2,5-Dichloro-N-(3-methyl­phen­yl)benzenesulfonamide

Mughal, S.Y.; Khan, I.U.; Harrison, W.T.A.; Khan, M.H.; Arshad, M.N.

doi:10.1107/S1600536812032023

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2476

https://doi.org/10.1107/S1600536812032023

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2,5-Dichloro-N-(3-methylphenyl)benzenesulfonamide

Shumaila Younas Mughal,^a Islam Ullah Khan,^a William T. A. Harrison,^b Muneeb Hayat Khan ^c ^* and Muhammad Nadeem Arshad ^d

^aMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore 54000, Pakistan, ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, ^cQuestioned Documents Unit, Punjab Forensic Science Agency, Home Department, Lahore, Pakistan, and ^dCenter of Excellence for Advanced Materials Research (CEAMR), Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia
^*Correspondence e-mail: koolmuneeb@yahoo.com

(Received 4 July 2012; accepted 13 July 2012; online 18 July 2012)

In the title compound, C₁₃H₁₁Cl₂NO₂S, the dihedral angle between the aromatic rings is 76.62 (10)° and the C—S—N—C linkage between the rings adopts a gauche conformation [torsion angle = −51.4 (2)°]. A weak intramolecular C—H⋯O interaction closes an S(6) ring. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds generate R₂²(8) loops.

Related literature

For related structures, see: Khan et al. (2011 ); Mughal et al. (2012 ).

Experimental

Crystal data

C₁₃H₁₁Cl₂NO₂S
M_r = 316.19
Monoclinic, P 2₁ /n
a = 9.0361 (10) Å
b = 11.6937 (11) Å
c = 13.6904 (15) Å
β = 100.588 (3)°
V = 1422.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.60 mm⁻¹
T = 296 K
0.41 × 0.32 × 0.26 mm

Data collection

Bruker APEXII CCD diffractometer
4252 measured reflections
2566 independent reflections
2019 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.159
S = 1.06
2566 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.09	2.946 (3)	178
C12—H12⋯O2	0.93	2.50	3.141 (3)	126
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812032023/xu5591sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812032023/xu5591Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812032023/xu5591Isup3.cml

checkCIF report

Comment top

The title compound, (I), (Fig. 1) was prepared and characterized in continuation of our interest in the structural chemistry of sulfonamides (Khan et al., 2011; Mughal et al., 2012).

The dihedral angle between the C1—C6 and C7—C12 benzene rings is 76.62 (10)°. The C1—S1—N1—C7 linkage between the rings adopts a gauche conformation [torsion angle = -51.4 (2)°] and the minimum and maximum bond angles at the S atom are 105.52 (12) and 118.51 (12)°, respectively. The largest of these corresponds to the O=S=O bond angle, which is usually the largest in sulfonamindes (Mughal et al., 2012). An intramolecular C—H···O interaction leads to an S(6) ring.

In the crystal, inversion dimers linked by pairs of N—H···O hydrogen bonds (Table 1) generate R₂²(8) loops (Fig. 2).

Related literature top

For related structures, see: Khan et al. (2011); Mughal et al. (2012).

Experimental top

0.2 g of m-toludine was dissolved in 15 ml dichloromethane and 0.45 g of 2,5-dichlorobenzene sulfonyl chloride was added to the mixture, which was stirred at room temperature overnight. The pH was maintained at 8–9 with triethyamine. On completion of the reaction (after TLC) the pH was adjusted to 1–2 using 1M HCl solution. The DCM fraction was separated and the solvent evaporated at room temperature. Colourless prisms of (I) were obtained in 97% yield.

Structure description top

The title compound, (I), (Fig. 1) was prepared and characterized in continuation of our interest in the structural chemistry of sulfonamides (Khan et al., 2011; Mughal et al., 2012).

In the crystal, inversion dimers linked by pairs of N—H···O hydrogen bonds (Table 1) generate R₂²(8) loops (Fig. 2).

For related structures, see: Khan et al. (2011); Mughal et al. (2012).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 50% probability level.
	Fig. 2. An inversion dimer in the crystal structure of (I). Hydrogen bonds are shown as double-dashed lines and all C-bound H atoms are omitted for clarity. Symmetry code: (i) 1–x, –y, 1–z.

