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Acta Cryst. (2009). E65, o717    [ doi:10.1107/S1600536809007880 ]

4-Chloro-N-(2-chlorophenyl)-2-methylbenzenesulfonamide

B. T. Gowda, S. Foro, P. G. Nirmala, K. S. Babitha and H. Fuess

Abstract top

In the crystal structure of the title compound, C13H11Cl2NO2S, the conformations of the N-C bond in the C-SO2-NH-C segment are trans and gauche with respect to the S=O bonds. The C-S(O2)-N(H)-C torsion angle is 74.8 (4)°, indicating that the molecule is bent at the S atom. In the crystal structure, inversion dimers linked by pairs of N-H...O hydrogen bonds occur. An intramolecular N-H...Cl interaction is also present.

Comment top

In the present work, as part of a study of substituent effects on the structures of N-(aryl)-arylsulfonamides (Gowda et al. 2008a,b, 2009), the structure of 2-methyl-4-chloro-N-(2-chlorophenyl)benzenesulfonamide (I) has been determined. The conformations of the N—C bond in the C—S(O2)—N(H)—C segment are trans and gauche with respect to the S=O bonds (Fig. 1). The torsion angle of C1—S1—N1—C1 is 74.8 (4)°, indicating the molecule is bent at the S1 atom. The two benzene rings are tilted relative to each other by 45.5 (2)°, compared with the values of 86.6 (2)° (molecule 1) and 83.0 (2)° (molecule 2), in the two independent molecules of 2-methyl-4-chloro-N-(phenyl)-benzenesulfonamide (II) (Gowda et al., 2009). Bond distance parameters in (I) are similar to those observed in (II), 2,4-dimethyl-N-(phenyl)benzenesulfonamide (Gowda et al., 2008b) and other aryl sulfonamides (Perlovich et al., 2006; Gelbrich et al., 2007). The crystal structure comprises the packing of centrosymmetric molecules connected via N—H···O hydrogen bonds (Table 1 & Fig. 2).

Related literature top

For related structures of N-(aryl)-arylsulfonamides, see: Gelbrich et al. (2007); Gowda et al. (2009a,b); Perlovich et al. (2006).

Experimental top

m-Chlorotoluene (10 ml) in chloroform (40 ml) was treated dropwise with chlorosulfonic acid (25 ml) at 0° C. After the initial evolution of HCl subsided, the reaction mixture was brought to room temperature and poured into crushed ice in a beaker. The chloroform layer was separated, washed with cold water and allowed to evaporate slowly. The residual 2-methyl-4-chlorobenzenesulfonylchloride was treated with 2-chloroaniline in a stoichiometric ratio and boiled for ten minutes. The reaction mixture was then cooled to room temperature and added to ice cold water (100 ml). The resultant solid 2-methyl-4-chloro-N-(2-chlorophenyl)-benzenesulfonamide was filtered under suction and washed thoroughly with cold water. It was then recrystallized to constant melting point from dilute ethanol. The purity of the compound was checked and characterized by recording its infrared and NMR spectra. The single crystals used in X-ray diffraction studies were grown from an ethanolic solution by slow evaporation at room temperature.

Refinement top

The N-bound H atom was located in difference map and its positional parameters refined; N—H = 0.88 (5) Å. The remaining H atoms were positioned with idealized geometries using a riding model with C—H = 0.93–0.96 Å. All H atoms were refined with isotropic displacement parameters set to 1.2 x Ueq(parent atom).

