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

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

doi:10.1107/S1600536812035787

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2748

doi:10.1107/S1600536812035787

Open

access

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

Shumaila Younas Mughal,^a Islam Ullah Khan,^a ^* William T. A. Harrison,^b Muneeb Hayat Khan ^c and Muhammad Nawaz Tahir ^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 ^dDepartment of Physics, University of Sargodha, Punjab, Pakistan.
^*Correspondence e-mail: koolmuneeb@yahoo.com

(Received 14 August 2012; accepted 14 August 2012; online 23 August 2012)

In the title compound, C₁₄H₁₃Cl₂NO₂S, the dihedral angle between the aromatic rings is 62.21 (7)° and the C—S—N—C group adopts a gauche conformation [torsion angle = 60.22 (17)°]. In the crystal, N—H⋯O hydrogen bonds link the molecules into C(4) chains propagating in [010]. A short intermolecular Cl⋯O contact of 3.1115 (17) Å is seen.

Related literature

For related structures, see: Mughal et al. (2012a ,b ).

Experimental

Crystal data

C₁₄H₁₃Cl₂NO₂S
M_r = 330.21
Orthorhombic, P b c a
a = 13.0069 (11) Å
b = 10.0775 (9) Å
c = 22.408 (2) Å
V = 2937.2 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
23820 measured reflections
3260 independent reflections
2377 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.090
S = 0.98
3260 reflections
186 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.87 (2)	2.14 (2)	2.975 (2)	162.9 (19)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

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: 10.1107/S1600536812035787/bt6820sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812035787/bt6820Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812035787/bt6820Isup3.cml

checkCIF report

Comment top

The title compound, (I), (Fig. 1) was examined as part of our ongoing interest in the structural chemistry of sulfonamides (Mughal et al., 2012a,b).

The dihedral angle between the C1—C6 and C9—C14 benzene rings in (I) is 62.21 (7)°. The C1—N1—S1—C9 linkage adopts a near-ideal gauche conformation [torsion angle = 60.22 (17)°] and the bond-angle sum about N1 (H atom freely refined) is 349°, possibly suggesting a hybridization state intermediate between sp² and sp³, which was also observed in a related compound (Mughal et al., 2012a). The largest bond angle at the distorted tetrahedral S atom is O1—S1—O2 [119.69 (9)°], which again is typical for this class of compound (Mughal et al., 2012b).

In the crystal, the molecules are linked by N—H···O hydrogen bonds (Table 1) to generate C(4) chains propagating in [010]: adjacent molecules are in the chain are generated by glide-symmetry. A similar chain occurs in N-(2,3-dihydro-1,4-benzodioxin-6-yl)-4-fluorobenzenesulfonamide (Mughal et al., 2012a), although in this case, adjacent molecules are generated by translational symmetry. Conversely, in 2,5-dichloro-N-(3-methylphenyl)benzenesulfonamide (Mughal et al., 2012b), pairs of N—H···O interactions lead to inversion dimers in the crystal.

Any aromatic π-π stacking in (I), if it exists at all, must be extremely weak, as the shortest inter-centroid ring separation is 4.0550 (12) Å between inversion-symmetry related C9–C14 rings (slippage = 1.906 Å). A short intermolecular Cl···O contact of 3.1115 (17) Å occurs (van der Waals' radius sum for these species = 3.27 Å).

Related literature top

For related structures, see: Mughal et al. (2012a,b).

Experimental top

0.1 g of 2,3 dimethyl aniline was dissolved in 15 ml dichloromethane and 0.2 g of 2,5-dichloro benzene sulfonylchloride was added: the mixture was stirred at room temperature overnight with the pH maintained at 8–9 with triethyamine. On completion of reaction (after TLC) the mixture was poured into a separating flask and 1 M HCl solution added. The lower DCM layer was separated and the solvent was allowed to evaporate at room temperature. Brown blocks of (I) were recrystallized from acetonitrile solution at room temperature in 96% yield.

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. Fragment of a C(4) chain in the crystal of (I), with N—H···O hydrogen bonds shown as double-dashed lines. All C-bound H atoms omitted for clarity. Symmetry code: (i) 1/2 - x, y + 1/2, z.

