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Acta Cryst. (2007). E63, m1646    [ doi:10.1107/S1600536807023045 ]

Sodium 2,4,N-trichlorobenzenesulfonamidate sesquihydrate

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

Abstract top

The structure of the title compound, Na+·C6H3Cl3NO2S-·1.5H2O, is similar to those of sodium N-chlorobenzenesulfonamidate, sodium N-chloro-4-methylbenzenesulfonamidate, sodium 4,N-dichlorobenzenesulfonamidate and sodium 4,N-dichloro-2-methylbenzenesulfonamidate. There is no interaction between the N and Na atoms. The S-N distance of 1.583 (2) Å is consistent with an S=N double bond. One water molecule is located on a twofold rotation axis.

Comment top

The chemistry of arylsulfonamides and their N-halo compounds is of interest as they show distinct physical, chemical and biological properties. Many of these compounds exhibit pharmacological, fungicidal and herbicidal activities due to their oxidizing action in aqueous, partial aqueous and non-aqueous media. Thus N-halo arylsulfonamides are of interest in synthetic, mechanistic, analytical and biological chemistry (Gowda & Kumar, 2003; Gowda & Shetty, 2004; Gowda et al., 2002; Gowda et al.,2005; Gowda, Srilatha et al., 2007). In the present work, the structure of sodium N-chloro-2,4-dichlorobenzenesulfonamide has been determined to explore the substituent effects on the solid state structures of sulfonamides and N-halo arylsulfonamides (Gowda, Jyothi et al., 2003; Gowda, Srilatha et al., 2007).

The crystal structure of is complex similar to those of sodium N-chloro-benzenesulfonamide (George et al., 2000), sodium N-chloro-4-chlorobenzenesulfonamide (Gowda, Srilatha, et al., 2007), sodium N-chloro-4-methylbenzenesulfonamide (Olmstead & Power, 1986) and sodium N-chloro-2-methyl-4-chlorobenzenesulfonamide (Gowda, Jyothi et al., 2007). There is no interaction between the nitrogen and sodium atoms in the molecule, and Na+ is attached to one of the sulfonyl oxygen atoms.

The effects of N-chlorination and substitution in the phenyl ring on the structural data of sulfonamides have been considered by comparing the geometric parameters of them. The comparison revealed that on mono N-chlorination of benzenesulfonamide (George et al., 2000) and 4-chlorbenzenesulfonamide (Gowda, Jyothi et al., 2003), the C—S and S—O bond lengths increased marginally, while the S—N bond length remained more or less the same or decreased marginally. Further, N-chlorination of N-chloro-4-chlorobenzenesulfonamide decreases the C—S, S—O and N—Cl, but increased the S—N bond length (Gowda, Jyothi et al., 2007). The introduction of an additional Cl atom to the benzene ring at the ortho position marginally increased the C—S bond length and decreased the S—N bond length, while the S—O and N—Cl bond lengths remained more or less the same. The bond angles also changed on both N-chlorination and introduction of Cl atoms to the benzene ring.

Related literature top

For related literature, see: George et al. (2000); Gowda & Kumar (2003); Gowda & Shetty (2004); Gowda et al. (2002, 2005); Gowda, D'Souza & Kumar (2003); Gowda, Jyothi, Kozisek & Fuess (2003); Gowda, Jyothi, Kozisek, Tokarcik & Fuess (2007); Gowda, Srilatha, Foro, Kozisek & Fuess (2007); Olmstead & Power (1986).

Experimental top

The title compound was prepared according to the literature method (Gowda, D'Souza et al., 2003 a). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared, and NMR spectra (Gowda, D'Souza et al., 2003 a). Single crystals of the title compound were obtained from a slow evaporation of its chloroform solution and used for X-ray diffraction studies at room temperature.

Refinement top

Crystals of the title compound are monoclinic; space group C2/c. H atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å and with Uiso(H) = 1.2 Ueq(C). No restraints were applied for non-hydrogen atoms. Friedel equivalents were merged prior to the final refinements.

H atoms bonded to O atoms were found in fourier map and finally refined with O—H bond length restrained to 0.82 (1)Å and Uiso(H) = 1.2 Ueq(O).