Computing details top

Data collection: CAD-4-PC (Enraf–Nonius, 1996); cell refinement: CAD-4-PC (Enraf–Nonius, 1996; data reduction: REDU4 (Stoe & Cie, 1987); 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 top
[Figure 1] Fig. 1. Molecular structure of (I), showing the atom labeling scheme. The displacement ellipsoids are drawn at the 50% probability level. The H atoms are represented as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Molecular packing of (I) with hydrogen bonding shown as dashed lines.
4-Chloro-N-(2-chlorophenyl)-2-methylbenzenesulfonamide top
Crystal data top
C13H11Cl2NO2SZ = 2
Mr = 316.19F(000) = 324
Triclinic, P1Dx = 1.549 Mg m−3
Hall symbol: -P 1Cu Kα radiation, λ = 1.54180 Å
a = 8.089 (2) ÅCell parameters from 25 reflections
b = 8.096 (2) Åθ = 5.7–19.7°
c = 10.946 (3) ŵ = 5.73 mm−1
α = 96.00 (1)°T = 299 K
β = 97.11 (2)°Plate, colourless
γ = 105.67 (2)°0.45 × 0.33 × 0.08 mm
V = 677.7 (3) Å3
Data collection top
Enraf–Nonius CAD-4
diffractometer		1932 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.037
graphiteθmax = 66.9°, θmin = 4.1°
ω scansh = −9→1
Absorption correction: ψ scan
(North et al., 1968)		k = −9→9
Tmin = 0.150, Tmax = 0.640l = −12→13
2684 measured reflections3 standard reflections every 120 min
2414 independent reflections intensity decay: 1.0%
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)] = 0.083H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.236 w = 1/[σ2(Fo2) + (0.179P)2 + 0.1079P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.008
2414 reflectionsΔρmax = 0.60 e Å−3
177 parametersΔρmin = −0.67 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.039 (6)
Crystal data top
C13H11Cl2NO2Sγ = 105.67 (2)°
Mr = 316.19V = 677.7 (3) Å3
Triclinic, P1Z = 2
a = 8.089 (2) ÅCu Kα radiation
b = 8.096 (2) ŵ = 5.73 mm−1
c = 10.946 (3) ÅT = 299 K
α = 96.00 (1)°0.45 × 0.33 × 0.08 mm
β = 97.11 (2)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		1932 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.037
Tmin = 0.150, Tmax = 0.640θmax = 66.9°
2684 measured reflections3 standard reflections every 120 min
2414 independent reflections intensity decay: 1.0%
Refinement top
R[F2 > 2σ(F2)] = 0.083H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.236Δρmax = 0.60 e Å−3
S = 1.05Δρmin = −0.67 e Å−3
2414 reflectionsAbsolute structure: ?
177 parametersFlack parameter: ?
0 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.

