supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsdisplay schemecited insimilar papers buy article online

dn2194 scheme

Acta Cryst. (2007). E63, m1957    [ doi:10.1107/S1600536807029248 ]

Sodium N-bromo-4-chloro-2-methylbenzenesulfonamidate sesquihydrate

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

Abstract top

The title compound, Na+·C7H6BrClNO2S-·1.5H2O, crystallizes with two cations, two anions and three water molecules in the asymmetric unit; its structure is similar to that of sodium N-bromobenzenesulfonamidate and sodium N-bromo-4-chlorobenzenesulfonamidate. The sodium ion shows octahedral coordination by three O atoms of water molecules and by three sulfonyl O atoms of three different N-bromo-4-chloro-2-methylbenzenesulfonamide anions. There is no interaction between the N atoms and sodium ions in the structure. The S-N distance of 1.584 (4) 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-halo-arylsulfonamides is of interest due to their diverse characteristics (Usha & Gowda, 2006). In the present work, the structure of sodium N-bromo-2-methyl-4-chloro-benzenesulfonamidate (NaNB2M4CBSA) has been determined to explore the substituent effects on the solid state structures of arylsulfonamides and N-halo arylsulfonamidates (Gowda et al., 2007a, b, c, d). The structure of NaNB2M4CBSA (Fig. 1) resembles those of sodium N-chloro-2-methyl- 4-chloro-benzenesulfonamidate (NaNC2M4CBSA)(Gowda, Srilatha et al., 2007), sodium N-bromo-benzenesulfonamidate (NaNBBSA) (Gowda, Usha et al., 2007) and sodium N-bromo-4-chloro-benzenesulfonamidate (NaNB4CBSA)(Gowda, Kožíšek et al., 2007) and other sodium N-chloro-arylsulfonamidates (George et al., 2000; Gowda, Jyothi et al., 2007). NaNB2M4CBSA 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 water molecules and by three sulfonyl O atoms of three different N-bromo-2-methyl- 4-chloro-benzenesulfonamide anions. There is no interaction between the nitrogen and sodium ions in the molecule. The S—N distances of N1—S1, 1.584 (4)Å is consistent with a S—N double bond and in agreement with those observed with NaNBBSA, NaNB4CBSA and NaNC2M4CBSA. O—H···N hydrogen bonding interactions result in the formation of a polymeric layer structure running parallel to the (0 0 1) plane (Table 1, Fig. 2).

Related literature top

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

All H atoms attached to C and O atoms were positioned geometrically and treated as riding with C—H = 0.93Å (aromatic) and C—H = 0.96Å (methyl). H atoms of water molecules were refined using restraint on O—H bond length 0.85 (3)Å and restraint on their mutual distance 1.45 (4) Å. All H atoms have Uiso(H) = 1.2 Ueq(C).

Regarding the discrepancy with reflection numbers, the number of reflections used in the refinement (2049) differs from the total number of reflections (2231) because of applying resolution shel 0.82 to 3.5 Å.

