N-(2-Chloro­phen­yl)-4-methyl­benzene­sulfonamide

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

doi:10.1107/S1600536809053756

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o188

doi:10.1107/S1600536809053756

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N-(2-Chlorophenyl)-4-methylbenzenesulfonamide

B. Thimme Gowda,^a ^* Sabine Foro,^b P. G. Nirmala ^a and Hartmut Fuess ^b

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, and ^bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 13 December 2009; accepted 14 December 2009; online 19 December 2009)

The molecule of the title compound, C₁₃H₁₂ClNO₂S, is bent at the S atom with a C—SO₂—NH—C torsion angle of −54.8 (2)°. The dihedral angle between the two aromatic rings is 71.6 (1)°. An intramolecular N—H⋯Cl hydrogen bond is observed. The crystal structure features inversion-related dimers formed by pairs of N—H⋯O hydrogen bonds.

Related literature

For the preparation of the title compound, see: Gowda et al. (2005 ). For our studies of the effects of substituents on the structures of N-(aryl)-arylsulfonamides, see: Gowda et al. (2009 ); Nirmala et al. (2009 ). For related structures, see: Gelbrich et al. (2007 ); Perlovich et al. (2006 ).

Experimental

Crystal data

C₁₃H₁₂ClNO₂S
M_r = 281.75
Monoclinic, P 2₁ /n
a = 8.661 (1) Å
b = 9.949 (1) Å
c = 15.509 (1) Å
β = 99.384 (8)°
V = 1318.5 (2) Å³
Z = 4
Cu Kα radiation
μ = 4.00 mm⁻¹
T = 299 K
0.50 × 0.13 × 0.08 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.240, T_max = 0.741
3151 measured reflections
2351 independent reflections
1792 reflections with I > 2σ(I)
R_int = 0.029
3 standard reflections every 3 min
intensity decay: 1.6%

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.117
S = 1.03
2351 reflections
168 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2ⁱ	0.83 (3)	2.40 (3)	3.181 (3)	156 (3)
N1—H1N⋯Cl1	0.83 (3)	2.46 (3)	2.952 (2)	119 (2)
Symmetry code: (i) -x+2, -y, -z.

Data collection: CAD-4-PC (Enraf–Nonius, 1996 ); cell refinement: CAD-4-PC; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809053756/ci2989sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809053756/ci2989Isup2.hkl

checkCIF report

Comment top

As part of a study of the effect of substituents on crystal structures of N-(aryl)-arylsulfonamides (Gowda et al., 2009; Nirmala et al., 2009), the crystal structure of N-(2-chlorophenyl)4-methylbenzenesulfonamide (I) has been determined. The conformation of the N—H bond is syn to the 2-chloro group in the aniline benzene ring. The molecule is bent at the S atom with a C1—S1—N1—C7 torsion angle of -54.8 (2)°, compared to the value of -51.6 (3)° in N-(phenyl)4-methylbenzenesulfonamide (II) (Gowda et al., 2009) and 60.0 (2)° in N-(2-methylphenyl)4-methylbenzenesulfonamide (III) (Nirmala et al., 2009).

The two benzene rings in (I) are tilted relative to each other by 71.6 (1)°, compared to 68.4 (1)° in (II) and 49.7 (1)° in (III). The other bond parameters are similar to those observed in (II), (III) and other aryl sulfonamides (Perlovich et al., 2006; Gelbrich et al., 2007).

The structure exhibits both the intramolecular N—H···Cl and the intermolecular N—H···O(S) hydrogen bonds.

In the crystal structure, pairs of intermolecular N—H···O hydrogen bonds (Table 1) link the molecules into inversion-related dimers. Part of the crystal structure is shown in Fig. 2.

Related literature top

For the preparation of the title compound, see: Gowda et al. (2005). For our studies of the effects of substituents on the structures of N-(aryl)-arylsulfonamides, see: Gowda et al. (2009); Nirmala et al. (2009). For related structures, see: Gelbrich et al. (2007); Perlovich et al. (2006).

Experimental top

A solution of toluene (10 ml) in chloroform (40 ml) was treated dropwise with chlorosulfonic acid (25 ml) at 273 K. 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 benzenesulfonylchloride was treated with 2-chloroaniline in the stoichiometric ratio and boiled for 10 min. The reaction mixture was then cooled to room temperature and added to ice cold water (100 ml). The resultant solid 4-methyl-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 IR and NMR spectra. Single crystals used in X-ray diffraction studies were grown by a slow evaporation of an ethanolic solution at room temperature.

