Potassium N-bromo-4-chloro­benzene­sulfonamidate monohydrate

In the structure of the title compound, K⁺·C₆H₄BrClNO₂S⁻·H₂O, the K⁺ cation is hepta­coordinated. It is connected to two water O atoms, four sulfonyl O atoms and one Br atom. Further, the sulfonyl and water O atoms in the structure are bridged in a bidentate fashion. The S—N distance of 1.584 (6) Å is consistent with an S—N double bond, The crystal structure is stabilized by inter­molecular O—H...N hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.010 Å
• R factor = 0.057
• wR factor = 0.156
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW .gt. 10 Outliers .          1

Alert level C
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..         10
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          4
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          7
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         11

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          1
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.       8.65
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.37 Ratio
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

To explore the effect of substitution and replacing sodium ion by potassium ion in the solid state structures of N-chloroarylsulfonamides (Gowda et al., 2007; 2011a,b; Usha & Gowda, 2006), in the present work, the structure of potassium N-bromo-4-chloro- 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., 2011b), potassium N,4-dichloro-benzenesulfonamidate monohydrate (III) (Gowda et al., 2011a), sodium N-bromo-4-chloro- benzenesulfonamidate sesquihydrate (IV)(Gowda et al., 2007) and other sodium N-chloro-arylsulfonamdes (George et al., 2000; Olmstead & Power, 1986). In particular, there is no interaction between the nitrogen and potassium atom in the molecule. Further, K⁺ is hepta co-ordinated in contrast to hexa co-ordination with Na⁺

K⁺ hepta coordination involves two O atoms from water molecules, four sulfonyl O atoms of N-bromo-4-chlorobenzenesulfonamide anions and one Br, in contrast to octahedral coordination of Na⁺ in (IV) by three O atoms of water molecules and by three sulfonyl O atoms of N-bromo-4-chloro- benzenesulfonamide anions (Gowda et al., 2007).

The S—N distance of N1—S1, 1.584 (6) Å is consistent with an S—N double bond and is in agreement with the observed values of 1.582 (4) Å in (II), 1.588 (2)Å in (III), and N1—S1, 1.574 (5)Å and N2—S2 1.579 (4)Å in (IV).

K⁺ ion coordination in the structure gives rise to several hydrogen bonding between coordinated water molecules and nitrogen atoms. The packing diagram consists of a two-dimensional polymeric layer running parallel to the b-axis (Fig. 2). The molecular packing is stabilized by O3—H31···N1 and O3—H32···N1 hydrogen bonds (Table 1).

Related literature

For our study of the effect of substituents on the structures of N-haloarylsulfonamides, see: Gowda et al. (2007, 2011a,b); and on the oxidative strengths of N-halolarylsulfonamides, see: Usha & Gowda (2006). For similar structures, see: George et al. (2000); Olmstead & Power (1986). For the preparation of the title compound, see: Gowda & Usha (2003).

S2. Experimental

The title compound was prepared similar to the literature method (Gowda & Usha, 2003). The purity of the compound was checked by determining its melting point (184 ° C). It was characterized by recording its infrared and NMR spectra.

Yellow prisms of the title compound used in X-ray diffraction studies were obtained from its aqueous solution at room temperature.

S3. Refinement

The O bound H atoms were located in difference map and later restrained to O—H = 0.82 (2) Å The other H atoms were positioned with idealized geometry using a riding model with C—H = 0.93 Å. All H atoms were refined with isotropic displacement parameters (set to 1.2 times of the U_eq of the parent atom).

The residual electron-density features are located in the region of Br1. The highest peak and the deepest hole are 1.70 and 0.93 Å from Br1, respectivily.

Computing details

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

	Fig. 1. Molecular structure of the title compound, showing the atom labelling scheme for the asymmetric unit and extended to show the coordination geometry for the K^+. 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-chlorobenzenesulfonamidate monohydrate

Crystal data

K^+·C6H4BrClNO2S^−·H2O	F(000) = 640
Mr = 326.64	Dx = 2.049 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2989 reflections
a = 15.596 (1) Å	θ = 3.0–27.8°
b = 10.188 (1) Å	µ = 4.70 mm^−1
c = 6.7649 (7) Å	T = 293 K
β = 99.947 (9)°	Prism, yellow
V = 1058.73 (17) Å^3	0.34 × 0.34 × 0.30 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2147 independent reflections
Radiation source: fine-focus sealed tube	1984 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Rotation method data acquisition using ω scans	θmax = 26.4°, θmin = 3.7°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −19→17
Tmin = 0.298, Tmax = 0.333	k = −5→12
3796 measured reflections	l = −8→6