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
Cl10.35954 (18)0.30027 (19)0.56480 (12)0.0932 (5)
Cl20.70514 (17)0.48939 (15)0.15780 (13)0.0901 (5)
S10.71199 (12)−0.00409 (12)0.15693 (9)0.0651 (4)
O10.8667 (4)−0.0424 (4)0.2054 (3)0.0761 (8)
O20.5732 (4)−0.1359 (4)0.0795 (3)0.0757 (8)
N10.7673 (4)0.1494 (4)0.0701 (3)0.0659 (9)
H1N0.678 (7)0.178 (6)0.034 (5)0.079*
C10.6225 (5)0.0807 (5)0.2792 (4)0.0637 (9)
C20.7215 (5)0.1757 (5)0.3907 (4)0.0660 (10)
C30.6344 (6)0.2423 (6)0.4761 (4)0.0719 (11)
H30.69740.30690.55070.086*
C40.4585 (6)0.2158 (6)0.4536 (4)0.0708 (10)
C50.3607 (6)0.1217 (6)0.3426 (4)0.0732 (11)
H50.24100.10360.32710.088*
C60.4441 (5)0.0565 (5)0.2569 (4)0.0686 (10)
H60.3800−0.00570.18180.082*
C70.9177 (5)0.2931 (5)0.1116 (4)0.0625 (9)
C80.9064 (6)0.4560 (5)0.1521 (4)0.0693 (10)
C91.0553 (7)0.5950 (6)0.1862 (4)0.0812 (12)
H91.04660.70530.21140.097*
C101.2140 (6)0.5692 (7)0.1826 (5)0.0900 (15)
H101.31390.66190.20690.108*
C111.2280 (6)0.4087 (7)0.1436 (5)0.0900 (15)
H111.33720.39210.14270.108*
C121.0796 (6)0.2698 (6)0.1052 (5)0.0760 (11)
H121.08910.16150.07530.091*
C130.9170 (6)0.2092 (8)0.4254 (4)0.0875 (14)
H13A0.94300.10110.43070.105*
H13B0.95670.28230.50440.105*
H13C0.97470.26550.36300.105*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0896 (9)0.1076 (10)0.0887 (9)0.0410 (7)0.0150 (6)0.0072 (7)
Cl20.0869 (8)0.0730 (8)0.1186 (10)0.0325 (6)0.0255 (7)0.0141 (6)
S10.0608 (6)0.0547 (6)0.0758 (7)0.0165 (4)−0.0011 (4)0.0066 (4)
O10.0695 (18)0.0690 (17)0.093 (2)0.0285 (14)0.0023 (15)0.0136 (14)
O20.0690 (17)0.0601 (16)0.0872 (19)0.0119 (13)−0.0024 (14)−0.0020 (13)
N10.0591 (18)0.0635 (19)0.0692 (19)0.0144 (14)−0.0032 (14)0.0074 (14)
C10.058 (2)0.060 (2)0.073 (2)0.0185 (16)−0.0008 (17)0.0152 (17)
C20.061 (2)0.071 (2)0.065 (2)0.0205 (17)−0.0021 (17)0.0108 (17)
C30.072 (2)0.073 (2)0.065 (2)0.0210 (19)−0.0043 (18)0.0072 (18)
C40.075 (2)0.070 (2)0.071 (2)0.0278 (19)0.0071 (19)0.0153 (18)
C50.062 (2)0.079 (3)0.079 (3)0.0260 (19)0.0022 (19)0.013 (2)
C60.061 (2)0.067 (2)0.072 (2)0.0168 (18)−0.0026 (18)0.0084 (17)
C70.058 (2)0.062 (2)0.063 (2)0.0149 (16)−0.0013 (15)0.0093 (15)
C80.072 (2)0.065 (2)0.068 (2)0.0178 (18)0.0016 (18)0.0123 (17)
C90.087 (3)0.067 (2)0.077 (3)0.006 (2)0.000 (2)0.0105 (19)
C100.070 (3)0.086 (3)0.095 (3)−0.005 (2)−0.011 (2)0.025 (2)
C110.061 (2)0.094 (3)0.109 (4)0.014 (2)−0.005 (2)0.032 (3)
C120.062 (2)0.080 (3)0.089 (3)0.023 (2)0.008 (2)0.022 (2)
C130.062 (3)0.114 (4)0.075 (3)0.022 (2)−0.008 (2)−0.003 (2)
Geometric parameters (Å, °) top
Cl1—C41.719 (5)C5—H50.9300
Cl2—C81.728 (5)C6—H60.9300
S1—O11.423 (3)C7—C81.378 (6)
S1—O21.430 (3)C7—C121.381 (6)
S1—N11.643 (4)C8—C91.388 (6)
S1—C11.761 (4)C9—C101.360 (8)
N1—C71.424 (5)C9—H90.9300
N1—H1N0.88 (5)C10—C111.364 (8)
C1—C61.390 (5)C10—H100.9300
