Potassium N-bromo-4-chloro-2-methyl-benzene-sulfonamidate monohydrate.

In the title compound, K(+)·C7H6BrClNO2S(-)·H2O, the K(+) cation is hepta-coordinated by two water O atoms, four sulfonyl O atoms of four different N-bromo-4-chloro-2-methyl-benzene-sulfonamidate 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. (2011 ▶, 2012 ▶); Olmstead & Power (1986 ▶). For restrained geometry, see: Nardelli (1999 ▶)

Experimental

Crystal data

K+·C7H6BrClNO2S·H2O

M = 340.66

Monoclinic,

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 ▶) 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[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.129

S = 1.10

2367 reflections

143 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.97 e Å−3

Δρmin = −1.18 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813014979/rz5069sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813014979/rz5069Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813014979/rz5069Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

K+·C7H6BrClNO2S·H2O	F(000) = 672
Mr = 340.66	Dx = 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

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	Rint = 0.030
Rotation method data acquisition using ω scans.	θmax = 26.4°, θmin = 3.3°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −19→14
Tmin = 0.265, Tmax = 0.627	k = −14→14
4387 measured reflections	l = −8→8

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(Fo2) + (0.0847P)2 + 0.3516P] where P = (Fo2 + 2Fc2)/3
2367 reflections	(Δ/σ)max = 0.001
143 parameters	Δρmax = 0.97 e Å−3
3 restraints	Δρmin = −1.18 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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—O1iv	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—K1v	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)	O1iv—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—O1iv	90.50 (9)	K1vi—K1—K1iii	156.16 (3)
O1ii—K1—O1iv	85.28 (9)	K1i—K1—K1iii	103.41 (4)
O3—K1—O1iv	77.35 (10)	O1—S1—O2	115.20 (18)
O3iii—K1—O1iv	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)
O1iv—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)
O1iv—K1—N1	99.80 (9)	S1—O1—K1v	131.38 (17)
O2—K1—N1	46.90 (8)	K1ii—O1—K1v	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)
O1iv—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)
O1iv—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—K1vi	127.95 (7)	C3—C2—C1	117.3 (4)
O1ii—K1—K1vi	43.70 (6)	C3—C2—C7	118.2 (4)
O3—K1—K1vi	73.95 (8)	C1—C2—C7	124.4 (3)
O3iii—K1—K1vi	120.81 (7)	C2—C3—C4	120.5 (4)
O1iv—K1—K1vi	41.58 (6)	C2—C3—H3	119.7
O2—K1—K1vi	140.40 (7)	C4—C3—H3	119.7
N1—K1—K1vi	94.21 (6)	C5—C4—C3	121.8 (4)
Br1—K1—K1vi	91.28 (3)	C5—C4—Cl1	119.9 (4)
S1—K1—K1vi	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)
O1iv—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
K1vi—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)	K1vi—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—O1iv	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—K1vi	95.82 (11)	O3iii—K1—O2—K1iii	24.11 (10)
N1—Br1—K1—K1i	−173.25 (11)	O1iv—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)	K1vi—K1—O2—K1iii	141.75 (6)
O3iii—K1—S1—O1	−46.60 (16)	K1i—K1—O2—K1iii	−60.78 (11)
O1iv—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)	O1iv—K1—O3—K1i	67.95 (11)
K1vi—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)	K1vi—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)
O1iv—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)
K1vi—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)
O1iv—K1—S1—N1	28.75 (16)	O3iii—K1—N1—S1	39.34 (16)
O2—K1—S1—N1	162.6 (2)	O1iv—K1—N1—S1	−155.74 (14)
Br1—K1—S1—N1	42.92 (15)	O2—K1—N1—S1	−8.83 (11)
K1vi—K1—S1—N1	−19.69 (15)	Br1—K1—N1—S1	−111.50 (18)
K1i—K1—S1—N1	124.39 (15)	K1vi—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)
O1iv—K1—S1—C1	−66.74 (19)	O3iii—K1—N1—Br1	150.84 (10)
O2—K1—S1—C1	67.1 (2)	O1iv—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)
K1vi—K1—S1—C1	−115.18 (18)	K1vi—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—K1v	56.0 (3)	O1—S1—C1—C2	−67.5 (3)
N1—S1—O1—K1v	−178.1 (2)	O2—S1—C1—C2	169.5 (3)
C1—S1—O1—K1v	−60.4 (3)	N1—S1—C1—C2	46.2 (4)
K1—S1—O1—K1v	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)
O1iv—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)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H31···N1vii	0.84 (2)	2.00 (2)	2.835 (5)	173 (5)
O3—H32···Br1vi	0.82 (2)	2.93 (2)	3.744 (3)	173 (4)

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) ; (ii) .