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Acta Cryst. (2007). E63, m1958    [ doi:10.1107/S1600536807029261 ]

Sodium N-bromo-4-fluorobenzenesulfonamidate sesquihydrate

B. T. Gowda, J. Kozísek, M. Tokarcík and H. Fuess

Abstract top

The structure of the title compound, Na+·C6H4BrFNO2S-·1.5H2O, like other sodium N-bromoarylfonamidates, crystallizes with two cations, two anions and three water molecules in the asymmetric unit. The sodium cation shows octahedral coordination by three O atoms of three different water molecules and by three sulfonyl O atoms of three different N-bromo-4-fluorobenzenesulfonamide anions. There is no interaction between the nitrogen atom and sodium ion in the molecule. The S-N distance of 1.591 (6) Å is consistent with an S=N double bond. The crystal structure is stabilized by O-H...N hydrogen bonds.

Comment top

The chemistry of N-bromo-arylsulfonamides is of interest due to their distinct physical, chemical and biological properties (Usha & Gowda, 2006). In the present work, the structure of sodium N-bromo-4-fluoro- benzenesulfonamidate (NaNB4FBSA) has been determined to study the substituent effects on the solid state structures of arylsulfonamides and N-halo arylsulfonamidates (Gowda, Jyothi et al., 2007; Gowda et al., 2007a,b; Gowda, Usha et al., 2007). The structure of NaNB4FBSA (Fig. 1) is similar to those of sodium N-bromo-benzenesulfonamidate(NaNBBSA)(Gowda, Usha et al., 2007) and sodium N-bromo-4-chloro-benzenesulfonamidate (NaNB4CBSA)(Gowda, Kožíšek et al., 2007a) and sodium N-chloro-arylsulfonamidates (George et al., 2000; Gowda, Jyothi et al., 2007). NaNB4FBSA crystallizes with two cations, two anions and three water molecules in the asymmetric unit. The sodium ion shows octahedral coordination by three O atoms of three different water molecules and by three sulfonyl O atoms of three different N-bromo-4-fluoro-benzenesulfonamide anions. There is no interaction between the nitrogen and sodium ions in the molecule. The S—N distances of N1—S1, 1.591 (6)Å is consistent with a S—N double bond and in agreement with those observed with NaNBBSA, NaNB4CBSA and sodium N-chloro- arylsulfonamidates. The occurrence of O—H···N hydrogen bonds between the wat er molecules and N atom associated with the presence of Na+ result in the formation of thick layered structure parallel to the (0 0 1) plane (Table 1, Fig. 1). This thick layer may be described as build up from an internal layer containing Na atoms and water molecules sandwiched by the benzenesulfonamidate with the fluorobenzene pointing outward.

Related literature top

For related literature, see: George et al. (2000); Gowda & Usha (2003); Gowda, Jyothi et al. (2007); Gowda, Kožíšek et al. (2007a,b); Gowda, Usha et al. (2007); Usha & Gowda (2006).

Experimental top

The title compound was prepared according to the literature method (Gowda & Usha, 2003). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared and NMR spectra (Gowda & Usha, 2003). Single crystals of the title compound were obtained from its aqueous solution and used for X-ray diffraction studies at room temperature.