2,5-Dichloro-N-(3-methylphenyl)benzenesulfonamide top

Crystal data top

C₁₃H₁₁Cl₂NO₂S	F(000) = 648
M_r = 316.19	D_x = 1.477 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.0361 (10) Å	Cell parameters from 4545 reflections
b = 11.6937 (11) Å	θ = 2.5–27.5°
c = 13.6904 (15) Å	µ = 0.60 mm⁻¹
β = 100.588 (3)°	T = 296 K
V = 1422.0 (3) Å³	Prism, colourless
Z = 4	0.41 × 0.32 × 0.26 mm

Data collection top

Bruker APEXII CCD diffractometer	2019 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.033
Graphite monochromator	θ_max = 25.5°, θ_min = 2.3°
ω scans	h = −5→10
4252 measured reflections	k = −13→7
2566 independent reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.159	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.1006P)² + 0.1252P] where P = (F_o² + 2F_c²)/3
2566 reflections	(Δ/σ)_max < 0.001
173 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₁₃H₁₁Cl₂NO₂S	V = 1422.0 (3) Å³
M_r = 316.19	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.0361 (10) Å	µ = 0.60 mm⁻¹
b = 11.6937 (11) Å	T = 296 K
c = 13.6904 (15) Å	0.41 × 0.32 × 0.26 mm
β = 100.588 (3)°

