 (6)	K1ⁱ—O3—H31	86 (4)
N1—K1—Br1	32.69 (6)	K1—O3—H32	117 (4)
O2ⁱ—K1—S1	103.26 (7)	K1ⁱ—O3—H32	122 (4)
O1ⁱⁱ—K1—S1	98.76 (7)	H31—O3—H32	112 (3)
O3—K1—S1	159.84 (8)	S1—N1—Br1	110.23 (19)
O3ⁱⁱⁱ—K1—S1	84.65 (8)	S1—N1—K1	88.56 (14)
O1^iv—K1—S1	122.67 (7)	Br1—N1—K1	74.25 (11)
O2—K1—S1	22.02 (6)	C6—C1—C2	121.6 (3)
N1—K1—S1	25.45 (6)	C6—C1—S1	116.6 (3)
Br1—K1—S1	47.56 (2)	C2—C1—S1	121.8 (3)
O2ⁱ—K1—K1^vi	127.95 (7)	C3—C2—C1	117.3 (4)
O1ⁱⁱ—K1—K1^vi	43.70 (6)	C3—C2—C7	118.2 (4)
O3—K1—K1^vi	73.95 (8)	C1—C2—C7	124.4 (3)
O3ⁱⁱⁱ—K1—K1^vi	120.81 (7)	C2—C3—C4	120.5 (4)
O1^iv—K1—K1^vi	41.58 (6)	C2—C3—H3	119.7
O2—K1—K1^vi	140.40 (7)	C4—C3—H3	119.7
N1—K1—K1^vi	94.21 (6)	C5—C4—C3	121.8 (4)
Br1—K1—K1^vi	91.28 (3)	C5—C4—Cl1	119.9 (4)
S1—K1—K1^vi	118.40 (4)	C3—C4—Cl1	118.4 (4)
O2ⁱ—K1—K1ⁱ	42.91 (6)	C4—C5—C6	118.6 (4)
O1ⁱⁱ—K1—K1ⁱ	115.00 (7)	C4—C5—H5	120.7
O3—K1—K1ⁱ	39.39 (7)	C6—C5—H5	120.7
O3ⁱⁱⁱ—K1—K1ⁱ	96.47 (8)	C5—C6—C1	120.2 (4)
O1^iv—K1—K1ⁱ	66.31 (6)	C5—C6—H6	119.9
O2—K1—K1ⁱ	127.22 (6)	C1—C6—H6	119.9
N1—K1—K1ⁱ	152.22 (6)	C2—C7—H7A	109.5
Br1—K1—K1ⁱ	119.924 (16)	C2—C7—H7B	109.5
S1—K1—K1ⁱ	146.08 (3)	H7A—C7—H7B	109.5
K1^vi—K1—K1ⁱ	90.17 (2)	C2—C7—H7C	109.5
O2ⁱ—K1—K1ⁱⁱⁱ	72.93 (7)	H7A—C7—H7C	109.5
O1ⁱⁱ—K1—K1ⁱⁱⁱ	112.48 (6)	H7B—C7—H7C	109.5