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.057	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.156	w = 1/[σ^2(Fo^2) + (0.0614P)^2 + 8.645P] where P = (Fo^2 + 2Fc^2)/3
S = 1.19	(Δ/σ)max = 0.014
2147 reflections	Δρmax = 1.22 e Å^−3
134 parameters	Δρmin = −0.95 e Å^−3
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.044 (3)

Special details

Experimental. CrysAlis RED (Oxford Diffraction, 2009) 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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.25575 (4)	0.43815 (7)	−0.31985 (10)	0.0299 (3)
K1	0.44027 (9)	0.61960 (15)	−0.3785 (2)	0.0252 (4)
Cl1	−0.02963 (13)	0.5964 (3)	0.2758 (3)	0.0534 (6)
S1	0.34113 (9)	0.53777 (15)	0.0566 (2)	0.0190 (4)
O1	0.3587 (3)	0.6607 (5)	−0.0369 (7)	0.0310 (11)
O2	0.4024 (3)	0.5053 (6)	0.2355 (7)	0.0329 (11)
O3	0.5513 (3)	0.7034 (5)	−0.6370 (8)	0.0318 (11)
H31	0.572 (5)	0.692 (9)	−0.739 (8)	0.038*
H32	0.589 (4)	0.753 (7)	−0.578 (12)	0.038*
N1	0.3390 (4)	0.4126 (6)	−0.0831 (8)	0.0258 (12)
C1	0.2367 (4)	0.5577 (6)	0.1250 (9)	0.0197 (12)
C2	0.1965 (4)	0.4475 (7)	0.1854 (11)	0.0278 (14)
H2	0.2239	0.3662	0.1914	0.033*
C3	0.1148 (5)	0.4602 (8)	0.2370 (11)	0.0341 (16)
H3	0.0867	0.3879	0.2806	0.041*
C4	0.0755 (4)	0.5829 (8)	0.2223 (10)	0.0306 (15)
C5	0.1156 (5)	0.6906 (8)	0.1639 (11)	0.0371 (17)
H5	0.0885	0.7721	0.1573	0.044*
C6	0.1977 (5)	0.6771 (7)	0.1141 (10)	0.0286 (14)
H6	0.2260	0.7499	0.0733	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0227 (4)	0.0383 (5)	0.0267 (4)	−0.0011 (3)	−0.0019 (3)	−0.0082 (3)
K1	0.0199 (7)	0.0332 (8)	0.0234 (7)	0.0037 (5)	0.0062 (5)	0.0010 (6)
Cl1	0.0198 (9)	0.0954 (18)	0.0479 (11)	0.0083 (10)	0.0137 (8)	0.0025 (11)
S1	0.0136 (7)	0.0251 (8)	0.0178 (7)	−0.0009 (5)	0.0013 (5)	−0.0026 (5)
O1	0.032 (3)	0.029 (2)	0.034 (3)	−0.009 (2)	0.014 (2)	−0.005 (2)
O2	0.019 (2)	0.052 (3)	0.024 (2)	0.006 (2)	−0.0043 (18)	−0.003 (2)
O3	0.023 (2)	0.042 (3)	0.032 (3)	−0.005 (2)	0.008 (2)	0.000 (2)
N1	0.021 (3)	0.032 (3)	0.024 (3)	0.005 (2)	0.002 (2)	−0.003 (2)
C1	0.018 (3)	0.025 (3)	0.016 (3)	0.000 (2)	0.001 (2)	−0.002 (2)
C2	0.020 (3)	0.027 (3)	0.037 (4)	0.002 (2)	0.007 (3)	0.002 (3)
C3	0.028 (4)	0.040 (4)	0.036 (4)	−0.010 (3)	0.009 (3)	0.002 (3)
C4	0.016 (3)	0.056 (5)	0.020 (3)	0.003 (3)	0.003 (2)	0.000 (3)
C5	0.036 (4)	0.040 (4)	0.036 (4)	0.015 (3)	0.010 (3)	0.002 (3)
C6	0.029 (3)	0.026 (3)	0.033 (3)	0.002 (3)	0.012 (3)	0.006 (3)

Geometric parameters (Å, º)