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. ORTEP view of the title compound showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Na O interactions are shown as dashed lines. H atoms are represented as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Partial packing diagram of (I) showing hydrogen bonds O3w—H31···N1(i) and O4w—-H41···N1(ii). Symmetry codes: (i) −x, y, −z + 1/2; (ii) x + 1/2, y − 1/2, z. H atoms not involved in hydrogen bonds have been omitted for clarity.
Sodium N-bromo-4-chloro-2-methylbenzenesulfonamidate sesquihydrate top
Crystal data top
Na+·C7H6BrClNO2S–·1.5H2OF000 = 1320
Mr = 333.56Dx = 1.929 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2337 reflections
a = 11.055 (2) Åθ = 2.5–26.4º
b = 6.7804 (14) ŵ = 4.06 mm−1
c = 30.727 (6) ÅT = 300 (2) K
β = 98.84 (3)ºBlock, pale yellow
V = 2275.9 (8) Å30.58 × 0.48 × 0.10 mm
Z = 8
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer		2066 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.067
T = 300(2) Kθmax = 26.4º
Rotation method data acquisition using ωand φ scansθmin = 4.6º
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2003) using a multifaceted crystal model (Clark & Reid, 1995)		h = −13→13
Tmin = 0.196, Tmax = 0.632k = −5→8
6929 measured reflectionsl = −38→38
2231 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)] = 0.070H-atom parameters constrained
wR(F2) = 0.091  w = 1/[σ2(Fo2) + (0.0001P)2 + 21.0707P]
where P = (Fo2 + 2Fc2)/3
S = 1.21(Δ/σ)max < 0.001
2049 reflectionsΔρmax = 0.46 e Å−3
142 parametersΔρmin = −0.68 e Å−3
4 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
Na+·C7H6BrClNO2S–·1.5H2OV = 2275.9 (8) Å3
Mr = 333.56Z = 8
Monoclinic, C2/cMo Kα
a = 11.055 (2) ŵ = 4.06 mm−1
b = 6.7804 (14) ÅT = 300 (2) K
c = 30.727 (6) Å0.58 × 0.48 × 0.10 mm
β = 98.84 (3)º
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer		2231 independent reflections
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2003) using a multifaceted crystal model (Clark & Reid, 1995)		2066 reflections with I > 2σ(I)
Tmin = 0.196, Tmax = 0.632Rint = 0.067
6929 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0704 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 1.21  w = 1/[σ2(Fo2) + (0.0001P)2 + 21.0707P]
where P = (Fo2 + 2Fc2)/3
2049 reflectionsΔρmax = 0.46 e Å−3
142 parametersΔρmin = −0.68 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
C10.6736 (4)−0.3263 (7)0.38143 (14)0.0199 (10)
C20.5880 (4)−0.3838 (7)0.40799 (15)0.0236 (11)
C30.6320 (5)−0.4536 (8)0.45013 (17)0.0331 (13)
H30.5773−0.49540.46840.040*
C40.7558 (6)−0.4611 (8)0.46494 (18)0.0371 (14)
C50.8403 (5)−0.4086 (9)0.43893 (19)0.0399 (14)
H50.9237−0.41770.44930.048*
C60.7983 (5)−0.3415 (9)0.39678 (18)0.0328 (12)
