Potassium N-bromo-2-nitro­benzene­sulfonamidate monohydrate

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.053
• wR factor = 0.145
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0065 Ang
PLAT774_ALERT_1_C Suspect X-Y Bond in CIF:   BR1    --  K1      ..       3.68 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.262
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         22
PLAT975_ALERT_2_C Positive Residual Density at 0.91A from N1     .       0.51 eA-3

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 .          2
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ          ?
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) .       1.29 Ratio
PLAT793_ALERT_4_G The Model has Chirality at S1      (Verify) ....          R
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         21

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

   4 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

---

S1. 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).

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).

S2. 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.

S3. Refinement

H atoms bonded to C were positioned with idealized geometry using a riding model with the aromatic C—H = 0.93 Å. The O-bound H atoms were located in a difference map and were refined with restrained geometry (Nardelli, 1999), viz. O—H distances were restrained to 0.85 (2) Å and the H—H distance was restrained to 1.365 Å, thus leading to the angle of 107°. All H atoms were refined with isotropic displacement parameters set at 1.2 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 0.80 and 0.84 Å from Br1, respectivily.

Computing details

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

	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^+ ion. The displacement ellipsoids are drawn at the 50% probability level. The H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Bridging of potassium cations, N-bromo-2-nitro-benzenesulfonamidate anions and water molecules in the structure of the title compound.
	Fig. 3. Molecular packing of the title compound with hydrogen bonding shown as dashed lines.

Potassium N-bromo-2-nitrobenzenesulfonamidate monohydrate

Crystal data

K^+·C6H4BrN2O4S^−·H2O	F(000) = 664
Mr = 337.20	Dx = 2.014 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2399 reflections
a = 13.034 (2) Å	θ = 3.1–27.8°
b = 12.815 (2) Å	µ = 4.27 mm^−1
c = 6.7741 (9) Å	T = 293 K
β = 100.65 (1)°	Prism, yellow
V = 1112.0 (3) Å^3	0.48 × 0.48 × 0.24 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector	2236 independent reflections
Radiation source: fine-focus sealed tube	1847 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Rotation method data acquisition using ω scans.	θmax = 26.4°, θmin = 3.2°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −16→12
Tmin = 0.234, Tmax = 0.428	k = −16→11
3896 measured reflections	l = −6→8

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)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.145	w = 1/[σ^2(Fo^2) + (0.0909P)^2 + 0.1082P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.002
2236 reflections	Δρmax = 0.79 e Å^−3
152 parameters	Δρmin = −1.21 e Å^−3
3 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: 0.082 (5)

Special details

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
C1	0.2873 (3)	−0.0123 (3)	0.3340 (6)	0.0272 (9)
C2	0.3529 (3)	0.0693 (3)	0.3079 (6)	0.0271 (8)
C3	0.4505 (3)	0.0546 (4)	0.2573 (6)	0.0346 (10)
H3	0.4930	0.1113	0.2430	0.042*
C4	0.4833 (4)	−0.0463 (4)	0.2286 (7)	0.0419 (11)
H4	0.5488	−0.0583	0.1975	0.050*
C5	0.4173 (4)	−0.1291 (4)	0.2469 (7)	0.0425 (11)
H5	0.4377	−0.1966	0.2221	0.051*
C6	0.3214 (4)	−0.1127 (3)	0.3015 (7)	0.0368 (10)
H6	0.2791	−0.1695	0.3167	0.044*
Br1	0.24804 (4)	−0.10055 (4)	0.78959 (7)	0.0470 (3)
K1	0.09562 (9)	0.13045 (8)	0.88211 (15)	0.0418 (3)
N1	0.1510 (3)	−0.1035 (3)	0.5411 (6)	0.0384 (9)
N2	0.3214 (3)	0.1792 (3)	0.3257 (5)	0.0316 (8)
O1	0.1685 (3)	0.0941 (2)	0.5295 (5)	0.0395 (8)
O2	0.0840 (3)	−0.0085 (2)	0.2371 (5)	0.0442 (8)
O3	0.2363 (3)	0.2061 (3)	0.2308 (5)	0.0454 (8)
O4	0.3826 (3)	0.2369 (3)	0.4304 (6)	0.0520 (9)
S1	0.16307 (8)	−0.00155 (7)	0.41728 (15)	0.0294 (3)
O5	−0.0180 (3)	0.2758 (3)	0.6363 (6)	0.0494 (9)
H51	−0.066 (3)	0.240 (3)	0.566 (7)	0.059*
H52	−0.044 (4)	0.326 (3)	0.689 (8)	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.027 (2)	0.0276 (19)	0.0253 (18)	0.0017 (17)	0.0016 (16)	−0.0018 (16)
C2	0.026 (2)	0.0279 (18)	0.0271 (18)	0.0015 (17)	0.0053 (16)	0.0028 (16)
C3	0.032 (2)	0.042 (2)	0.032 (2)	0.000 (2)	0.0101 (18)	0.0059 (19)
C4	0.036 (3)	0.054 (3)	0.038 (2)	0.014 (2)	0.015 (2)	0.001 (2)
C5	0.047 (3)	0.036 (2)	0.045 (3)	0.020 (2)	0.012 (2)	−0.003 (2)
C6	0.041 (3)	0.030 (2)	0.040 (2)	0.0028 (19)	0.009 (2)	−0.0020 (18)
Br1	0.0516 (4)	0.0461 (4)	0.0432 (4)	−0.0034 (2)	0.0087 (2)	0.0096 (2)
K1	0.0378 (6)	0.0498 (6)	0.0380 (5)	0.0041 (5)	0.0076 (4)	−0.0024 (5)
N1	0.036 (2)	0.034 (2)	0.047 (2)	−0.0106 (16)	0.0122 (19)	0.0010 (16)
N2	0.032 (2)	0.0279 (17)	0.0369 (18)	−0.0005 (15)	0.0100 (16)	0.0052 (15)
O1	0.046 (2)	0.0313 (15)	0.0463 (18)	−0.0007 (13)	0.0206 (16)	−0.0100 (13)
O2	0.0293 (17)	0.0527 (19)	0.0465 (18)	−0.0035 (15)	−0.0039 (15)	−0.0014 (16)
O3	0.045 (2)	0.0325 (17)	0.0564 (19)	0.0096 (15)	0.0025 (16)	0.0113 (15)
O4	0.048 (2)	0.0379 (17)	0.070 (2)	−0.0146 (16)	0.0112 (19)	−0.0130 (17)
S1	0.0254 (6)	0.0274 (5)	0.0360 (5)	−0.0033 (4)	0.0069 (4)	−0.0032 (4)
O5	0.043 (2)	0.0443 (19)	0.063 (2)	−0.0011 (16)	0.0146 (18)	0.0010 (17)