Refinement top

H atoms of the benzene ring were positioned geometrically and refined using a riding model with C—H = 0.93 Å and Uiso(H) = 1.2 Ueq(C). H atoms of the water molecules (O3w, O4w) were visible in difference map and were subsequently treated as riding with mutual distance restrained to 1.35 (5) Å and O—H bond length 0.82 (5) Å. No restraints were applied to non-hydrogen atoms.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2002); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2003) and WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. ORTEP view of the title compound showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Na—O contacts are shown as dashed lines. H atoms are represented as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Partial packing view down the b axis of the title compound showing the formation of layers through O—H···N hydrogen bonds. H bonds are represented as dashed lines. H atoms not involved in H bonds have been omitted for clarity. [Symmetry codes:(i) x − 1/2,y + 1/2,z; (ii) x − 1/2,y − 1/2,z]
Sodium N-bromo-4-fluorobenzenesulfonamidate sesquihydrate top
Crystal data top
Na+·C6H4BrFNO2S–·1.5H2OZ = 8
Mr = 303.09F000 = 1192
Monoclinic, C2/cDx = 1.946 Mg m−3
Hall symbol: -C 2ycMo Kα radiation
λ = 0.71073 Å
a = 10.3985 (8) ŵ = 4.22 mm−1
b = 6.7027 (4) ÅT = 299 (2) K
c = 29.892 (2) ÅPlate, yellow
β = 96.710 (8)º0.44 × 0.34 × 0.15 mm
V = 2069.1 (2) Å3
Data collection top
Oxford Diffraction Xcalibur
diffractometer		2009 independent reflections
Radiation source: Enhance (Mo) X-ray Source1798 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.025
T = 299(2) Kθmax = 26.0º
Rotation method data acquisition using ω and φ scansθmin = 5.2º
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2006) using a multifaceted crystal model (Clark & Reid, 1995)		h = −12→12
Tmin = 0.187, Tmax = 0.561k = −8→7
6114 measured reflectionsl = −36→36
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.070H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.151  w = 1/[σ2(Fo2) + (0.021P)2 + 67.2P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
2009 reflectionsΔρmax = 0.60 e Å−3
141 parametersΔρmin = −0.94 e Å−3
4 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
Na+·C6H4BrFNO2S–·1.5H2OV = 2069.1 (2) Å3
Mr = 303.09Z = 8
Monoclinic, C2/cMo Kα
a = 10.3985 (8) ŵ = 4.22 mm−1
b = 6.7027 (4) ÅT = 299 (2) K
c = 29.892 (2) Å0.44 × 0.34 × 0.15 mm
β = 96.710 (8)º
Data collection top
Oxford Diffraction Xcalibur
diffractometer		2009 independent reflections
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2006) using a multifaceted crystal model (Clark & Reid, 1995)		1798 reflections with I > 2σ(I)
Tmin = 0.187, Tmax = 0.561Rint = 0.025
6114 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0704 restraints
wR(F2) = 0.151H atoms treated by a mixture of
independent and constrained refinement
S = 1.04  w = 1/[σ2(Fo2) + (0.021P)2 + 67.2P]
where P = (Fo2 + 2Fc2)/3
2009 reflectionsΔρmax = 0.60 e Å−3
141 parametersΔρmin = −0.94 e Å−3
Special details top