H60.8543−0.30600.37850.039*
C70.4501 (4)−0.3698 (8)0.39352 (17)0.0286 (12)
H7A0.4086−0.42120.41630.043*
H7B0.4274−0.44500.36710.043*
H7C0.4274−0.23430.38810.043*
N10.5374 (4)−0.0524 (6)0.32821 (13)0.0242 (9)
O10.5613 (3)−0.3788 (5)0.30020 (11)0.0292 (8)
O20.7460 (3)−0.1762 (6)0.31310 (12)0.0339 (9)
O3W0.7076 (3)−0.1898 (6)0.20927 (12)0.0341 (9)
H310.6490−0.11900.20010.051*
H320.7490−0.21700.18860.051*
O4W1.0000−0.2798 (8)0.25000.0337 (12)
H411.0070−0.36520.26950.050*
S10.63097 (10)−0.22859 (19)0.32722 (4)0.0210 (3)
Cl110.80599 (19)−0.5332 (3)0.51941 (5)0.0600 (5)
Br10.60784 (5)0.15106 (9)0.366127 (17)0.03129 (16)
Na10.85419 (18)−0.0126 (3)0.26251 (7)0.0323 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.023 (2)0.016 (3)0.020 (2)0.000 (2)−0.0012 (18)−0.003 (2)
C20.028 (2)0.020 (3)0.022 (2)0.000 (2)0.004 (2)−0.002 (2)
C30.045 (3)0.029 (3)0.026 (3)−0.003 (3)0.008 (2)0.004 (2)
C40.052 (4)0.023 (3)0.030 (3)0.001 (3)−0.017 (3)0.002 (2)
C50.030 (3)0.041 (4)0.043 (3)0.007 (3)−0.011 (3)0.003 (3)
C60.026 (2)0.032 (3)0.039 (3)0.004 (3)0.002 (2)0.001 (3)
C70.027 (2)0.030 (3)0.031 (3)−0.006 (2)0.009 (2)0.004 (2)
N10.025 (2)0.024 (2)0.0217 (19)0.0010 (19)−0.0035 (16)0.0016 (18)
O10.0325 (18)0.031 (2)0.0236 (17)−0.0036 (17)0.0021 (14)−0.0051 (15)
O20.0286 (18)0.042 (2)0.034 (2)−0.0017 (18)0.0140 (16)0.0030 (18)
O3W0.0277 (18)0.039 (3)0.035 (2)0.0013 (17)0.0058 (15)−0.0010 (18)
O4W0.049 (3)0.027 (3)0.024 (2)0.0000.001 (2)0.000
S10.0214 (6)0.0237 (7)0.0179 (5)0.0006 (5)0.0031 (4)0.0003 (5)
Cl110.0932 (13)0.0454 (11)0.0324 (8)−0.0005 (10)−0.0190 (8)0.0083 (7)
Br10.0338 (3)0.0274 (3)0.0330 (3)−0.0024 (3)0.0062 (2)−0.0056 (2)
Na10.0316 (11)0.0338 (12)0.0330 (11)−0.0065 (10)0.0101 (9)−0.0003 (10)
Geometric parameters (Å, °) top
C1—C61.390 (6)N1—Br11.894 (4)
C1—C21.397 (6)O1—S11.457 (4)
C1—S11.788 (5)O1—Na1i2.441 (4)
C2—C31.394 (7)O2—S11.449 (3)
C2—C71.524 (7)O2—Na12.377 (4)
C3—C41.375 (8)O3W—Na12.436 (4)
C3—H30.9300O3W—Na1i2.488 (4)
C4—C51.366 (8)O3W—H310.8208
C4—Cl111.750 (5)O3W—H320.8585
C5—C61.384 (8)O4W—Na12.494 (4)
C5—H50.9300O4W—H410.8283
C6—H60.9300S1—Na1i3.388 (2)
C7—H7A0.9600Na1—O1ii2.568 (4)
C7—H7B0.9600Na1—S1iii3.388 (2)
C7—H7C0.9600Na1—Na1iv3.427 (4)
N1—S11.584 (4)Na1—Na1i4.105 (3)
C6—C1—C2120.4 (4)C1—S1—Na1i120.60 (16)
C6—C1—S1116.7 (4)O2—Na1—O3W81.90 (14)
C2—C1—S1122.9 (3)O2—Na1—O1iii168.96 (16)
C3—C2—C1117.8 (4)O3W—Na1—O1iii87.06 (14)
C3—C2—C7118.9 (4)O2—Na1—O3Wiii89.42 (14)
C1—C2—C7123.3 (4)O3W—Na1—O3Wiii118.56 (11)
C4—C3—C2120.5 (5)O1iii—Na1—O3Wiii96.15 (14)
C4—C3—H3119.7O2—Na1—O4W99.44 (14)
C2—C3—H3119.7O3W—Na1—O4W85.24 (12)
C5—C4—C3122.1 (5)O1iii—Na1—O4W79.25 (12)
C5—C4—Cl11119.2 (4)O3Wiii—Na1—O4W155.70 (14)
C3—C4—Cl11118.7 (5)O2—Na1—O1ii111.94 (14)