C1—C21.398 (5)C11—C121.389 (6)
C2—C31.387 (7)C11—H110.9300
C2—C131.522 (6)C12—H120.9300
C3—C41.366 (6)C13—H13A0.9600
C3—H30.9300C13—H13B0.9600
C4—C51.388 (6)C13—H13C0.9600
C5—C61.364 (7)
O1—S1—O2120.08 (19)C1—C6—H6119.2
O1—S1—N1107.27 (18)C8—C7—C12119.1 (4)
O2—S1—N1104.75 (18)C8—C7—N1122.1 (4)
O1—S1—C1109.99 (19)C12—C7—N1118.8 (4)
O2—S1—C1106.96 (19)C7—C8—C9120.6 (4)
N1—S1—C1107.03 (18)C7—C8—Cl2120.0 (3)
C7—N1—S1120.4 (3)C9—C8—Cl2119.4 (4)
C7—N1—H1N114 (3)C10—C9—C8119.6 (5)
S1—N1—H1N113 (3)C10—C9—H9120.2
C6—C1—C2120.1 (4)C8—C9—H9120.2
C6—C1—S1116.1 (3)C9—C10—C11120.6 (4)
C2—C1—S1123.7 (3)C9—C10—H10119.7
C3—C2—C1117.4 (4)C11—C10—H10119.7
C3—C2—C13118.0 (4)C10—C11—C12120.2 (5)
C1—C2—C13124.6 (4)C10—C11—H11119.9
C4—C3—C2121.9 (4)C12—C11—H11119.9
C4—C3—H3119.0C7—C12—C11119.8 (5)
C2—C3—H3119.0C7—C12—H12120.1
C3—C4—C5120.6 (4)C11—C12—H12120.1
C3—C4—Cl1119.2 (4)C2—C13—H13A109.5
C5—C4—Cl1120.3 (4)C2—C13—H13B109.5
C6—C5—C4118.5 (4)H13A—C13—H13B109.5
C6—C5—H5120.8C2—C13—H13C109.5
C4—C5—H5120.8H13A—C13—H13C109.5
C5—C6—C1121.6 (4)H13B—C13—H13C109.5
C5—C6—H6119.2
O1—S1—N1—C7−43.2 (4)Cl1—C4—C5—C6−179.9 (3)
O2—S1—N1—C7−171.9 (3)C4—C5—C6—C10.7 (6)
C1—S1—N1—C774.8 (4)C2—C1—C6—C5−0.9 (6)
O1—S1—C1—C6−153.8 (3)S1—C1—C6—C5−177.6 (3)
O2—S1—C1—C6−21.8 (3)S1—N1—C7—C8−106.8 (4)
N1—S1—C1—C690.0 (3)S1—N1—C7—C1276.4 (5)
O1—S1—C1—C229.7 (4)C12—C7—C8—C9−0.1 (6)
O2—S1—C1—C2161.6 (3)N1—C7—C8—C9−176.9 (4)
N1—S1—C1—C2−86.6 (4)C12—C7—C8—Cl2178.6 (3)
C6—C1—C2—C30.2 (6)N1—C7—C8—Cl21.9 (6)
S1—C1—C2—C3176.7 (3)C7—C8—C9—C10−1.7 (7)
C6—C1—C2—C13179.5 (4)Cl2—C8—C9—C10179.6 (4)
S1—C1—C2—C13−4.0 (6)C8—C9—C10—C111.2 (8)
C1—C2—C3—C40.6 (6)C9—C10—C11—C121.0 (8)
C13—C2—C3—C4−178.8 (4)C8—C7—C12—C112.3 (6)
C2—C3—C4—C5−0.7 (7)N1—C7—C12—C11179.2 (4)
C2—C3—C4—Cl1179.2 (3)C10—C11—C12—C7−2.7 (7)
C3—C4—C5—C60.1 (6)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.88 (5)2.17 (5)2.994 (5)157 (4)
N1—H1N···Cl20.88 (5)2.67 (5)3.011 (4)104 (4)
Symmetry codes: (i) −x+1, −y, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.88 (5)2.17 (5)2.994 (5)157 (4)
N1—H1N···Cl20.88 (5)2.67 (5)3.011 (4)104 (4)
Symmetry codes: (i) −x+1, −y, −z.
references
References top

Enraf–Nonius (1996). CAD-4-PC. Enraf–Nonius, Delft, The Netherlands.

Gelbrich, T., Hursthouse, M. B. & Threlfall, T. L. (2007). Acta Cryst. B63, 621–632.

Gowda, B. T., Foro, S., Nirmala, P. G., Babitha, K. S. & Fuess, H. (2009a). Acta Cryst. E65, o476.

Gowda, B. T., Foro, S., Nirmala, P. G., Babitha, K. S. & Fuess, H. (2009b). Acta Cryst. E65, o576.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

Perlovich, G. L., Tkachev, V. V., Schaper, K.-J. & Raevsky, O. A. (2006). Acta Cryst. E62, o780–o782.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Stoe & Cie (1987). REDU4. Stoe & Cie GmbH, Darmstadt, Germany.