Br1—N1	1.897 (5)	O2—K1^ii	2.784 (5)
Br1—K1	3.5001 (16)	O2—K1^vi	2.827 (5)
K1—O1^i	2.704 (5)	O3—K1^i	2.818 (6)
K1—O2^ii	2.784 (5)	O3—K1^v	3.295 (6)
K1—O3	2.799 (5)	O3—H31	0.82 (2)
K1—O3^iii	2.818 (6)	O3—H32	0.82 (2)
K1—O2^iv	2.827 (5)	C1—C6	1.356 (9)
K1—O1	2.855 (5)	C1—C2	1.382 (9)
K1—O3^v	3.295 (6)	C2—C3	1.384 (10)
K1—N1	3.468 (6)	C2—H2	0.9300
Cl1—C4	1.745 (7)	C3—C4	1.388 (11)
S1—O2	1.446 (5)	C3—H3	0.9300
S1—O1	1.450 (5)	C4—C5	1.355 (11)
S1—N1	1.584 (6)	C5—C6	1.386 (10)
S1—C1	1.780 (6)	C5—H5	0.9300
O1—K1^iii	2.704 (5)	C6—H6	0.9300
N1—Br1—K1	73.28 (18)	O2—S1—C1	108.1 (3)
O1^i—K1—O2^ii	147.39 (17)	O1—S1—C1	105.3 (3)
O1^i—K1—O3	78.43 (15)	N1—S1—C1	108.7 (3)
O2^ii—K1—O3	75.72 (16)	S1—O1—K1^iii	130.8 (3)
O1^i—K1—O3^iii	84.28 (16)	S1—O1—K1	111.7 (3)
O2^ii—K1—O3^iii	71.01 (15)	K1^iii—O1—K1	101.36 (15)
O3—K1—O3^iii	77.42 (11)	S1—O2—K1^ii	144.2 (3)
O1^i—K1—O2^iv	88.05 (16)	S1—O2—K1^vi	133.0 (3)
O2^ii—K1—O2^iv	99.40 (13)	K1^ii—O2—K1^vi	80.60 (12)
O3—K1—O2^iv	66.52 (15)	K1—O3—K1^i	99.95 (16)
O3^iii—K1—O2^iv	143.94 (16)	K1—O3—K1^v	72.59 (13)
O1^i—K1—O1	87.38 (13)	K1^i—O3—K1^v	132.42 (18)
O2^ii—K1—O1	105.97 (15)	K1—O3—H31	149 (6)
O3—K1—O1	150.63 (16)	K1^i—O3—H31	84 (6)
O3^iii—K1—O1	75.66 (14)	K1^v—O3—H31	82 (6)
O2^iv—K1—O1	139.19 (15)	K1—O3—H32	110 (6)
O1^i—K1—O3^v	148.56 (15)	K1^i—O3—H32	102 (6)
O2^ii—K1—O3^v	60.31 (15)	K1^v—O3—H32	125 (6)
O3—K1—O3^v	107.41 (13)	H31—O3—H32	98 (9)
O3^iii—K1—O3^v	127.12 (10)	S1—N1—Br1	109.5 (3)
O2^iv—K1—O3^v	67.58 (15)	S1—N1—K1	83.6 (2)
O1—K1—O3^v	98.14 (14)	Br1—N1—K1	75.12 (18)
O1^i—K1—N1	120.12 (14)	C6—C1—C2	121.5 (6)
O2^ii—K1—N1	89.06 (15)	C6—C1—S1	120.7 (5)
O3—K1—N1	159.76 (16)	C2—C1—S1	117.8 (5)
O3^iii—K1—N1	110.52 (14)	C1—C2—C3	118.9 (6)
O2^iv—K1—N1	103.80 (15)	C1—C2—H2	120.6
O1—K1—N1	46.50 (13)	C3—C2—H2	120.6
O3^v—K1—N1	52.68 (13)	C2—C3—C4	118.7 (7)
O1^i—K1—Br1	98.17 (12)	C2—C3—H3	120.7
O2^ii—K1—Br1	114.30 (12)	C4—C3—H3	120.7
O3—K1—Br1	147.31 (12)	C5—C4—C3	122.0 (7)
O3^iii—K1—Br1	135.01 (11)	C5—C4—Cl1	119.6 (6)
O2^iv—K1—Br1	80.94 (11)	C3—C4—Cl1	118.4 (6)
O1—K1—Br1	59.70 (10)	C4—C5—C6	118.8 (7)
O3^v—K1—Br1	59.85 (9)	C4—C5—H5	120.6
N1—K1—Br1	31.60 (9)	C6—C5—H5	120.6
O2—S1—O1	114.6 (3)	C1—C6—C5	120.1 (7)
O2—S1—N1	105.0 (3)	C1—C6—H6	120.0
O1—S1—N1	114.9 (3)	C5—C6—H6	120.0
N1—Br1—K1—O1^i	−137.2 (2)	O3^iii—K1—O3—K1^v	125.32 (11)