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

	Fig. 1. Molecular structure of the title compound, showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.

N-(2-Chlorophenyl)-4-methylbenzenesulfonamide top

Crystal data top

C₁₃H₁₂ClNO₂S	F(000) = 584
M_r = 281.75	D_x = 1.419 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 8.661 (1) Å	θ = 6.3–21.3°
b = 9.949 (1) Å	µ = 4.00 mm⁻¹
c = 15.509 (1) Å	T = 299 K
β = 99.384 (8)°	Needle, colourless
V = 1318.5 (2) Å³	0.50 × 0.13 × 0.08 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1792 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
Graphite monochromator	θ_max = 67.5°, θ_min = 5.3°
ω/2θ scans	h = −10→2
Absorption correction: ψ scan (North et al., 1968)	k = −11→0
T_min = 0.240, T_max = 0.741	l = −18→18
3151 measured reflections	3 standard reflections every 120 min
2351 independent reflections	intensity decay: 1.6%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0678P)² + 0.203P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.003
2351 reflections	Δρ_max = 0.26 e Å⁻³
168 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0074 (7)

Crystal data top

C₁₃H₁₂ClNO₂S	V = 1318.5 (2) Å³
M_r = 281.75	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 8.661 (1) Å	µ = 4.00 mm⁻¹
b = 9.949 (1) Å	T = 299 K
c = 15.509 (1) Å	0.50 × 0.13 × 0.08 mm
β = 99.384 (8)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1792 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.029
T_min = 0.240, T_max = 0.741	3 standard reflections every 120 min
3151 measured reflections	intensity decay: 1.6%
2351 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.26 e Å⁻³
2351 reflections	Δρ_min = −0.32 e Å⁻³
168 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.61691 (9)	−0.13179 (7)	0.05985 (5)	0.0700 (3)
S1	1.00511 (7)	0.16393 (6)	0.10719 (4)	0.0503 (2)
O1	1.0698 (2)	0.2235 (2)	0.18850 (12)	0.0636 (5)
O2	1.1070 (2)	0.0996 (2)	0.05640 (13)	0.0656 (5)
N1	0.8841 (2)	0.0448 (2)	0.12574 (15)	0.0521 (5)
H1N	0.867 (3)	−0.009 (3)	0.0838 (19)	0.062*
C1	0.8918 (3)	0.2840 (2)	0.04327 (15)	0.0471 (6)
C2	0.8224 (3)	0.2501 (3)	−0.04057 (16)	0.0574 (7)
H2	0.8376	0.1651	−0.0627	0.069*
C3	0.7314 (4)	0.3424 (3)	−0.09075 (19)	0.0626 (7)