Geometric parameters (Å, º)

C1—C2	1.383 (6)	K1—O2^ii	2.806 (3)
C1—C6	1.391 (5)	K1—O3^iii	2.877 (4)
C1—S1	1.815 (4)	K1—O2^iii	3.018 (4)
C2—C3	1.390 (6)	K1—O3^i	3.081 (4)
C2—N2	1.479 (5)	K1—H51	3.06 (5)
C3—C4	1.386 (6)	N1—S1	1.576 (4)
C3—H3	0.9300	N2—O4	1.215 (5)
C4—C5	1.385 (7)	N2—O3	1.225 (5)
C4—H4	0.9300	O1—S1	1.437 (3)
C5—C6	1.384 (7)	O2—S1	1.448 (3)
C5—H5	0.9300	O2—K1^ii	2.806 (3)
C6—H6	0.9300	O2—K1^iv	3.018 (4)
Br1—N1	1.910 (4)	O3—K1^iv	2.877 (4)
Br1—K1	3.6829 (12)	O3—K1^v	3.081 (4)
K1—O5	2.743 (4)	O5—K1^v	2.746 (4)
K1—O5^i	2.746 (4)	O5—H51	0.844 (19)
K1—O1	2.768 (3)	O5—H52	0.841 (19)
C2—C1—C6	117.1 (4)	O2^iii—K1—O3^i	141.88 (10)
C2—C1—S1	126.2 (3)	O5—K1—Br1	133.65 (9)
C6—C1—S1	116.7 (3)	O5^i—K1—Br1	145.95 (9)
C1—C2—C3	123.0 (4)	O1—K1—Br1	55.66 (7)
C1—C2—N2	121.5 (4)	O2^ii—K1—Br1	87.19 (8)
C3—C2—N2	115.4 (4)	O3^iii—K1—Br1	97.38 (7)
C4—C3—C2	118.7 (4)	O2^iii—K1—Br1	76.67 (7)
C4—C3—H3	120.6	O3^i—K1—Br1	96.72 (7)
C2—C3—H3	120.6	O5—K1—H51	15.6 (6)
C5—C4—C3	119.3 (4)	O5^i—K1—H51	81.7 (9)
C5—C4—H4	120.4	O1—K1—H51	77.0 (10)
C3—C4—H4	120.4	O2^ii—K1—H51	68.0 (7)
C6—C5—C4	120.9 (4)	O3^iii—K1—H51	132.2 (6)
C6—C5—H5	119.5	O2^iii—K1—H51	134.5 (10)
C4—C5—H5	119.5	O3^i—K1—H51	80.1 (8)
C5—C6—C1	120.9 (4)	Br1—K1—H51	125.1 (8)
C5—C6—H6	119.5	S1—N1—Br1	109.8 (2)
C1—C6—H6	119.5	O4—N2—O3	124.7 (4)
N1—Br1—K1	82.87 (12)	O4—N2—C2	117.7 (4)
O5—K1—O5^i	77.92 (8)	O3—N2—C2	117.6 (3)
O5—K1—O1	79.82 (11)	S1—O1—K1	127.53 (18)
O5^i—K1—O1	157.72 (11)	S1—O2—K1^ii	134.68 (19)
O5—K1—O2^ii	82.86 (11)	S1—O2—K1^iv	120.16 (18)
O5^i—K1—O2^ii	84.62 (11)	K1^ii—O2—K1^iv	105.16 (10)
O1—K1—O2^ii	93.37 (11)	N2—O3—K1^iv	135.6 (3)
O5—K1—O3^iii	117.39 (11)	N2—O3—K1^v	123.6 (3)
O5^i—K1—O3^iii	70.94 (11)	K1^iv—O3—K1^v	100.02 (11)
O1—K1—O3^iii	119.80 (11)	O1—S1—O2	117.1 (2)
O2^ii—K1—O3^iii	142.64 (11)	O1—S1—N1	115.2 (2)
O5—K1—O2^iii	141.57 (11)	O2—S1—N1	105.8 (2)
O5^i—K1—O2^iii	69.28 (11)	O1—S1—C1	105.67 (19)
O1—K1—O2^iii	131.59 (10)	O2—S1—C1	105.7 (2)