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 (50% probability displacement ellipsoids)
[Figure 2] Fig. 2. Packing diagram of the title compound viewed down the axis b.
Sodium 2,4,N-trichlorobenzenesulfonamidate sesquihydrate top
Crystal data top
Na+·C6H3Cl3NO2S−·1.5H2OF(000) = 1240.0
Mr = 309.52Dx = 1.834 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3687 reflections
a = 11.033 (2) Åθ = 3.6–30.1°
b = 6.7410 (13) ŵ = 1.04 mm−1
c = 30.187 (6) ÅT = 294 K
β = 98.51 (3)°Block, yellow
V = 2220.4 (8) Å30.46 × 0.32 × 0.16 mm
Z = 8
Data collection top
Oxford Diffraction Xcalibur System
diffractometer		2162 independent reflections
Radiation source: fine-focus sealed tube1872 reflections with I > 2σ(I)
graphiteRint = 0.047
Rotation method data acquisition using ω and phi scansθmax = 26.2°, θmin = 6.8°
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2003)		h = −13→13
Tmin = 0.646, Tmax = 0.851k = 0→8
3256 measured reflectionsl = 0→37
Refinement top
Refinement on F2H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0305P)2 + 4.9463P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.038(Δ/σ)max = 0.001
wR(F2) = 0.081Δρmax = 0.40 e Å−3
S = 1.09Δρmin = −0.41 e Å−3
2162 reflectionsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
151 parametersExtinction coefficient: 0.0083 (6)
7 restraints
Crystal data top
Na+·C6H3Cl3NO2S−·1.5H2OV = 2220.4 (8) Å3
Mr = 309.52Z = 8
Monoclinic, C2/cMo Kα radiation
a = 11.033 (2) ŵ = 1.04 mm−1
b = 6.7410 (13) ÅT = 294 K
c = 30.187 (6) Å0.46 × 0.32 × 0.16 mm
β = 98.51 (3)°
Data collection top
Oxford Diffraction Xcalibur System
diffractometer		1872 reflections with I > 2σ(I)
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2003)		Rint = 0.047
Tmin = 0.646, Tmax = 0.851θmax = 26.2°
3256 measured reflectionsStandard reflections: 0
2162 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.081Δρmax = 0.40 e Å−3
S = 1.09Δρmin = −0.41 e Å−3
2162 reflectionsAbsolute structure: ?
151 parametersFlack parameter: ?
7 restraintsRogers parameter: ?
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3266 (2)0.3152 (3)0.61865 (8)0.0221 (5)
C20.4082 (2)0.3777 (4)0.59049 (8)0.0260 (5)
C30.3651 (3)0.4513 (4)0.54803 (9)0.0348 (6)
H30.41980.49370.52930.042*
C40.2411 (3)0.4607 (4)0.53402 (9)0.0374 (7)
C50.1587 (3)0.4044 (5)0.56120 (10)0.0413 (7)
H50.07490.41460.55140.05*
C60.2020 (2)0.3320 (4)0.60359 (9)0.0329 (6)
H60.14630.29390.62230.039*
N10.46541 (19)0.0345 (3)0.66974 (7)0.0267 (5)
O10.44434 (16)0.3586 (3)0.70026 (6)0.0317 (4)
O20.25872 (17)0.1563 (3)0.68763 (6)0.0359 (5)
S10.37271 (5)0.21142 (9)0.672848 (19)0.02257 (18)
Cl10.39467 (6)−0.15130 (10)0.63434 (2)0.0345 (2)
Cl20.56526 (6)0.36763 (12)0.60616 (3)0.0424 (2)
Cl30.18902 (9)0.53791 (12)0.47951 (3)0.0579 (3)