H3	0.6840	0.3189	−0.1469	0.075*
C4	0.7084 (4)	0.4705 (3)	−0.0596 (2)	0.0669 (8)
C5	0.7801 (4)	0.5015 (3)	0.0238 (2)	0.0827 (10)
H5	0.7666	0.5868	0.0459	0.099*
C6	0.8711 (4)	0.4099 (3)	0.07551 (19)	0.0691 (8)
H6	0.9182	0.4331	0.1318	0.083*
C7	0.7485 (3)	0.0701 (2)	0.16324 (15)	0.0460 (5)
C8	0.6155 (3)	−0.0057 (2)	0.13720 (15)	0.0505 (6)
C9	0.4813 (3)	0.0161 (3)	0.17153 (18)	0.0641 (7)
H9	0.3933	−0.0368	0.1538	0.077*
C10	0.4771 (4)	0.1159 (3)	0.23198 (19)	0.0688 (8)
H10	0.3854	0.1333	0.2539	0.083*
C11	0.6092 (4)	0.1897 (3)	0.25992 (19)	0.0660 (7)
H11	0.6073	0.2561	0.3019	0.079*
C12	0.7438 (4)	0.1671 (3)	0.22683 (17)	0.0597 (7)
H12	0.8329	0.2173	0.2472	0.072*
C13	0.6086 (5)	0.5708 (4)	−0.1163 (3)	0.1005 (12)
H13A	0.5015	0.5415	−0.1254	0.121*
H13B	0.6440	0.5777	−0.1717	0.121*
H13C	0.6166	0.6569	−0.0881	0.121*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0684 (5)	0.0636 (4)	0.0769 (5)	−0.0086 (3)	0.0080 (4)	−0.0160 (3)
S1	0.0432 (3)	0.0513 (4)	0.0539 (4)	−0.0004 (3)	0.0003 (2)	−0.0079 (3)
O1	0.0575 (11)	0.0704 (13)	0.0567 (11)	−0.0045 (9)	−0.0093 (8)	−0.0096 (9)
O2	0.0466 (10)	0.0718 (12)	0.0789 (13)	0.0026 (9)	0.0112 (9)	−0.0164 (11)
N1	0.0515 (11)	0.0439 (12)	0.0604 (13)	0.0025 (9)	0.0078 (10)	−0.0039 (9)
C1	0.0456 (12)	0.0466 (13)	0.0480 (13)	−0.0063 (10)	0.0048 (10)	−0.0050 (10)
C2	0.0664 (17)	0.0524 (15)	0.0499 (14)	−0.0071 (13)	−0.0012 (12)	−0.0088 (11)
C3	0.0664 (17)	0.0697 (18)	0.0486 (14)	−0.0134 (14)	0.0001 (12)	0.0021 (13)
C4	0.0685 (18)	0.0590 (17)	0.0723 (19)	−0.0021 (14)	0.0087 (15)	0.0189 (14)
C5	0.116 (3)	0.0499 (17)	0.076 (2)	0.0135 (18)	−0.0039 (18)	−0.0046 (15)
C6	0.091 (2)	0.0537 (16)	0.0577 (16)	0.0036 (15)	−0.0025 (15)	−0.0152 (13)
C7	0.0493 (13)	0.0429 (12)	0.0446 (12)	0.0071 (10)	0.0038 (10)	0.0078 (10)
C8	0.0556 (14)	0.0453 (13)	0.0479 (13)	0.0042 (11)	0.0003 (11)	0.0054 (11)
C9	0.0512 (15)	0.078 (2)	0.0612 (16)	−0.0008 (14)	0.0050 (12)	0.0063 (15)
C10	0.0616 (17)	0.086 (2)	0.0607 (17)	0.0153 (16)	0.0168 (14)	0.0080 (16)
C11	0.078 (2)	0.0641 (17)	0.0570 (16)	0.0117 (15)	0.0133 (14)	−0.0037 (14)
C12	0.0629 (16)	0.0589 (16)	0.0566 (16)	−0.0002 (13)	0.0076 (13)	−0.0083 (13)
C13	0.107 (3)	0.085 (3)	0.102 (3)	0.011 (2)	−0.005 (2)	0.034 (2)

