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Acta Cryst. (2010). E66, o2000    [ doi:10.1107/S1600536810026930 ]

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

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

Abstract top

In the title compound, C13H11Cl2NO2S, the conformations of the N-C bonds in the C-SO2-NH-C segment have gauche torsions with respect to the S=O bonds. Further, the conformation of the N-H bond is syn to the ortho-methyl group in the sulfonyl benzene ring. The torsion angle of the C-SO2-NH-C segment in the molecule is 55.0 (2)°. The two benzene rings are tilted relative to each other by 67.0 (1)°. In the crystal, intermolecular N-H...O hydrogen bonds link the molecules into infinite column-like chains.

Comment top

As part of a study of the substituent effects on the crystal structures of N-(aryl)-arylsulfonamides (Gowda et al., 2009a,b; 2010), in the present work, the structure of 4-chloro-2-methyl-N-(4-chlorophenyl)benzenesulfonamide (I) has been determined (Fig. 1). The conformations of the N—C bonds in the C—SO2—NH—C segment have gauche torsions with respect to the S═O bonds. Further, the conformation of the N—H bond in the C—SO2—NH—C segment is syn to the ortho-methyl group in the sulfonyl benzene ring.

The torsion angle of the segment C—SO2—NH—C in (I) is 55.0 (2)°, compared to the values of -61.9 (4)° and 69.7 (4)° in the two independent molecules of 4-chloro-2-methyl-N-(phenyl)-benzenesulfonamide(II) (Gowda et al., 2009a), 74.8 (4)° in 4-chloro-2-methyl-N-(2-chlorophenyl)-benzenesulfonamide (III) (Gowda et al., 2009b) and 80.1 (3)° in 4-chloro-2-methyl-N-(3-chlorophenyl)benzenesulfonamide (IV) (Gowda et al., 2010).

The sulfonyl and the aniline benzene rings in (I) are tilted relative to each other by 67.0 (1)°, compared to the values of 86.6 (2)° and 83.0 (2)° in the two independent molecules of (II), 45.5 (2)° in (III) and 70.9 (1)° in (IV).

The other bond parameters in (I) are similar to those observed in (II), (III), (IV) and other aryl sulfonamides (Perlovich et al., 2006; Gelbrich et al., 2007).

In the crystal, the intermolecular N–H···O hydrogen bonds (Table 1) link the molecules via inversion-related dimers, into infinite column like chains. Part of the crystal structure is shown in Fig. 2.

Related literature top

For the preparation of the title compound, see: Savitha & Gowda (2006). For our studies of the effect of substituents on the structures of N-(aryl)arylsulfonamides, see: Gowda et al. (2009a,b; 2010). For related structures, see: Gelbrich et al. (2007); Perlovich et al. (2006).

Experimental top

The solution of m-chlorotoluene (10 cc) in chloroform (40 cc) was treated dropwise with chlorosulfonic acid (25 cc) at 0 ° C. After the initial evolution of hydrogen chloride 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 4-chloroaniline in the stoichiometric ratio and boiled for ten minutes. The reaction mixture was then cooled to room temperature and added to ice cold water (100 cc). The resultant solid 4-chloro-2-methyl-N- (4-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 (Savitha & Gowda, 2006).

The rod like colorless single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation at room temperature.

Refinement top

The H atom of the NH group was located in a difference map and later restrained to N—H = 0.85 (1) Å. The other H atoms were positioned with idealized geometry 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 times of the Ueq of the parent atom).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); 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 labelling scheme and displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Molecular packing of (I) with hydrogen bonding shown as dashed lines.
4-Chloro-N-(4-chlorophenyl)-2-methylbenzenesulfonamide top
Crystal data top
C13H11Cl2NO2SF(000) = 648
Mr = 316.19Dx = 1.459 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4597 reflections
a = 9.2696 (5) Åθ = 2.6–27.9°
b = 9.8591 (5) ŵ = 0.59 mm−1
c = 15.813 (1) ÅT = 299 K
β = 95.222 (6)°Rod, colorless
V = 1439.15 (14) Å30.40 × 0.32 × 0.28 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector		2938 independent reflections
Radiation source: fine-focus sealed tube2408 reflections with I > 2σ(I)
graphiteRint = 0.015
Rotation method data acquisition using ω and phi scansθmax = 26.4°, θmin = 2.6°
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)		h = −11→11
Tmin = 0.798, Tmax = 0.852k = −12→12
9765 measured reflectionsl = −19→19
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0617P)2 + 0.6589P]
where P = (Fo2 + 2Fc2)/3
2938 reflections(Δ/σ)max = 0.016
175 parametersΔρmax = 0.30 e Å−3
1 restraintΔρmin = −0.41 e Å−3
Crystal data top
C13H11Cl2NO2SV = 1439.15 (14) Å3
Mr = 316.19Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.2696 (5) ŵ = 0.59 mm−1
b = 9.8591 (5) ÅT = 299 K
c = 15.813 (1) Å0.40 × 0.32 × 0.28 mm
β = 95.222 (6)°
Data collection top
Oxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector		2938 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)		2408 reflections with I > 2σ(I)
Tmin = 0.798, Tmax = 0.852Rint = 0.015
9765 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.043H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.122Δρmax = 0.30 e Å−3
S = 1.04Δρmin = −0.41 e Å−3
2938 reflectionsAbsolute structure: ?
175 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Special details top