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 > 2sigma(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
xyzUiso*/Ueq
C10.4571 (7)0.5495 (10)0.3857 (2)0.0287 (15)
C20.5860 (10)0.5823 (15)0.4020 (3)0.052 (2)
H20.65090.54690.38460.062*
C30.6180 (14)0.6670 (16)0.4437 (4)0.070 (3)
H30.7040.68910.4550.084*
C40.5215 (18)0.7165 (16)0.4674 (4)0.078 (4)
C50.3931 (16)0.6915 (18)0.4527 (3)0.078 (4)
H50.32960.73110.47030.093*
C60.3601 (10)0.6044 (14)0.4102 (3)0.051 (2)
H60.27380.58460.3990.061*
N10.5170 (6)0.2609 (9)0.3281 (2)0.0274 (13)
O10.4650 (4)0.5891 (8)0.29942 (16)0.0280 (11)
O20.2871 (5)0.4018 (9)0.32575 (17)0.0350 (12)
O3W00.4971 (10)0.250.0273 (15)
H310.000 (8)0.541 (12)0.2754 (12)0.033*
O4W0.2379 (5)−0.0996 (8)0.28949 (18)0.0339 (12)
H410.183 (5)−0.158 (12)0.302 (2)0.041*
H420.307 (4)−0.102 (13)0.306 (2)0.041*
Na10.1560 (3)0.2298 (4)0.26819 (9)0.0285 (6)
S10.42385 (15)0.4474 (3)0.33121 (5)0.0214 (4)
F10.5471 (12)0.7988 (13)0.5096 (2)0.141 (4)
Br10.48476 (9)0.06776 (13)0.37091 (3)0.0481 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.046 (4)0.018 (3)0.022 (3)0.006 (3)0.001 (3)0.001 (3)
C20.059 (6)0.054 (6)0.037 (5)−0.011 (5)−0.016 (4)0.000 (4)
C30.107 (10)0.041 (6)0.051 (6)−0.006 (6)−0.035 (6)−0.006 (5)
C40.150 (13)0.035 (6)0.040 (6)−0.003 (7)−0.025 (7)−0.002 (5)
C50.139 (12)0.064 (7)0.036 (5)0.024 (8)0.038 (7)−0.003 (5)
C60.067 (6)0.051 (6)0.039 (5)0.014 (5)0.020 (4)0.000 (4)
N10.031 (3)0.021 (3)0.032 (3)0.010 (3)0.008 (2)0.004 (2)
O10.027 (2)0.028 (3)0.029 (2)0.000 (2)0.0027 (19)0.009 (2)
O20.022 (2)0.042 (3)0.040 (3)−0.002 (2)0.001 (2)0.001 (2)
O3W0.038 (4)0.021 (3)0.023 (3)00.006 (3)0
O4W0.020 (2)0.032 (3)0.050 (3)0.001 (2)0.007 (2)0.003 (2)
Na10.0212 (13)0.0253 (15)0.0383 (15)−0.0031 (11)0.0001 (11)0.0013 (12)
S10.0207 (8)0.0201 (8)0.0230 (8)−0.0002 (6)0.0006 (6)0.0019 (6)
F10.275 (13)0.089 (6)0.045 (4)0.023 (7)−0.039 (5)−0.030 (4)
Br10.0596 (6)0.0303 (4)0.0524 (5)−0.0024 (4)−0.0012 (4)0.0134 (4)
Geometric parameters (Å, °) top
C1—C61.365 (11)O1—S11.444 (5)
C1—C21.388 (12)O1—Na1i2.442 (5)
C1—S11.764 (7)O1—Na1ii2.478 (5)
C2—C31.374 (13)O2—S11.445 (5)
C2—H20.93O2—Na12.367 (6)
C3—C41.338 (19)O3W—Na12.435 (6)
C3—H30.93O3W—H310.81 (5)
C4—C51.366 (19)O4W—Na12.425 (6)
C4—F11.373 (12)O4W—H410.82 (5)
C5—C61.402 (14)O4W—H420.82 (5)
C5—H50.93Na1—O4Wi2.438 (6)
C6—H60.93Na1—Na1iii3.299 (5)
N1—S11.591 (6)Na1—Na1i4.091 (3)
N1—Br11.879 (6)Na1—H312.66 (8)
C6—C1—C2120.9 (8)O2—Na1—O1v109.3 (2)
C6—C1—S1121.5 (7)O4W—Na1—O1v80.03 (18)
C2—C1—S1117.5 (6)O3W—Na1—O1v79.74 (16)
C3—C2—C1120.3 (11)O4Wi—Na1—O1v153.4 (2)
C3—C2—H2119.9O1iv—Na1—O1v78.8 (2)
C1—C2—H2119.9O2—Na1—Na1iii134.46 (17)
C4—C3—C2117.8 (11)O4W—Na1—Na1iii112.85 (14)
C4—C3—H3121.1O3W—Na1—Na1iii47.37 (13)
C2—C3—H3121.1O4Wi—Na1—Na1iii106.01 (17)
C3—C4—C5124.3 (10)O1iv—Na1—Na1iii48.35 (13)
C3—C4—F1120.7 (14)O1v—Na1—Na1iii47.43 (13)
C5—C4—F1115.0 (15)O2—Na1—Na1iv109.86 (17)
C4—C5—C6118.0 (11)O4W—Na1—Na1iv32.82 (13)
C4—C5—H5121O3W—Na1—Na1iv150.46 (15)
C6—C5—H5121O4Wi—Na1—Na1iv85.78 (17)