N1—Br1—K1—O2^ii	39.8 (2)	O2^iv—K1—O3—K1^v	−55.11 (13)
N1—Br1—K1—O3	141.5 (3)	O1—K1—O3—K1^v	149.3 (3)
N1—Br1—K1—O3^iii	−47.2 (2)	O3^v—K1—O3—K1^v	0.0
N1—Br1—K1—O2^iv	136.1 (2)	N1—K1—O3—K1^v	9.7 (4)
N1—Br1—K1—O1	−55.1 (2)	Br1—K1—O3—K1^v	−60.9 (2)
N1—Br1—K1—O3^v	66.8 (2)	O2—S1—N1—Br1	177.0 (3)
O2—S1—O1—K1^iii	−27.2 (5)	O1—S1—N1—Br1	−56.3 (4)
N1—S1—O1—K1^iii	−148.9 (3)	C1—S1—N1—Br1	61.5 (4)
C1—S1—O1—K1^iii	91.5 (4)	O2—S1—N1—K1	−111.3 (2)
O2—S1—O1—K1	101.4 (3)	O1—S1—N1—K1	15.5 (3)
N1—S1—O1—K1	−20.3 (4)	C1—S1—N1—K1	133.2 (2)
C1—S1—O1—K1	−139.9 (3)	K1—Br1—N1—S1	77.5 (3)
O1^i—K1—O1—S1	148.80 (19)	O1^i—K1—N1—S1	−61.2 (3)
O2^ii—K1—O1—S1	−61.4 (3)	O2^ii—K1—N1—S1	103.5 (2)
O3—K1—O1—S1	−150.6 (3)	O3—K1—N1—S1	144.3 (4)
O3^iii—K1—O1—S1	−126.4 (3)	O3^iii—K1—N1—S1	34.2 (2)
O2^iv—K1—O1—S1	64.8 (4)	O2^iv—K1—N1—S1	−157.0 (2)
O3^v—K1—O1—S1	−0.1 (3)	O1—K1—N1—S1	−9.74 (19)
N1—K1—O1—S1	11.4 (2)	O3^v—K1—N1—S1	155.9 (3)
Br1—K1—O1—S1	47.7 (2)	Br1—K1—N1—S1	−112.2 (3)
O1^i—K1—O1—K1^iii	−68.3 (3)	O1^i—K1—N1—Br1	51.0 (2)
O2^ii—K1—O1—K1^iii	81.47 (19)	O2^ii—K1—N1—Br1	−144.32 (18)
O3—K1—O1—K1^iii	−7.7 (4)	O3—K1—N1—Br1	−103.5 (4)
O3^iii—K1—O1—K1^iii	16.46 (16)	O3^iii—K1—N1—Br1	146.39 (17)
O2^iv—K1—O1—K1^iii	−152.3 (2)	O2^iv—K1—N1—Br1	−44.9 (2)
O3^v—K1—O1—K1^iii	142.81 (15)	O1—K1—N1—Br1	102.4 (2)
N1—K1—O1—K1^iii	154.3 (3)	O3^v—K1—N1—Br1	−91.9 (2)
Br1—K1—O1—K1^iii	−169.3 (2)	O2—S1—C1—C6	112.9 (6)
O1—S1—O2—K1^ii	−88.7 (6)	O1—S1—C1—C6	−10.0 (6)
N1—S1—O2—K1^ii	38.3 (6)	N1—S1—C1—C6	−133.7 (6)
C1—S1—O2—K1^ii	154.2 (5)	O2—S1—C1—C2	−68.3 (6)
O1—S1—O2—K1^vi	66.9 (5)	O1—S1—C1—C2	168.8 (5)
N1—S1—O2—K1^vi	−166.1 (4)	N1—S1—C1—C2	45.1 (6)
C1—S1—O2—K1^vi	−50.2 (5)	C6—C1—C2—C3	−0.4 (10)
O1^i—K1—O3—K1^i	−16.53 (16)	S1—C1—C2—C3	−179.2 (5)
O2^ii—K1—O3—K1^i	−176.5 (2)	C1—C2—C3—C4	1.2 (11)
O3^iii—K1—O3—K1^i	−103.2 (2)	C2—C3—C4—C5	−1.6 (11)
O2^iv—K1—O3—K1^i	76.40 (17)	C2—C3—C4—Cl1	176.9 (6)
O1—K1—O3—K1^i	−79.2 (3)	C3—C4—C5—C6	1.1 (11)
O3^v—K1—O3—K1^i	131.51 (17)	Cl1—C4—C5—C6	−177.4 (6)
N1—K1—O3—K1^i	141.2 (4)	C2—C1—C6—C5	−0.1 (10)
Br1—K1—O3—K1^i	70.6 (3)	S1—C1—C6—C5	178.6 (5)
O1^i—K1—O3—K1^v	−148.04 (15)	C4—C5—C6—C1	−0.2 (11)
O2^ii—K1—O3—K1^v	52.01 (12)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H31···N1^v	0.82 (2)	2.25 (5)	3.005 (8)	152 (8)
O3—H32···N1^vii	0.82 (2)	2.16 (3)	2.967 (8)	166 (9)

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