Experimental. CrysAlis RED (Oxford Diffraction, 2009) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
C10.3936 (2)0.0472 (2)0.60770 (13)0.0447 (5)
C20.3558 (3)0.1435 (2)0.54392 (14)0.0506 (5)
C30.2576 (3)0.1023 (3)0.47744 (15)0.0605 (6)
H30.23020.16330.43410.073*
C40.1994 (3)−0.0269 (3)0.47382 (15)0.0578 (6)
C50.2377 (3)−0.1203 (3)0.53603 (16)0.0614 (6)
H50.1986−0.20720.53320.074*
C60.3354 (3)−0.0827 (2)0.60306 (16)0.0554 (6)
H60.3625−0.14510.64570.066*
C70.2731 (2)0.1334 (2)0.78675 (12)0.0438 (5)
C80.2587 (3)0.0085 (2)0.82521 (18)0.0632 (6)
H80.3367−0.05110.83110.076*
C90.1286 (3)−0.0271 (3)0.85470 (19)0.0733 (8)
H90.1179−0.11180.87920.088*
C100.0148 (3)0.0622 (3)0.84792 (16)0.0640 (7)
C110.0271 (3)0.1854 (3)0.80905 (16)0.0639 (6)
H11−0.05100.24490.80380.077*
C120.1557 (3)0.2203 (2)0.77793 (14)0.0540 (5)
H120.16380.30320.75070.065*
C130.4155 (3)0.2892 (2)0.54425 (16)0.0620 (6)
H13A0.51910.28660.54490.074*
H13B0.38910.33600.59380.074*
H13C0.37550.33590.49420.074*
N10.4080 (2)0.17773 (16)0.75967 (12)0.0480 (4)
H1N0.419 (3)0.2615 (11)0.7493 (15)0.058*
O10.54310 (18)−0.03518 (15)0.74327 (11)0.0608 (5)
O20.62082 (18)0.17858 (17)0.68063 (12)0.0647 (5)
Cl10.07375 (8)−0.06943 (10)0.39055 (5)0.0866 (3)
Cl2−0.14664 (10)0.01749 (11)0.88891 (7)0.1049 (4)
S10.50716 (6)0.08928 (5)0.69990 (4)0.04710 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0496 (11)0.0353 (10)0.0493 (11)0.0072 (8)0.0051 (9)−0.0033 (8)
C20.0611 (13)0.0453 (11)0.0469 (11)0.0087 (10)0.0122 (10)0.0014 (9)
C30.0727 (16)0.0628 (15)0.0462 (12)0.0138 (12)0.0067 (11)0.0053 (11)
C40.0528 (13)0.0721 (16)0.0485 (12)0.0095 (11)0.0047 (10)−0.0154 (11)
C50.0651 (15)0.0505 (13)0.0676 (15)−0.0028 (11)0.0009 (12)−0.0119 (11)
C60.0657 (14)0.0378 (11)0.0614 (14)0.0029 (10)−0.0013 (11)−0.0011 (10)
C70.0594 (12)0.0331 (9)0.0378 (10)−0.0032 (9)−0.0008 (9)−0.0051 (8)
C80.0736 (16)0.0394 (12)0.0773 (16)0.0034 (11)0.0120 (13)0.0088 (11)
C90.097 (2)0.0469 (14)0.0788 (18)−0.0168 (14)0.0209 (15)0.0040 (13)
C100.0672 (15)0.0653 (16)0.0602 (14)−0.0184 (13)0.0099 (12)−0.0189 (12)
C110.0607 (14)0.0665 (16)0.0634 (15)0.0036 (12)0.0000 (11)−0.0088 (12)
C120.0679 (14)0.0436 (12)0.0493 (12)0.0048 (10)−0.0019 (10)0.0004 (9)
C130.0809 (17)0.0437 (12)0.0613 (14)0.0034 (11)0.0059 (12)0.0148 (11)
N10.0615 (11)0.0253 (8)0.0569 (10)−0.0020 (7)0.0044 (8)−0.0027 (7)
O10.0686 (11)0.0367 (8)0.0735 (11)0.0115 (7)−0.0136 (8)0.0025 (7)
O20.0521 (9)0.0510 (9)0.0914 (13)−0.0034 (7)0.0080 (8)−0.0011 (9)
Cl10.0733 (5)0.1143 (7)0.0691 (4)0.0115 (4)−0.0096 (3)−0.0264 (4)
Cl20.0898 (6)0.1106 (7)0.1198 (7)−0.0418 (5)0.0403 (5)−0.0334 (6)
S10.0496 (3)0.0310 (3)0.0596 (3)0.0042 (2)−0.0010 (2)−0.0008 (2)
Geometric parameters (Å, °) top
C1—C61.389 (3)C8—H80.9300
C1—C21.406 (3)C9—C101.370 (4)