N1—Br1—K1—O2ⁱ	−135.87 (12)	Br1—K1—O2—S1	47.29 (13)
N1—Br1—K1—O1ⁱⁱ	54.15 (12)	K1^vi—K1—O2—S1	−3.2 (2)
N1—Br1—K1—O3	152.19 (19)	K1ⁱ—K1—O2—S1	154.31 (11)
N1—Br1—K1—O3ⁱⁱⁱ	−39.37 (14)	K1ⁱⁱⁱ—K1—O2—S1	−144.9 (2)
N1—Br1—K1—O1^iv	134.94 (12)	O2ⁱ—K1—O2—K1ⁱⁱⁱ	−68.74 (14)
N1—Br1—K1—O2	−54.73 (12)	O1ⁱⁱ—K1—O2—K1ⁱⁱⁱ	96.32 (10)
N1—Br1—K1—S1	−32.81 (11)	O3—K1—O2—K1ⁱⁱⁱ	−8.0 (2)
N1—Br1—K1—K1^vi	95.82 (11)	O3ⁱⁱⁱ—K1—O2—K1ⁱⁱⁱ	24.11 (10)
N1—Br1—K1—K1ⁱ	−173.25 (11)	O1^iv—K1—O2—K1ⁱⁱⁱ	−154.21 (10)
N1—Br1—K1—K1ⁱⁱⁱ	−62.37 (10)	N1—K1—O2—K1ⁱⁱⁱ	155.05 (16)
O2ⁱ—K1—S1—O1	−136.58 (16)	Br1—K1—O2—K1ⁱⁱⁱ	−167.79 (11)
O1ⁱⁱ—K1—S1—O1	34.1 (2)	S1—K1—O2—K1ⁱⁱⁱ	144.9 (2)
O3—K1—S1—O1	−48.4 (3)	K1^vi—K1—O2—K1ⁱⁱⁱ	141.75 (6)
O3ⁱⁱⁱ—K1—S1—O1	−46.60 (16)	K1ⁱ—K1—O2—K1ⁱⁱⁱ	−60.78 (11)
O1^iv—K1—S1—O1	124.12 (19)	O2ⁱ—K1—O3—K1ⁱ	−25.56 (10)
O2—K1—S1—O1	−102.0 (2)	O1ⁱⁱ—K1—O3—K1ⁱ	155.48 (12)
N1—K1—S1—O1	95.4 (2)	O3ⁱⁱⁱ—K1—O3—K1ⁱ	−120.36 (16)
Br1—K1—S1—O1	138.29 (15)	O1^iv—K1—O3—K1ⁱ	67.95 (11)
K1^vi—K1—S1—O1	75.68 (15)	O2—K1—O3—K1ⁱ	−88.74 (18)
K1ⁱ—K1—S1—O1	−140.24 (14)	N1—K1—O3—K1ⁱ	148.3 (3)
K1ⁱⁱⁱ—K1—S1—O1	−77.00 (14)	Br1—K1—O3—K1ⁱ	50.8 (2)
O2ⁱ—K1—S1—O2	−34.55 (11)	S1—K1—O3—K1ⁱ	−118.5 (2)
O1ⁱⁱ—K1—S1—O2	136.15 (17)	K1^vi—K1—O3—K1ⁱ	110.80 (10)
O3—K1—S1—O2	53.6 (3)	K1ⁱⁱⁱ—K1—O3—K1ⁱ	−93.84 (10)
O3ⁱⁱⁱ—K1—S1—O2	55.42 (18)	O1—S1—N1—Br1	175.11 (18)
O1^iv—K1—S1—O2	−133.86 (18)	O2—S1—N1—Br1	−58.1 (2)
N1—K1—S1—O2	−162.6 (2)	C1—S1—N1—Br1	59.8 (2)
Br1—K1—S1—O2	−119.69 (16)	K1—S1—N1—Br1	−72.62 (15)
K1^vi—K1—S1—O2	177.70 (17)	O1—S1—N1—K1	−112.27 (15)
K1ⁱ—K1—S1—O2	−38.22 (17)	O2—S1—N1—K1	14.48 (18)
K1ⁱⁱⁱ—K1—S1—O2	25.03 (16)	C1—S1—N1—K1	132.46 (14)
O2ⁱ—K1—S1—N1	128.05 (16)	K1—Br1—N1—S1	82.43 (18)
O1ⁱⁱ—K1—S1—N1	−61.25 (16)	O2ⁱ—K1—N1—S1	−59.97 (17)
O3—K1—S1—N1	−143.8 (3)	O1ⁱⁱ—K1—N1—S1	119.72 (15)
O3ⁱⁱⁱ—K1—S1—N1	−141.97 (16)	O3—K1—N1—S1	126.8 (4)
O1^iv—K1—S1—N1	28.75 (16)	O3ⁱⁱⁱ—K1—N1—S1	39.34 (16)
O2—K1—S1—N1	162.6 (2)	O1^iv—K1—N1—S1	−155.74 (14)
Br1—K1—S1—N1	42.92 (15)	O2—K1—N1—S1	−8.83 (11)
K1^vi—K1—S1—N1	−19.69 (15)	Br1—K1—N1—S1	−111.50 (18)
K1ⁱ—K1—S1—N1	124.39 (15)	K1^vi—K1—N1—S1	162.71 (13)
K1ⁱⁱⁱ—K1—S1—N1	−172.37 (15)	K1ⁱ—K1—N1—S1	−98.89 (17)
O2ⁱ—K1—S1—C1	32.56 (19)	K1ⁱⁱⁱ—K1—N1—S1	6.49 (13)
O1ⁱⁱ—K1—S1—C1	−156.73 (19)	O2ⁱ—K1—N1—Br1	51.53 (13)
O3—K1—S1—C1	120.7 (3)	O1ⁱⁱ—K1—N1—Br1	−128.78 (11)
O3ⁱⁱⁱ—K1—S1—C1	122.54 (19)	O3—K1—N1—Br1	−121.7 (4)
O1^iv—K1—S1—C1	−66.74 (19)	O3ⁱⁱⁱ—K1—N1—Br1	150.84 (10)
O2—K1—S1—C1	67.1 (2)	O1^iv—K1—N1—Br1	−44.24 (11)
N1—K1—S1—C1	−95.5 (2)	O2—K1—N1—Br1	102.67 (14)
Br1—K1—S1—C1	−52.57 (18)	S1—K1—N1—Br1	111.50 (18)
K1^vi—K1—S1—C1	−115.18 (18)	K1^vi—K1—N1—Br1	−85.79 (9)
K1ⁱ—K1—S1—C1	28.90 (19)	K1ⁱ—K1—N1—Br1	12.6 (2)
K1ⁱⁱⁱ—K1—S1—C1	92.15 (18)	K1ⁱⁱⁱ—K1—N1—Br1	117.99 (9)
O2—S1—O1—K1ⁱⁱ	−104.0 (2)	O1—S1—C1—C6	110.7 (3)
N1—S1—O1—K1ⁱⁱ	22.0 (3)	O2—S1—C1—C6	−12.3 (3)
C1—S1—O1—K1ⁱⁱ	139.7 (2)	N1—S1—C1—C6	−135.6 (3)
K1—S1—O1—K1ⁱⁱ	−48.2 (3)	K1—S1—C1—C6	−59.1 (4)
O2—S1—O1—K1^v	56.0 (3)	O1—S1—C1—C2	−67.5 (3)
N1—S1—O1—K1^v	−178.1 (2)	O2—S1—C1—C2	169.5 (3)
C1—S1—O1—K1^v	−60.4 (3)	N1—S1—C1—C2	46.2 (4)
K1—S1—O1—K1^v	111.75 (18)	K1—S1—C1—C2	122.7 (3)
O1—S1—O2—K1ⁱⁱⁱ	−21.0 (3)	C6—C1—C2—C3	0.8 (5)
N1—S1—O2—K1ⁱⁱⁱ	−142.1 (2)	S1—C1—C2—C3	178.9 (3)
C1—S1—O2—K1ⁱⁱⁱ	96.6 (2)	C6—C1—C2—C7	179.2 (4)
K1—S1—O2—K1ⁱⁱⁱ	−124.7 (3)	S1—C1—C2—C7	−2.7 (5)
O1—S1—O2—K1	103.73 (18)	C1—C2—C3—C4	−0.6 (6)
N1—S1—O2—K1	−17.4 (2)	C7—C2—C3—C4	−179.1 (4)
C1—S1—O2—K1	−138.62 (14)	C2—C3—C4—C5	0.1 (7)
O2ⁱ—K1—O2—S1	146.34 (11)	C2—C3—C4—Cl1	−179.8 (3)
O1ⁱⁱ—K1—O2—S1	−48.60 (18)	C3—C4—C5—C6	0.3 (7)
O3—K1—O2—S1	−152.88 (15)	Cl1—C4—C5—C6	−179.8 (3)
O3ⁱⁱⁱ—K1—O2—S1	−120.81 (18)	C4—C5—C6—C1	−0.1 (6)
O1^iv—K1—O2—S1	60.9 (2)	C2—C1—C6—C5	−0.4 (6)
N1—K1—O2—S1	10.13 (13)	S1—C1—C6—C5	−178.6 (3)