C1—C6—C5118.6 (10)O1iv—Na1—Na1iv71.32 (14)
C1—C6—H6120.7O1v—Na1—Na1iv102.55 (14)
C5—C6—H6120.7Na1iii—Na1—Na1iv113.24 (9)
S1—N1—Br1110.0 (3)O2—Na1—Na1i62.71 (15)
S1—O1—Na1i129.4 (3)O4W—Na1—Na1i130.67 (17)
S1—O1—Na1ii144.2 (3)O3W—Na1—Na1i70.39 (11)
Na1i—O1—Na1ii84.22 (17)O4Wi—Na1—Na1i32.63 (14)
S1—O2—Na1131.4 (3)O1iv—Na1—Na1i108.21 (17)
Na1iii—O3W—Na185.3 (3)O1v—Na1—Na1i147.25 (16)
Na1iii—O3W—H31114 (6)Na1iii—Na1—Na1i113.24 (9)
Na1—O3W—H3197 (6)Na1iv—Na1—Na1i110.02 (12)
Na1—O4W—Na1iv114.6 (2)O2—Na1—H3182.2 (12)
Na1—O4W—H41108 (6)O4W—Na1—H31152.8 (15)
Na1iv—O4W—H41120 (6)O3W—Na1—H3117.7 (8)
Na1—O4W—H42116 (6)O4Wi—Na1—H3191.2 (16)
Na1iv—O4W—H4288 (6)O1iv—Na1—H3196.3 (11)
H41—O4W—H42109 (3)O1v—Na1—H3175.3 (18)
O2—Na1—O4W95.6 (2)Na1iii—Na1—H3156.2 (15)
O2—Na1—O3W96.66 (19)Na1iv—Na1—H31167.6 (10)
O4W—Na1—O3W158.9 (2)Na1i—Na1—H3172.2 (18)
O2—Na1—O4Wi90.9 (2)O1—S1—O2115.4 (3)
O4W—Na1—O4Wi116.02 (17)O1—S1—N1104.4 (3)
O3W—Na1—O4Wi80.89 (16)O2—S1—N1115.2 (3)
O2—Na1—O1iv170.9 (2)O1—S1—C1108.2 (3)
O4W—Na1—O1iv89.8 (2)O2—S1—C1105.7 (3)
O3W—Na1—O1iv80.45 (17)N1—S1—C1107.7 (3)
O4Wi—Na1—O1iv80.09 (19)
C6—C1—C2—C31.5 (14)Na1iii—O3W—Na1—O4Wi121.82 (17)
S1—C1—C2—C3178.1 (8)Na1iii—O3W—Na1—O1iv40.44 (13)
C1—C2—C3—C4−0.3 (16)Na1iii—O3W—Na1—O1v−39.84 (12)
C2—C3—C4—C5−1.1 (18)Na1iii—O3W—Na1—Na1iv57.5 (2)
C2—C3—C4—F1179.0 (10)Na1iii—O3W—Na1—Na1i153.79 (13)
C3—C4—C5—C61.4 (18)Na1i—O1—S1—O2−9.1 (5)
F1—C4—C5—C6−178.7 (9)Na1ii—O1—S1—O2−165.6 (5)
C2—C1—C6—C5−1.2 (13)Na1i—O1—S1—N1118.3 (4)
S1—C1—C6—C5−177.6 (8)Na1ii—O1—S1—N1−38.2 (6)
C4—C5—C6—C1−0.2 (16)Na1i—O1—S1—C1−127.2 (4)
S1—O2—Na1—O4W73.4 (5)Na1ii—O1—S1—C176.3 (6)
S1—O2—Na1—O3W−123.8 (4)Na1—O2—S1—O168.3 (5)
S1—O2—Na1—O1v154.8 (4)Na1—O2—S1—N1−53.5 (5)
S1—O2—Na1—Na1iii−156.5 (3)Na1—O2—S1—C1−172.3 (4)
S1—O2—Na1—Na1iv43.0 (5)Br1—N1—S1—O1175.7 (3)
Na1iv—O4W—Na1—O2−118.5 (2)Br1—N1—S1—O2−56.8 (4)
Na1iv—O4W—Na1—O3W116.1 (5)Br1—N1—S1—C160.9 (4)
Na1iv—O4W—Na1—O4Wi−24.8 (2)C6—C1—S1—O1112.3 (7)
Na1iv—O4W—Na1—O1iv54.1 (2)C2—C1—S1—O1−64.2 (7)
Na1iv—O4W—Na1—O1v132.8 (3)C6—C1—S1—O2−11.8 (8)
Na1iv—O4W—Na1—Na1iii97.9 (2)C2—C1—S1—O2171.7 (7)
Na1iv—O4W—Na1—Na1i−60.1 (3)C6—C1—S1—N1−135.4 (7)
Na1iii—O3W—Na1—O2−148.33 (19)C2—C1—S1—N148.1 (7)
Na1iii—O3W—Na1—O4W−23.1 (5)
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x+1/2, y+1/2, z; (iii) −x, y, −z+1/2; (iv) −x+1/2, y−1/2, −z+1/2; (v) x−1/2, y−1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3W—H31···N1vi0.81 (5)2.15 (4)2.916 (7)157 (8)
O4W—H41···N1v0.82 (5)2.05 (3)2.846 (8)165 (8)
Symmetry codes: (vi) x−1/2, y+1/2, z; (v) x−1/2, y−1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3W—H31···N1i0.81 (5)2.15 (4)2.916 (7)157 (8)
O4W—H41···N1ii0.82 (5)2.05 (3)2.846 (8)165 (8)
Symmetry codes: (i) x−1/2, y+1/2, z; (ii) x−1/2, y−1/2, z.
Acknowledgements top

BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany for extensions of his research fellowship. JK and MT thank the Grant Agency of the Slovak Republic (grant No. 1/2449/05).

references
References top

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