Data collection top

Bruker APEXII CCD diffractometer	2019 reflections with I > 2σ(I)
4252 measured reflections	R_int = 0.033
2566 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.159	H-atom parameters constrained
S = 1.06	Δρ_max = 0.55 e Å⁻³
2566 reflections	Δρ_min = −0.46 e Å⁻³
173 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
C1	0.6508 (3)	0.2746 (2)	0.5229 (2)	0.0434 (6)
C2	0.7492 (3)	0.3602 (2)	0.5641 (2)	0.0518 (7)
H2	0.8171	0.3473	0.6229	0.062*
C3	0.7453 (4)	0.4650 (3)	0.5166 (3)	0.0600 (9)
C4	0.6466 (4)	0.4856 (3)	0.4299 (3)	0.0662 (9)
H4	0.6460	0.5562	0.3985	0.079*
C5	0.5481 (4)	0.4010 (3)	0.3895 (3)	0.0614 (8)
H5	0.4805	0.4145	0.3308	0.074*
C6	0.5494 (3)	0.2971 (2)	0.4355 (2)	0.0455 (7)
C7	0.4253 (3)	0.1890 (2)	0.66797 (19)	0.0412 (6)
C8	0.2706 (3)	0.1896 (3)	0.6440 (2)	0.0558 (8)
H8	0.2211	0.1433	0.5930	0.067*
C9	0.1896 (4)	0.2589 (4)	0.6959 (3)	0.0667 (9)
H9	0.0851	0.2590	0.6800	0.080*
C10	0.2613 (4)	0.3283 (3)	0.7712 (3)	0.0585 (8)
H10	0.2053	0.3753	0.8054	0.070*
C11	0.4159 (3)	0.3281 (3)	0.7957 (2)	0.0500 (7)
C12	0.4979 (3)	0.2580 (3)	0.7441 (2)	0.0450 (7)
H12	0.6025	0.2573	0.7606	0.054*
C13	0.4965 (4)	0.4020 (4)	0.8794 (3)	0.0768 (11)
H13A	0.6001	0.3789	0.8961	0.115*
H13B	0.4496	0.3934	0.9364	0.115*
H13C	0.4912	0.4806	0.8588	0.115*
S1	0.66516 (7)	0.13999 (6)	0.58357 (5)	0.0423 (3)
N1	0.5049 (3)	0.1135 (2)	0.61442 (17)	0.0453 (6)
H1	0.4508	0.0653	0.5765	0.054*
O1	0.6848 (2)	0.05302 (16)	0.51318 (15)	0.0499 (5)
O2	0.7776 (2)	0.15261 (18)	0.67029 (16)	0.0548 (6)
Cl1	0.42138 (9)	0.19405 (7)	0.38259 (6)	0.0597 (3)
Cl2	0.86761 (14)	0.57071 (9)	0.57067 (10)	0.0941 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0399 (15)	0.0476 (15)	0.0414 (15)	0.0030 (12)	0.0040 (12)	−0.0048 (12)
C2	0.0420 (16)	0.0568 (18)	0.0538 (19)	−0.0010 (13)	0.0014 (13)	−0.0093 (14)
C3	0.0599 (19)	0.0472 (18)	0.076 (2)	−0.0077 (14)	0.0209 (18)	−0.0136 (16)
C4	0.087 (2)	0.0502 (19)	0.065 (2)	0.0030 (17)	0.024 (2)	0.0066 (16)
C5	0.070 (2)	0.061 (2)	0.0507 (19)	0.0029 (16)	0.0039 (16)	0.0112 (15)
C6	0.0462 (16)	0.0493 (16)	0.0382 (15)	0.0026 (12)	0.0006 (12)	−0.0016 (12)
C7	0.0460 (15)	0.0441 (15)	0.0312 (14)	−0.0006 (11)	0.0012 (11)	0.0037 (11)
C8	0.0439 (17)	0.071 (2)	0.0488 (18)	−0.0107 (14)	−0.0007 (14)	−0.0142 (15)
C9	0.0389 (17)	0.093 (3)	0.066 (2)	−0.0041 (16)	0.0035 (15)	−0.0102 (19)
C10	0.0505 (18)	0.069 (2)	0.058 (2)	0.0003 (15)	0.0148 (16)	−0.0098 (16)
C11	0.0496 (17)	0.0591 (18)	0.0402 (16)	−0.0040 (13)	0.0053 (13)	−0.0038 (13)
C12	0.0409 (15)	0.0536 (17)	0.0368 (14)	−0.0033 (12)	−0.0024 (12)	−0.0035 (12)
C13	0.070 (2)	0.085 (3)	0.072 (2)	−0.0048 (19)	0.0063 (19)	−0.038 (2)
S1	0.0405 (4)	0.0450 (4)	0.0364 (4)	0.0049 (3)	−0.0060 (3)	−0.0037 (3)
N1	0.0494 (14)	0.0462 (13)	0.0369 (13)	−0.0051 (10)	−0.0008 (10)	−0.0077 (10)
O1	0.0494 (11)	0.0508 (12)	0.0460 (11)	0.0072 (9)	0.0000 (9)	−0.0093 (9)
O2	0.0464 (12)	0.0668 (14)	0.0420 (12)	0.0069 (9)	−0.0158 (9)	−0.0045 (9)
Cl1	0.0523 (5)	0.0712 (6)	0.0468 (5)	−0.0060 (4)	−0.0143 (3)	0.0039 (3)
Cl2	0.1001 (8)	0.0623 (6)	0.1198 (10)	−0.0296 (5)	0.0204 (7)	−0.0255 (6)

Geometric parameters (Å, º) top

C1—C2	1.388 (4)	C8—H8	0.9300
C1—C6	1.392 (4)	C9—C10	1.376 (5)
C1—S1	1.773 (3)	C9—H9	0.9300
C2—C3	1.385 (4)	C10—C11	1.375 (5)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.369 (5)	C11—C12	1.384 (4)
C3—Cl2	1.732 (3)	C11—C13	1.510 (4)
C4—C5	1.377 (5)	C12—H12	0.9300
C4—H4	0.9300	C13—H13A	0.9600
C5—C6	1.367 (4)	C13—H13B	0.9600
C5—H5	0.9300	C13—H13C	0.9600
C6—Cl1	1.734 (3)	S1—O2	1.421 (2)
C7—C8	1.376 (4)	S1—O1	1.434 (2)
C7—C12	1.384 (4)	S1—N1	1.611 (3)
C7—N1	1.425 (4)	N1—H1	0.8562
C8—C9	1.374 (5)

