supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportcited insimilar papers buy article online

Acta Cryst. (2007). E63, m1739-m1740    [ doi:10.1107/S1600536807025184 ]

Sodium N-bromobenzenesulfonamidate sesquihydrate

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

Abstract top

In the title compound, Na+·C6H5BrNO2S-·1.5H2O, there is no interaction between the N atom and the Na+ cation, and the Na cation exhibits octahedral coordination by three O atoms from water molecules and by three sulfonyl O atoms of three different N-bromobenzenesulfonamide anions. The S-N distance of 1.578 (4) Å is consistent with an S=N double bond, similar to the distance of 1.582 (5) Å observed for the corresponding N-chloro compound. A two-dimensional polymeric layer runs parallel to the ab plane. The water molecules participate in O-H...N hydrogen bonds.

Comment top

The chemistry of arylsulfonamides and their N-halo compounds is of interest as they show diverse physical, chemical and biological properties. Thus N-halo arylsulfonamides are of interest in synthetic, mechanistic, analytical and biological chemistry (Gowda et al., 2005; Gowda & Shetty, 2004; Usha & Gowda, 2006). In the present work, the structure of sodium N-bromo- benzenesulfonamde (NaNBBSA) has been determined to explore the effects substitution on the solid state structures of sulfonamides and N-halo arylsulfonamides (Gowda et al., 2003; Gowda, Foro et al., 2007; Gowda, Jyothi et al., 2007; Gowda, Kozisek et al., 2007; Gowda, Savitha et al., 2007; Gowda, Srilatha et al., 2007).

The structure of NaNBBSA (Fig. 1) resembles those of sodium N-chloro- arylsulfonamdes (George et al., 2000; Gowda, Foro et al., 2007; Gowda, Jyothi et al., 2007; Gowda, Savitha et al., 2007; Gowda, Srilatha et al., 2007; Olmstead & Power, 1986). NaNBBSA is the parent or unsubstituted N-bromo-arylsulphonamide. The structure confirms that there is no interaction between the nitrogen and sodium atoms. The sodium ion exhibits octahedral coordination by three O atoms from water molecules and by three sulfonyl O atoms of three different N-bromobenzenesulfonamide anions. The S—N distance of 1.578 (4)Å is consistent with a S—N double bond, similar to the distance of 1.582 (5)Å observed with the corresponding N-chloro compound. Packing diagram of the title compound involving hydrogen bonds is shown in Fig.2.