O2^ii—K1—O2^iii	74.84 (10)	N1—S1—C1	106.5 (2)
O3^iii—K1—O2^iii	70.30 (9)	K1—O5—K1^v	112.63 (13)
O5—K1—O3^i	67.90 (10)	K1—O5—H51	104 (4)
O5^i—K1—O3^i	109.52 (11)	K1^v—O5—H51	108 (4)
O1—K1—O3^i	60.50 (9)	K1—O5—H52	118 (4)
O2^ii—K1—O3^i	143.02 (10)	K1^v—O5—H52	104 (4)
O3^iii—K1—O3^i	73.50 (8)	H51—O5—H52	110 (3)
C6—C1—C2—C3	−1.9 (6)	O4—N2—O3—K1^iv	156.5 (3)
S1—C1—C2—C3	175.3 (3)	C2—N2—O3—K1^iv	−22.1 (5)
C6—C1—C2—N2	176.0 (4)	O4—N2—O3—K1^v	−35.7 (5)
S1—C1—C2—N2	−6.8 (6)	C2—N2—O3—K1^v	145.7 (3)
C1—C2—C3—C4	1.0 (6)	K1—O1—S1—O2	102.7 (3)
N2—C2—C3—C4	−177.0 (4)	K1—O1—S1—N1	−22.6 (3)
C2—C3—C4—C5	1.3 (7)	K1—O1—S1—C1	−139.9 (2)
C3—C4—C5—C6	−2.8 (7)	K1^ii—O2—S1—O1	−114.6 (3)
C4—C5—C6—C1	1.8 (8)	K1^iv—O2—S1—O1	65.8 (3)
C2—C1—C6—C5	0.5 (7)	K1^ii—O2—S1—N1	15.4 (3)
S1—C1—C6—C5	−177.0 (4)	K1^iv—O2—S1—N1	−164.3 (2)
N1—Br1—K1—O5	−28.49 (17)	K1^ii—O2—S1—C1	128.1 (3)
N1—Br1—K1—O5^i	124.97 (19)	K1^iv—O2—S1—C1	−51.6 (2)
N1—Br1—K1—O1	−47.15 (14)	Br1—N1—S1—O1	−46.5 (3)
N1—Br1—K1—O2^ii	48.87 (14)	Br1—N1—S1—O2	−177.5 (2)
N1—Br1—K1—O3^iii	−168.38 (14)	Br1—N1—S1—C1	70.3 (2)
N1—Br1—K1—O2^iii	123.95 (13)	C2—C1—S1—O1	−24.4 (4)
N1—Br1—K1—O3^i	−94.22 (13)	C6—C1—S1—O1	152.8 (3)
K1—Br1—N1—S1	63.0 (2)	C2—C1—S1—O2	100.4 (4)
C1—C2—N2—O4	131.2 (4)	C6—C1—S1—O2	−82.4 (4)
C3—C2—N2—O4	−50.8 (5)	C2—C1—S1—N1	−147.4 (4)
C1—C2—N2—O3	−50.2 (5)	C6—C1—S1—N1	29.8 (4)
C3—C2—N2—O3	127.9 (4)	O5^i—K1—O5—K1^v	140.66 (16)
O5—K1—O1—S1	−120.6 (3)	O1—K1—O5—K1^v	−38.60 (13)
O5^i—K1—O1—S1	−122.5 (3)	O2^ii—K1—O5—K1^v	−133.34 (15)
O2^ii—K1—O1—S1	−38.5 (3)	O3^iii—K1—O5—K1^v	79.80 (16)
O3^iii—K1—O1—S1	123.5 (2)	O2^iii—K1—O5—K1^v	172.23 (12)
O2^iii—K1—O1—S1	34.2 (3)	O3^i—K1—O5—K1^v	23.55 (11)
O3^i—K1—O1—S1	169.1 (3)	Br1—K1—O5—K1^v	−54.17 (18)
Br1—K1—O1—S1	45.8 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H51···N1^ii	0.84 (2)	2.13 (3)	2.926 (5)	157 (5)
O5—H52···Br1^vi	0.84 (2)	2.85 (4)	3.509 (4)	137 (4)

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