C2—C1—C6	119.0 (3)	C10—C9—H9	119.6
C2—C1—S1	117.6 (2)	C11—C10—C9	120.0 (3)
C6—C1—S1	123.4 (2)	C11—C10—H10	120.0
C3—C2—C1	119.2 (3)	C9—C10—H10	120.0
C3—C2—H2	120.4	C10—C11—C12	119.4 (3)
C1—C2—H2	120.4	C10—C11—C13	120.8 (3)
C4—C3—C2	121.3 (3)	C12—C11—C13	119.8 (3)
C4—C3—Cl2	120.5 (3)	C11—C12—C7	120.3 (3)
C2—C3—Cl2	118.1 (3)	C11—C12—H12	119.8
C3—C4—C5	119.4 (3)	C7—C12—H12	119.8
C3—C4—H4	120.3	C11—C13—H13A	109.5
C5—C4—H4	120.3	C11—C13—H13B	109.5
C6—C5—C4	120.3 (3)	H13A—C13—H13B	109.5
C6—C5—H5	119.9	C11—C13—H13C	109.5
C4—C5—H5	119.9	H13A—C13—H13C	109.5
C5—C6—C1	120.8 (3)	H13B—C13—H13C	109.5
C5—C6—Cl1	118.5 (2)	O2—S1—O1	118.51 (12)
C1—C6—Cl1	120.7 (2)	O2—S1—N1	109.86 (13)
C8—C7—C12	119.8 (3)	O1—S1—N1	105.52 (12)
C8—C7—N1	117.9 (3)	O2—S1—C1	106.17 (13)
C12—C7—N1	122.3 (3)	O1—S1—C1	108.81 (13)
C9—C8—C7	119.5 (3)	N1—S1—C1	107.55 (13)
C9—C8—H8	120.2	C7—N1—S1	125.4 (2)
C7—C8—H8	120.2	C7—N1—H1	115.7
C8—C9—C10	120.9 (3)	S1—N1—H1	114.1
C8—C9—H9	119.6

C6—C1—C2—C3	−0.7 (4)	C9—C10—C11—C12	0.1 (5)
S1—C1—C2—C3	177.4 (2)	C9—C10—C11—C13	−178.8 (4)
C1—C2—C3—C4	−0.1 (5)	C10—C11—C12—C7	0.3 (5)
C1—C2—C3—Cl2	179.1 (2)	C13—C11—C12—C7	179.3 (3)
C2—C3—C4—C5	0.6 (5)	C8—C7—C12—C11	−0.4 (4)
Cl2—C3—C4—C5	−178.6 (3)	N1—C7—C12—C11	−178.4 (3)
C3—C4—C5—C6	−0.2 (5)	C2—C1—S1—O2	3.2 (3)
C4—C5—C6—C1	−0.6 (5)	C6—C1—S1—O2	−178.7 (2)
C4—C5—C6—Cl1	179.1 (3)	C2—C1—S1—O1	−125.3 (2)
C2—C1—C6—C5	1.1 (4)	C6—C1—S1—O1	52.7 (3)
S1—C1—C6—C5	−176.9 (2)	C2—C1—S1—N1	120.8 (2)
C2—C1—C6—Cl1	−178.6 (2)	C6—C1—S1—N1	−61.1 (3)
S1—C1—C6—Cl1	3.4 (4)	C8—C7—N1—S1	144.7 (2)
C12—C7—C8—C9	0.1 (5)	C12—C7—N1—S1	−37.2 (4)
N1—C7—C8—C9	178.2 (3)	O2—S1—N1—C7	63.7 (2)
C7—C8—C9—C10	0.4 (6)	O1—S1—N1—C7	−167.5 (2)
C8—C9—C10—C11	−0.5 (6)	C1—S1—N1—C7	−51.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.09	2.946 (3)	178
C12—H12···O2	0.93	2.50	3.141 (3)	126

Symmetry code: (i) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁Cl₂NO₂S
M_r	316.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	9.0361 (10), 11.6937 (11), 13.6904 (15)
β (°)	100.588 (3)
V (Å³)	1422.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.60
Crystal size (mm)	0.41 × 0.32 × 0.26

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4252, 2566, 2019
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.159, 1.06
No. of reflections	2566
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.46

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.09	2.946 (3)	178
C12—H12···O2	0.93	2.50	3.141 (3)	126

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

The authors are thankful to the Higher Education Commission of Pakistan for providing a grant under the project to strengthen the Materials Chemistry Laboratory at GC University, Lahore.

References

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