Related literature top

For related literature, see: George et al. (2000); Gowda & Shetty (2004); Gowda & Usha (2003); Gowda et al. (2005); Gowda, Foro et al. (2007); Gowda, Jyothi et al. (2007); Gowda, Kozisek et al. (2007); Gowda, Savitha et al. (2007); Gowda, Srilatha et al. (2007); Gowda et al. (2003); Olmstead & Power (1986); 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 with 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 O—H bond length restrained to 0.85 (1) Å and mutual distance of H atoms 1.35 (1) Å. No restraints were applied for non-hydrogen atoms.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); 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. View of the asymmetric unit showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Partial packing view of the title compound showing hydrogen bonds network. Hydrogen atoms bonded to benzene C atoms have been omitted.. Symmetry codes: (i) -x + 3/2, y - 1/2,-z + 1; (ii) -x + 2, y, -z + 1].
Sodium N-bromobenzenesulfonamidate sesquihydrate top
Crystal data top
Na+·C6H5BrNO2S−·1.5H2OF(000) = 564
Mr = 285.10Dx = 1.847 Mg m−3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2yCell parameters from 2235 reflections
a = 10.521 (3) Åθ = 2.5–26.4°
b = 6.760 (2) ŵ = 4.24 mm−1
c = 14.853 (4) ÅT = 293 K
β = 103.97 (2)°Plate, yellow
V = 1025.1 (5) Å30.50 × 0.50 × 0.10 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur
diffractometer		1704 reflections with I > 2σ(I)
graphiteRint = 0.032
ω and φ scansθmax = 26.0°, θmin = 4.6°
Absorption correction: analytical
(Clark & Reid, 1995)		h = −12→9
Tmin = 0.155, Tmax = 0.652k = −8→8
2957 measured reflectionsl = −18→18
1880 independent reflections
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)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.088 w = 1/[σ2(Fo2) + (0.0547P)2 + 0.3614P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.002
1880 reflectionsΔρmax = 0.32 e Å−3
132 parametersΔρmin = −0.44 e Å−3
5 restraintsAbsolute structure: Flack (1983), 778 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.018 (12)
Crystal data top
Na+·C6H5BrNO2S−·1.5H2OV = 1025.1 (5) Å3
Mr = 285.10Z = 4
Monoclinic, C2Mo Kα radiation
a = 10.521 (3) ŵ = 4.24 mm−1
b = 6.760 (2) ÅT = 293 K
c = 14.853 (4) Å0.50 × 0.50 × 0.10 mm
β = 103.97 (2)°
Data collection top
Oxford Diffraction Xcalibur
diffractometer		1704 reflections with I > 2σ(I)
Absorption correction: analytical
(Clark & Reid, 1995)		Rint = 0.032
Tmin = 0.155, Tmax = 0.652θmax = 26.0°
2957 measured reflectionsStandard reflections: 0
1880 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.088Δρmax = 0.32 e Å−3
S = 1.05Δρmin = −0.44 e Å−3
1880 reflectionsAbsolute structure: Flack (1983), 778 Friedel pairs
132 parametersFlack parameter: −0.018 (12)
5 restraints
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 > 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
xyzUiso*/Ueq
C10.8171 (4)0.2054 (7)0.2212 (3)0.0356 (9)
C20.9260 (6)0.1722 (13)0.1867 (3)0.0563 (13)
H21.00850.20910.22130.068*
C30.9128 (10)0.0846 (11)0.1011 (5)0.087 (3)
H30.98620.06450.07770.105*
C40.7953 (12)0.0290 (12)0.0518 (5)0.092 (3)
H40.7869−0.0257−0.00680.111*
C50.6873 (11)0.0508 (15)0.0859 (6)0.101 (3)
H50.6070.00260.05240.122*
C60.6962 (6)0.1473 (11)0.1726 (4)0.0657 (18)
H60.62220.16950.19510.079*
S10.84086 (9)0.31275 (15)0.33360 (7)0.0271 (2)
O10.9150 (3)0.1703 (6)0.39966 (19)0.0350 (6)
O20.7112 (3)0.3566 (6)0.3454 (2)0.0437 (8)
O3W0.50.2619 (7)0.50.0364 (10)
H310.505 (5)0.178 (6)0.543 (3)0.044*
O4W0.8026 (3)0.3538 (5)0.5824 (2)0.0415 (8)
H410.758 (4)0.348 (9)0.623 (2)0.05*