Na10.14565 (9)−0.00688 (16)0.73657 (3)0.0328 (3)
O300.2632 (4)0.750.0346 (6)
H31−0.010 (3)0.339 (3)0.7290 (7)0.041*
O40.28754 (17)0.1707 (3)0.79286 (6)0.0350 (5)
H410.247 (2)0.196 (4)0.8128 (6)0.042*
H420.3478 (17)0.111 (4)0.8039 (8)0.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0252 (12)0.0203 (12)0.0208 (11)0.0009 (10)0.0029 (9)−0.0014 (9)
C20.0301 (13)0.0220 (12)0.0255 (12)−0.0008 (10)0.0031 (10)−0.0002 (10)
C30.0514 (18)0.0274 (14)0.0264 (13)−0.0040 (13)0.0084 (12)0.0034 (11)
C40.0562 (19)0.0245 (14)0.0272 (13)0.0024 (13)−0.0080 (13)0.0030 (11)
C50.0357 (16)0.0397 (16)0.0429 (17)0.0060 (13)−0.0124 (13)0.0002 (14)
C60.0288 (14)0.0348 (15)0.0343 (14)0.0027 (11)0.0025 (11)0.0006 (12)
N10.0279 (11)0.0251 (11)0.0259 (11)0.0004 (9)−0.0003 (9)−0.0017 (9)
O10.0341 (10)0.0343 (10)0.0258 (9)−0.0022 (8)0.0010 (8)−0.0077 (8)
O20.0307 (10)0.0484 (12)0.0314 (10)−0.0019 (9)0.0142 (8)0.0066 (9)
S10.0237 (3)0.0258 (3)0.0183 (3)−0.0003 (2)0.0035 (2)−0.0003 (2)
Cl10.0408 (4)0.0289 (4)0.0344 (4)−0.0029 (3)0.0080 (3)−0.0068 (3)
Cl20.0277 (4)0.0522 (5)0.0487 (4)−0.0044 (3)0.0104 (3)0.0122 (4)
Cl30.0932 (7)0.0384 (4)0.0331 (4)−0.0024 (4)−0.0209 (4)0.0076 (3)
Na10.0320 (6)0.0350 (6)0.0330 (6)−0.0054 (4)0.0105 (4)0.0002 (5)
O30.0487 (16)0.0275 (15)0.0256 (14)0−0.0007 (12)0
O40.0287 (10)0.0442 (12)0.0321 (10)0.0026 (9)0.0047 (8)−0.0021 (9)
Geometric parameters (Å, °) top
C1—C61.387 (4)O2—S11.4440 (19)
C1—C21.392 (3)O2—Na12.344 (2)
C1—S11.783 (2)S1—Na1i3.3597 (13)
C2—C31.391 (4)Na1—O42.446 (2)
C2—Cl21.729 (3)Na1—O1iii2.450 (2)
C3—C41.372 (4)Na1—O1iv2.497 (2)
C3—H30.93Na1—O4iii2.500 (2)
C4—C51.366 (4)Na1—O32.501 (2)
C4—Cl31.741 (3)Na1—S1iii3.3597 (13)
C5—C61.387 (4)Na1—Na1v3.429 (2)
C5—H50.93Na1—Na1i4.0948 (13)
C6—H60.93Na1—Na1iii4.0948 (13)
N1—S11.583 (2)O3—Na1v2.501 (2)
N1—Cl11.753 (2)O3—H310.809 (10)
O1—S11.4493 (18)O4—Na1i2.500 (2)
O1—Na1i2.450 (2)O4—H410.817 (10)
O1—Na1ii2.497 (2)O4—H420.806 (10)
C6—C1—C2118.3 (2)O4—Na1—O383.78 (6)
C6—C1—S1117.86 (19)O1iii—Na1—O378.42 (6)
C2—C1—S1123.82 (19)O1iv—Na1—O377.55 (6)
C3—C2—C1120.5 (2)O4iii—Na1—O3157.05 (7)
C3—C2—Cl2117.3 (2)O2—Na1—S1iii151.64 (6)
C1—C2—Cl2122.25 (19)O4—Na1—S1iii79.67 (6)
C4—C3—C2119.3 (3)O1iii—Na1—S1iii22.68 (4)
C4—C3—H3120.3O1iv—Na1—S1iii89.73 (6)
C2—C3—H3120.3O4iii—Na1—S1iii81.63 (6)
C5—C4—C3121.6 (3)O3—Na1—S1iii99.33 (5)
C5—C4—Cl3119.7 (2)O2—Na1—Na1v138.93 (7)
C3—C4—Cl3118.7 (2)O4—Na1—Na1v111.20 (6)
C4—C5—C6118.9 (3)O1iii—Na1—Na1v46.70 (5)
C4—C5—H5120.6O1iv—Na1—Na1v45.57 (5)
C6—C5—H5120.6O4iii—Na1—Na1v114.84 (5)
C5—C6—C1121.4 (3)O3—Na1—Na1v46.72 (5)
C5—C6—H6119.3S1iii—Na1—Na1v68.66 (4)
C1—C6—H6119.3O2—Na1—Na1i53.30 (6)
S1—N1—Cl1109.95 (12)O4—Na1—Na1i34.54 (5)
S1—O1—Na1i116.63 (10)O1iii—Na1—Na1i115.54 (6)