C4—C5—C6118.1 (5)O3W—Na1—O1ii158.82 (14)
C4—C5—H5120.9O1iii—Na1—O1ii78.58 (14)
C6—C5—H5120.9O3Wiii—Na1—O1ii78.81 (13)
C5—C6—C1120.9 (5)O4W—Na1—O1ii76.89 (12)
C5—C6—H6119.5O2—Na1—S1iii152.84 (12)
C1—C6—H6119.5O3W—Na1—S1iii81.03 (11)
C2—C7—H7A109.5O3Wiii—Na1—S1iii80.44 (10)
C2—C7—H7B109.5O4W—Na1—S1iii100.03 (9)
H7A—C7—H7B109.5O1ii—Na1—S1iii90.86 (10)
C2—C7—H7C109.5O2—Na1—Na1iv137.06 (13)
H7A—C7—H7C109.5O3W—Na1—Na1iv113.64 (12)
H7B—C7—H7C109.5O1iii—Na1—Na1iv48.38 (10)
S1—N1—Br1110.7 (2)O3Wiii—Na1—Na1iv113.35 (10)
S1—O1—Na1i118.48 (19)O4W—Na1—Na1iv46.60 (10)
S1—O1—Na1v149.3 (2)O1ii—Na1—Na1iv45.30 (9)
Na1i—O1—Na1v86.31 (13)S1iii—Na1—Na1iv69.67 (6)
S1—O2—Na1149.7 (2)O2—Na1—Na1i54.02 (10)
Na1—O3W—Na1i112.95 (15)O3W—Na1—Na1i33.93 (10)
Na1—O3W—H31110.6O1iii—Na1—Na1i115.51 (12)
Na1i—O3W—H31112.9O3Wiii—Na1—Na1i127.99 (12)
Na1—O3W—H32103.2O4W—Na1—Na1i74.25 (9)
Na1i—O3W—H32106.0O1ii—Na1—Na1i144.31 (12)
H31—O3W—H32110.7S1iii—Na1—Na1i114.39 (9)
Na1iv—O4W—Na186.81 (19)Na1iv—Na1—Na1i118.57 (6)
Na1iv—O4W—H41129.0O2—Na1—Na1iii100.58 (12)
Na1—O4W—H41112.8O3W—Na1—Na1iii89.16 (13)
O2—S1—O1114.3 (2)O1iii—Na1—Na1iii79.46 (10)
O2—S1—N1115.3 (2)O3Wiii—Na1—Na1iii33.12 (9)
O1—S1—N1104.4 (2)O4W—Na1—Na1iii158.22 (11)
O2—S1—C1104.6 (2)O1ii—Na1—Na1iii103.23 (10)
O1—S1—C1108.2 (2)S1iii—Na1—Na1iii58.26 (5)
N1—S1—C1109.9 (2)Na1iv—Na1—Na1iii118.57 (6)
O2—S1—Na1i75.00 (16)Na1i—Na1—Na1iii111.37 (10)
N1—S1—Na1i123.91 (16)
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x+1/2, y+1/2, z; (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+2, y, −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···N1vi0.822.162.927 (5)156
O4W—H41···N1vii0.832.193.010 (5)171
Symmetry codes: (vi) −x+1, y, −z+1/2; (vii) x+1/2, y−1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3W—H31···N1i0.822.162.927 (5)156
O4W—H41···N1ii0.832.193.010 (5)171
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) x+1/2, y−1/2, z.
Acknowledgements top

BTG gratefully 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

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

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

Farrugia, L. J. (1997). ORTEP-3 for Windows. J.Appl.Cryst. 30, 565.

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

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

Gowda, B. T., Jyothi, K., Foro, S., Kožíšek, J. & Fuess, H. (2007). Acta Cryst. E63, m1644–m1645.

Gowda, B. T., Kožíšek, J., Tokarčík, M. & Fuess, H. (2007). Acta Cryst. E63, m1647–m1648.

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

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

Gowda, B. T., Usha, K. M., Kožíšek, J., Tokarčík, M. & Fuess, H. (2007). Acta Cryst. E63, m1739–m1740.

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.