H420.870 (3)0.421 (8)0.607 (3)0.05*
N10.9361 (4)0.4949 (5)0.3388 (3)0.0347 (8)
Br10.86056 (5)0.68675 (6)0.24930 (3)0.05208 (18)
Na10.63738 (16)0.5271 (3)0.46276 (12)0.0365 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.053 (2)0.024 (2)0.0294 (19)0.002 (2)0.0084 (17)0.0042 (19)
C20.081 (3)0.059 (3)0.038 (2)0.010 (4)0.031 (2)0.002 (3)
C30.154 (8)0.060 (4)0.062 (4)0.024 (5)0.053 (5)−0.006 (4)
C40.169 (9)0.057 (4)0.046 (4)−0.009 (6)0.019 (5)−0.017 (3)
C50.115 (7)0.094 (6)0.071 (5)−0.037 (5)−0.023 (5)−0.020 (5)
C60.072 (3)0.078 (5)0.041 (3)−0.022 (3)0.001 (2)−0.009 (3)
S10.0296 (4)0.0250 (5)0.0281 (5)0.0014 (4)0.0094 (4)0.0013 (4)
O10.0403 (14)0.0319 (15)0.0323 (14)0.0045 (15)0.0078 (11)0.0090 (15)
O20.0321 (15)0.053 (2)0.0496 (19)0.0076 (15)0.0175 (13)−0.0002 (17)
O3W0.048 (2)0.027 (2)0.035 (2)00.011 (2)0
O4W0.0332 (14)0.042 (2)0.048 (2)0.0001 (14)0.0090 (14)−0.0032 (15)
N10.0377 (18)0.0267 (18)0.038 (2)−0.0028 (15)0.0053 (15)0.0008 (15)
Br10.0708 (3)0.0315 (2)0.0569 (3)0.0070 (3)0.0214 (2)0.0136 (3)
Na10.0365 (8)0.0316 (9)0.0442 (10)0.0041 (7)0.0156 (7)−0.0005 (7)
Geometric parameters (Å, °) top
C1—C61.360 (7)S1—N11.578 (4)
C1—C21.382 (7)O1—Na1i2.441 (3)
C1—S11.781 (4)O1—Na1ii2.496 (3)
C2—C31.379 (9)O2—Na12.372 (4)
C2—H20.93O3W—Na12.448 (4)
C3—C41.330 (12)O3W—H310.85 (4)
C3—H30.93O4W—Na1i2.436 (4)
C4—C51.359 (13)O4W—Na12.461 (4)
C4—H40.93O4W—H410.85 (4)
C5—C61.427 (12)O4W—H420.85 (4)
C5—H50.93N1—Br11.890 (4)
C6—H60.93Na1—Na1iii3.335 (3)
S1—O21.447 (3)Na1—Na1iv4.123 (2)
S1—O11.459 (3)
C6—C1—C2120.6 (5)S1—N1—Br1110.3 (2)
C6—C1—S1121.1 (4)O2—Na1—O4Wiv94.90 (14)
C2—C1—S1118.2 (4)O2—Na1—O1iv171.17 (14)
C3—C2—C1120.3 (7)O4Wiv—Na1—O1iv89.82 (14)
C3—C2—H2119.9O2—Na1—O3W97.26 (13)
C1—C2—H2119.9O4Wiv—Na1—O3W158.86 (12)
C4—C3—C2120.2 (8)O1iv—Na1—O3W80.58 (12)
C4—C3—H3119.9O2—Na1—O4W90.00 (13)
C2—C3—H3119.9O4Wiv—Na1—O4W116.45 (11)
C3—C4—C5120.9 (7)O1iv—Na1—O4W81.21 (12)
C3—C4—H4119.5O3W—Na1—O4W80.85 (11)
C5—C4—H4119.5O2—Na1—O1v110.86 (13)
C4—C5—C6120.5 (7)O4Wiv—Na1—O1v80.02 (13)
C4—C5—H5119.8O1iv—Na1—O1v77.29 (13)
C6—C5—H5119.8O3W—Na1—O1v79.51 (11)
C1—C6—C5117.4 (7)O4W—Na1—O1v152.89 (13)
C1—C6—H6121.3O2—Na1—Na1iii135.06 (11)
C5—C6—H6121.3O4Wiv—Na1—Na1iii113.23 (9)
O2—S1—O1114.88 (19)O1iv—Na1—Na1iii48.20 (8)
O2—S1—N1116.1 (2)O3W—Na1—Na1iii47.07 (8)
O1—S1—N1104.6 (2)O4W—Na1—Na1iii106.15 (11)
O2—S1—C1105.9 (2)O1v—Na1—Na1iii46.82 (8)
O1—S1—C1107.0 (2)O2—Na1—Na1iv109.05 (11)
N1—S1—C1107.9 (2)O4Wiv—Na1—Na1iv32.85 (8)
S1—O1—Na1i129.23 (17)O1iv—Na1—Na1iv71.44 (10)
S1—O1—Na1ii144.00 (18)O3W—Na1—Na1iv150.70 (10)
Na1i—O1—Na1ii84.98 (12)O4W—Na1—Na1iv86.36 (11)
S1—O2—Na1132.4 (2)O1v—Na1—Na1iv102.05 (10)
Na1iii—O3W—Na185.86 (16)Na1iii—Na1—Na1iv113.52 (6)
Na1iii—O3W—H31105 (4)O2—Na1—Na1i61.96 (9)
Na1—O3W—H31137 (4)O4Wiv—Na1—Na1i130.31 (11)
Na1i—O4W—Na1114.68 (14)O1iv—Na1—Na1i109.38 (11)
Na1i—O4W—H41112 (4)O3W—Na1—Na1i70.83 (7)
Na1—O4W—H4197 (4)O4W—Na1—Na1i32.46 (9)
Na1i—O4W—H42111 (4)O1v—Na1—Na1i147.63 (11)
Na1—O4W—H42116 (4)Na1iv—Na1—Na1i110.13 (8)
H41—O4W—H42106 (4)
Symmetry codes: (i) −x+3/2, y−1/2, −z+1; (ii) x+1/2, y−1/2, z; (iii) −x+1, y, −z+1; (iv) −x+3/2, y+1/2, −z+1; (v) x−1/2, y+1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3W—H31···N1i0.85 (4)2.12 (4)2.943 (5)167 (5)
O4W—H42···N1vi0.85 (4)2.07 (2)2.878 (5)161 (5)
Symmetry codes: (i) −x+3/2, y−1/2, −z+1; (vi) −x+2, y, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3W—H31···N1i0.85 (4)2.12 (4)2.943 (5)167 (5)
O4W—H42···N1ii0.85 (4)2.07 (2)2.878 (5)161 (5)
Symmetry codes: (i) −x+3/2, y−1/2, −z+1; (ii) −x+2, y, −z+1.
Acknowledgements top