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, −y+1, −z+2; (iii) x, −y+3/2, z−1/2; (iv) x, y, z+1; (v) x, y, z−1; (vi) −x, −y+1, −z+3.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H31···N1^vii	0.84 (2)	2.00 (2)	2.835 (5)	173 (5)
O3—H32···Br1^vi	0.82 (2)	2.93 (2)	3.744 (3)	173 (4)

Symmetry codes: (vi) −x, −y+1, −z+3; (vii) −x, y+1/2, −z+5/2.

Experimental details

Crystal data
Chemical formula	K⁺·C₇H₆BrClNO₂S·H₂O
M_r	340.66
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	15.265 (1), 11.4817 (8), 6.7552 (5)
β (°)	101.617 (7)
V (Å³)	1159.72 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.30
Crystal size (mm)	0.42 × 0.30 × 0.12

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)
T_min, T_max	0.265, 0.627
No. of measured, independent and observed [I > 2σ(I)] reflections	4387, 2367, 1971
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.129, 1.10
No. of reflections	2367
No. of parameters	143
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.97, −1.18

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H31···N1ⁱ	0.842 (19)	2.00 (2)	2.835 (5)	173 (5)
O3—H32···Br1ⁱⁱ	0.824 (19)	2.925 (19)	3.744 (3)	173 (4)

Symmetry codes: (i) −x, y+1/2, −z+5/2; (ii) −x, −y+1, −z+3.

Acknowledgements

HSS thanks the Department of Science and Technology, Government of India, New Delhi, for a Research Fellowship through PURSE grants. BTG thanks the University Grants Commission, Government of India, New Delhi, for a grant under the UGC–BSR one-time grant to Faculty/Professors.

References

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