Geometric parameters (Å, º) top

Cl1—C8	1.737 (3)	C5—H5	0.93
S1—O1	1.4233 (18)	C6—H6	0.93
S1—O2	1.4266 (19)	C7—C8	1.381 (3)
S1—N1	1.639 (2)	C7—C12	1.385 (3)
S1—C1	1.748 (3)	C8—C9	1.373 (4)
N1—C7	1.415 (3)	C9—C10	1.370 (4)
N1—H1N	0.83 (3)	C9—H9	0.93
C1—C6	1.371 (4)	C10—C11	1.369 (4)
C1—C2	1.382 (3)	C10—H10	0.93
C2—C3	1.368 (4)	C11—C12	1.367 (4)
C2—H2	0.93	C11—H11	0.93
C3—C4	1.388 (4)	C12—H12	0.93
C3—H3	0.93	C13—H13A	0.96
C4—C5	1.376 (4)	C13—H13B	0.96
C4—C13	1.506 (4)	C13—H13C	0.96
C5—C6	1.374 (4)

O1—S1—O2	119.12 (12)	C5—C6—H6	120.3
O1—S1—N1	108.46 (12)	C8—C7—C12	118.0 (2)
O2—S1—N1	104.08 (12)	C8—C7—N1	119.4 (2)
O1—S1—C1	108.75 (12)	C12—C7—N1	122.6 (2)
O2—S1—C1	109.52 (12)	C9—C8—C7	121.3 (2)
N1—S1—C1	106.12 (11)	C9—C8—Cl1	118.9 (2)
C7—N1—S1	122.74 (17)	C7—C8—Cl1	119.8 (2)
C7—N1—H1N	112 (2)	C10—C9—C8	119.9 (3)
S1—N1—H1N	111 (2)	C10—C9—H9	120.1
C6—C1—C2	120.2 (3)	C8—C9—H9	120.1
C6—C1—S1	120.8 (2)	C11—C10—C9	119.5 (3)
C2—C1—S1	119.0 (2)	C11—C10—H10	120.3
C3—C2—C1	119.5 (3)	C9—C10—H10	120.3
C3—C2—H2	120.2	C12—C11—C10	120.8 (3)
C1—C2—H2	120.2	C12—C11—H11	119.6
C2—C3—C4	121.4 (3)	C10—C11—H11	119.6
C2—C3—H3	119.3	C11—C12—C7	120.5 (3)
C4—C3—H3	119.3	C11—C12—H12	119.7
C5—C4—C3	117.7 (3)	C7—C12—H12	119.7
C5—C4—C13	121.9 (3)	C4—C13—H13A	109.5
C3—C4—C13	120.4 (3)	C4—C13—H13B	109.5
C6—C5—C4	121.9 (3)	H13A—C13—H13B	109.5
C6—C5—H5	119.1	C4—C13—H13C	109.5
C4—C5—H5	119.1	H13A—C13—H13C	109.5
C1—C6—C5	119.3 (3)	H13B—C13—H13C	109.5
C1—C6—H6	120.3

O1—S1—N1—C7	61.9 (2)	C2—C1—C6—C5	0.4 (4)
O2—S1—N1—C7	−170.36 (19)	S1—C1—C6—C5	−179.4 (3)
C1—S1—N1—C7	−54.8 (2)	C4—C5—C6—C1	0.2 (5)
O1—S1—C1—C6	−3.0 (3)	S1—N1—C7—C8	145.7 (2)
O2—S1—C1—C6	−134.7 (2)	S1—N1—C7—C12	−35.5 (3)
N1—S1—C1—C6	113.5 (2)	C12—C7—C8—C9	1.5 (4)
O1—S1—C1—C2	177.2 (2)	N1—C7—C8—C9	−179.6 (2)
O2—S1—C1—C2	45.5 (2)	C12—C7—C8—Cl1	−178.24 (19)
N1—S1—C1—C2	−66.3 (2)	N1—C7—C8—Cl1	0.6 (3)
C6—C1—C2—C3	−0.8 (4)	C7—C8—C9—C10	0.9 (4)
S1—C1—C2—C3	179.0 (2)	Cl1—C8—C9—C10	−179.4 (2)
C1—C2—C3—C4	0.7 (4)	C8—C9—C10—C11	−2.4 (4)
C2—C3—C4—C5	−0.2 (5)	C9—C10—C11—C12	1.5 (5)
C2—C3—C4—C13	179.6 (3)	C10—C11—C12—C7	1.0 (4)
C3—C4—C5—C6	−0.3 (5)	C8—C7—C12—C11	−2.5 (4)
C13—C4—C5—C6	180.0 (3)	N1—C7—C12—C11	178.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.83 (3)	2.40 (3)	3.181 (3)	156 (3)
N1—H1N···Cl1	0.83 (3)	2.46 (3)	2.952 (2)	119 (2)

Symmetry code: (i) −x+2, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂ClNO₂S
M_r	281.75
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	299
a, b, c (Å)	8.661 (1), 9.949 (1), 15.509 (1)
β (°)	99.384 (8)
V (Å³)	1318.5 (2)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	4.00
Crystal size (mm)	0.50 × 0.13 × 0.08

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.240, 0.741
No. of measured, independent and observed [I > 2σ(I)] reflections	3151, 2351, 1792
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.117, 1.03
No. of reflections	2351
No. of parameters	168
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.32

Computer programs: CAD-4-PC (Enraf–Nonius, 1996), REDU4 (Stoe & Cie, 1987), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.83 (3)	2.40 (3)	3.181 (3)	156 (3)
N1—H1N···Cl1	0.83 (3)	2.46 (3)	2.952 (2)	119 (2)

Symmetry code: (i) −x+2, −y, −z.

References

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o188

doi:10.1107/S1600536809053756

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