S1—O1—Na1ii150.88 (11)O1iv—Na1—Na1i145.42 (6)
Na1i—O1—Na1ii87.74 (7)O4iii—Na1—Na1i126.81 (6)
S1—O2—Na1152.22 (13)O3—Na1—Na1i74.01 (5)
O2—S1—O1115.22 (11)S1iii—Na1—Na1i113.82 (5)
O2—S1—N1115.11 (12)Na1v—Na1—Na1i118.20 (3)
O1—S1—N1104.31 (11)O2—Na1—Na1iii100.07 (7)
O2—S1—C1103.96 (11)O4—Na1—Na1iii88.97 (7)
O1—S1—C1108.23 (11)O1iii—Na1—Na1iii79.75 (5)
N1—S1—C1109.90 (11)O1iv—Na1—Na1iii103.04 (5)
O2—S1—Na1i74.56 (9)O4iii—Na1—Na1iii33.70 (4)
O1—S1—Na1i40.69 (8)O3—Na1—Na1iii157.39 (5)
N1—S1—Na1i126.25 (8)S1iii—Na1—Na1iii58.23 (3)
C1—S1—Na1i118.80 (8)Na1v—Na1—Na1iii118.20 (3)
O2—Na1—O482.10 (8)Na1i—Na1—Na1iii110.80 (5)
O2—Na1—O1iii168.19 (8)Na1v—O3—Na186.55 (10)
O4—Na1—O1iii86.09 (7)Na1v—O3—H31125 (2)
O2—Na1—O1iv114.55 (8)Na1—O3—H31110 (2)
O4—Na1—O1iv156.75 (8)Na1—O4—Na1i111.76 (8)
O1iii—Na1—O1iv76.75 (8)Na1—O4—H41104.5 (19)
O2—Na1—O4iii88.36 (8)Na1i—O4—H41108 (2)
O4—Na1—O4iii118.70 (6)Na1—O4—H42117 (2)
O1iii—Na1—O4iii97.45 (7)Na1i—O4—H42108 (2)
O1iv—Na1—O4iii79.53 (7)H41—O4—H42108 (2)
O2—Na1—O3100.09 (8)
C6—C1—C2—C3−1.3 (4)C2—C1—S1—O161.2 (2)
S1—C1—C2—C3177.9 (2)C6—C1—S1—N1127.0 (2)
C6—C1—C2—Cl2178.9 (2)C2—C1—S1—N1−52.1 (2)
S1—C1—C2—Cl2−2.0 (3)C6—C1—S1—Na1i−76.5 (2)
C1—C2—C3—C4−0.4 (4)C2—C1—S1—Na1i104.3 (2)
Cl2—C2—C3—C4179.5 (2)S1—O2—Na1—O451.6 (3)
C2—C3—C4—C51.8 (4)S1—O2—Na1—O1iii52.1 (6)
C2—C3—C4—Cl3−175.9 (2)S1—O2—Na1—O1iv−145.4 (3)
C3—C4—C5—C6−1.5 (4)S1—O2—Na1—O4iii−67.7 (3)
Cl3—C4—C5—C6176.1 (2)S1—O2—Na1—O3133.8 (3)
C4—C5—C6—C1−0.2 (4)S1—O2—Na1—S1iii1.2 (4)
C2—C1—C6—C51.6 (4)S1—O2—Na1—Na1v165.0 (2)
S1—C1—C6—C5−177.6 (2)S1—O2—Na1—Na1i72.6 (3)
Na1—O2—S1—O1−73.5 (3)S1—O2—Na1—Na1iii−35.9 (3)
Na1—O2—S1—N147.9 (3)O2—Na1—O3—Na1v152.16 (7)
Na1—O2—S1—C1168.2 (3)O4—Na1—O3—Na1v−127.04 (6)
Na1—O2—S1—Na1i−75.3 (3)O1iii—Na1—O3—Na1v−39.77 (5)
Na1i—O1—S1—O2−2.58 (16)O1iv—Na1—O3—Na1v39.03 (5)
Na1ii—O1—S1—O2141.4 (2)O4iii—Na1—O3—Na1v41.92 (16)
Na1i—O1—S1—N1−129.75 (11)S1iii—Na1—O3—Na1v−48.61 (3)
Na1ii—O1—S1—N114.3 (3)Na1i—Na1—O3—Na1v−160.87 (5)
Na1i—O1—S1—C1113.26 (12)Na1iii—Na1—O3—Na1v−55.04 (13)
Na1ii—O1—S1—C1−102.7 (2)O2—Na1—O4—Na1i30.41 (8)
Na1ii—O1—S1—Na1i144.0 (3)O1iii—Na1—O4—Na1i−149.48 (8)
Cl1—N1—S1—O256.49 (15)O1iv—Na1—O4—Na1i−107.28 (19)
Cl1—N1—S1—O1−176.27 (11)O4iii—Na1—O4—Na1i114.16 (12)
Cl1—N1—S1—C1−60.44 (15)O3—Na1—O4—Na1i−70.72 (7)
Cl1—N1—S1—Na1i145.30 (7)S1iii—Na1—O4—Na1i−171.42 (8)
C6—C1—S1—O23.3 (2)Na1v—Na1—O4—Na1i−109.28 (7)
C2—C1—S1—O2−175.8 (2)Na1iii—Na1—O4—Na1i130.72 (8)
C6—C1—S1—O1−119.6 (2)
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) x+1/2, y+1/2, z; (iii) −x+1/2, y−1/2, −z+3/2; (iv) x−1/2, y−1/2, z; (v) −x, y, −z+3/2.
Acknowledgements top

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

references
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