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

references
References top

Brandenburg, K. (2002). DIAMOND. Release ???. Crystal Impact GbR, Bonn, Germany.

Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

George, E., Vivekanandan, S. & Sivakumar, K. (2000). Acta Cryst. C56, 1208–1209.

Gowda, B. T., Damodara, N. & Jyothi, K. (2005). Int. J. Chem. Kinet. 37, 572–582.

Gowda, B. T., Foro, S., Kozisek, J. & Fuess, H. (2007). Acta Cryst. E63. In the press (bt2364). Update?

Gowda, B. T., Jyothi, K., Foro, S., Kozisek, J. & Fuess, H. (2007). Acta Cryst. E63. In the press (bt2356). Update?

Gowda, B. T., Jyothi, K., Kozisek, J. & Fuess, H. (2003). Z. Naturforsch. Teil A, 58, 656–660.

Gowda, B. T., Kozisek, J., Tokarcik, M. T. & Fuess, H. (2007). Acta Cryst. E63. In the press (dn2171). Update?

Gowda, B. T., Savitha, M. B., Kozisek, J., Tokarcik, M. T. & Fuess, H. (2007). Acta Cryst. E63. In the press (bt2359). Update?

Gowda, B. T. & Shetty, M. (2004). J. Phys. Org. Chem. 17, 848–864.

Gowda, B. T., Srilatha, , Foro, S., Kozisek, J. & Fuess, H. (2007). Z. Naturforsch.Teil A, 62. In the press. Update?

Gowda, B. T. & Usha, K. M. (2003). Z. Naturforsch. Teil A, 58, 351–356.

Olmstead, M. M. & Power, P. P. (1986). Inorg. Chem. 25, 4057–4058.

Oxford Diffraction (2003). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Usha, K. M. & Gowda, B. T. (2006). J. Chem. Sci. 118, 351–359.