C1—S11.768 (2)C9—H90.9300
C2—C31.387 (3)C10—C111.371 (4)
C2—C131.540 (3)C10—Cl21.741 (3)
C3—C41.383 (4)C11—C121.374 (3)
C3—H30.9300C11—H110.9300
C4—C51.370 (4)C12—H120.9300
C4—Cl11.728 (2)C13—H13A0.9600
C5—C61.381 (3)C13—H13B0.9600
C5—H50.9300C13—H13C0.9600
C6—H60.9300N1—S11.6299 (19)
C7—C121.382 (3)N1—H1N0.850 (10)
C7—C81.385 (3)O1—S11.4302 (15)
C7—N11.426 (3)O2—S11.4271 (17)
C8—C91.378 (4)
C6—C1—C2121.0 (2)C8—C9—H9120.0
C6—C1—S1117.35 (17)C9—C10—C11120.7 (2)
C2—C1—S1121.56 (17)C9—C10—Cl2119.3 (2)
C3—C2—C1116.7 (2)C11—C10—Cl2120.0 (2)
C3—C2—C13119.1 (2)C10—C11—C12119.5 (2)
C1—C2—C13124.2 (2)C10—C11—H11120.2
C4—C3—C2121.9 (2)C12—C11—H11120.2
C4—C3—H3119.1C11—C12—C7120.6 (2)
C2—C3—H3119.1C11—C12—H12119.7
C5—C4—C3121.0 (2)C7—C12—H12119.7
C5—C4—Cl1119.8 (2)C2—C13—H13A109.5
C3—C4—Cl1119.2 (2)C2—C13—H13B109.5
C4—C5—C6118.7 (2)H13A—C13—H13B109.5
C4—C5—H5120.7C2—C13—H13C109.5
C6—C5—H5120.7H13A—C13—H13C109.5
C5—C6—C1120.8 (2)H13B—C13—H13C109.5
C5—C6—H6119.6C7—N1—S1124.49 (13)
C1—C6—H6119.6C7—N1—H1N118.8 (17)
C12—C7—C8119.3 (2)S1—N1—H1N108.8 (17)
C12—C7—N1118.93 (19)O2—S1—O1119.17 (11)
C8—C7—N1121.7 (2)O2—S1—N1105.07 (10)
C9—C8—C7119.8 (2)O1—S1—N1107.46 (10)
C9—C8—H8120.1O2—S1—C1111.38 (11)
C7—C8—H8120.1O1—S1—C1106.80 (10)
C10—C9—C8120.1 (2)N1—S1—C1106.20 (10)
C10—C9—H9120.0
C6—C1—C2—C30.5 (3)C8—C9—C10—Cl2−177.8 (2)
S1—C1—C2—C3−175.33 (17)C9—C10—C11—C12−1.1 (4)
C6—C1—C2—C13−180.0 (2)Cl2—C10—C11—C12179.15 (19)
S1—C1—C2—C134.2 (3)C10—C11—C12—C7−1.1 (3)
C1—C2—C3—C40.0 (3)C8—C7—C12—C111.9 (3)
C13—C2—C3—C4−179.5 (2)N1—C7—C12—C11−175.1 (2)
C2—C3—C4—C5−0.4 (4)C12—C7—N1—S1−131.68 (18)
C2—C3—C4—Cl1178.18 (18)C8—C7—N1—S151.4 (3)
C3—C4—C5—C60.3 (4)C7—N1—S1—O2173.07 (17)
Cl1—C4—C5—C6−178.28 (19)C7—N1—S1—O1−59.06 (19)
C4—C5—C6—C10.2 (4)C7—N1—S1—C154.95 (19)
C2—C1—C6—C5−0.6 (4)C6—C1—S1—O2145.42 (18)
S1—C1—C6—C5175.39 (19)C2—C1—S1—O2−38.6 (2)
C12—C7—C8—C9−0.5 (4)C6—C1—S1—O113.7 (2)
N1—C7—C8—C9176.4 (2)C2—C1—S1—O1−170.27 (18)
C7—C8—C9—C10−1.6 (4)C6—C1—S1—N1−100.72 (18)
C8—C9—C10—C112.5 (4)C2—C1—S1—N175.27 (19)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.85 (1)2.04 (1)2.868 (2)166 (2)
Symmetry codes: (i) −x+1, y+1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.85 (1)2.04 (1)2.868 (2)166 (2)
Symmetry codes: (i) −x+1, y+1/2, −z+3/2.
Acknowledgements top

Nil

references
References top

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, o717.

Gowda, B. T., Foro, S., Nirmala, P. G. & Fuess, H. (2010). Acta Cryst. E66, o1702.

Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.

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

Savitha, M. B. & Gowda, B. T. (2006). Z. Naturforsch. Teil A, 60, 600–606.

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

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