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

Crystal data top

C₁₄H₁₃Cl₂NO₂S	D_x = 1.494 Mg m⁻³
M_r = 330.21	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 1890 reflections
a = 13.0069 (11) Å	θ = 4.2–21.6°
b = 10.0775 (9) Å	µ = 0.58 mm⁻¹
c = 22.408 (2) Å	T = 296 K
V = 2937.2 (4) Å³	Block, colourless
Z = 8	0.30 × 0.20 × 0.18 mm
F(000) = 1360

Data collection top

Bruker APEXII CCD diffractometer	2377 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.045
Graphite monochromator	θ_max = 27.2°, θ_min = 1.8°
ω scans	h = −16→15
23820 measured reflections	k = −12→12
3260 independent reflections	l = −28→28

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0396P)² + 1.0864P] where P = (F_o² + 2F_c²)/3
3260 reflections	(Δ/σ)_max = 0.001
186 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₄H₁₃Cl₂NO₂S	V = 2937.2 (4) Å³
M_r = 330.21	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 13.0069 (11) Å	µ = 0.58 mm⁻¹
b = 10.0775 (9) Å	T = 296 K
c = 22.408 (2) Å	0.30 × 0.20 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	2377 reflections with I > 2σ(I)
23820 measured reflections	R_int = 0.045
3260 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.26 e Å⁻³
3260 reflections	Δρ_min = −0.31 e Å⁻³
186 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	0.36432 (15)	0.2392 (2)	0.27761 (9)	0.0380 (5)
C2	0.34175 (15)	0.1626 (2)	0.22779 (9)	0.0403 (5)
C3	0.41472 (17)	0.1589 (2)	0.18170 (10)	0.0471 (6)
C4	0.50361 (19)	0.2333 (3)	0.18622 (11)	0.0607 (7)
H1A	0.5523	0.2287	0.1559	0.073*
C5	0.52163 (19)	0.3142 (3)	0.23476 (12)	0.0648 (7)
H13	0.5802	0.3670	0.2362	0.078*
C6	0.45235 (17)	0.3159 (2)	0.28092 (11)	0.0510 (6)
H14	0.4645	0.3685	0.3143	0.061*
C7	0.24248 (18)	0.0871 (3)	0.22183 (11)	0.0593 (7)
H11A	0.2014	0.1006	0.2569	0.089*
H11B	0.2570	−0.0058	0.2174	0.089*
H11C	0.2057	0.1183	0.1874	0.089*
C8	0.3960 (2)	0.0772 (3)	0.12657 (11)	0.0689 (8)
H12A	0.4552	0.0817	0.1011	0.103*
H12B	0.3371	0.1111	0.1057	0.103*
H12C	0.3838	−0.0134	0.1377	0.103*
C9	0.42663 (14)	0.14693 (19)	0.41375 (8)	0.0334 (4)
C10	0.45813 (15)	0.2588 (2)	0.44538 (9)	0.0376 (5)
C11	0.55332 (16)	0.2609 (2)	0.47257 (10)	0.0469 (5)
H7	0.5742	0.3358	0.4936	0.056*
C12	0.61758 (16)	0.1526 (2)	0.46883 (10)	0.0490 (6)
H8	0.6814	0.1538	0.4875	0.059*
C13	0.58658 (16)	0.0429 (2)	0.43732 (9)	0.0416 (5)
C14	0.49226 (15)	0.0390 (2)	0.40944 (9)	0.0389 (5)
H10	0.4727	−0.0356	0.3878	0.047*
Cl1	0.38122 (4)	0.39770 (5)	0.45093 (3)	0.04880 (16)
Cl2	0.66673 (5)	−0.09408 (7)	0.43314 (3)	0.0630 (2)
S1	0.30265 (4)	0.13320 (5)	0.38004 (2)	0.03558 (14)
N1	0.29345 (12)	0.24200 (17)	0.32771 (8)	0.0376 (4)
H1	0.2777 (16)	0.322 (2)	0.3392 (10)	0.045*
O1	0.30173 (10)	0.00454 (14)	0.35289 (7)	0.0443 (4)
O2	0.22658 (11)	0.16635 (16)	0.42321 (7)	0.0487 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0366 (10)	0.0394 (12)	0.0381 (11)	0.0035 (9)	−0.0028 (8)	0.0021 (10)
C2	0.0406 (11)	0.0416 (12)	0.0386 (12)	0.0063 (10)	−0.0032 (9)	−0.0006 (10)
C3	0.0519 (13)	0.0519 (14)	0.0375 (12)	0.0134 (11)	0.0019 (10)	0.0036 (11)
C4	0.0500 (13)	0.0814 (19)	0.0506 (15)	0.0037 (13)	0.0089 (11)	0.0181 (14)
C5	0.0498 (14)	0.0821 (19)	0.0627 (17)	−0.0222 (14)	−0.0005 (12)	0.0166 (15)
C6	0.0541 (13)	0.0544 (14)	0.0446 (13)	−0.0158 (12)	−0.0040 (11)	0.0014 (12)
C7	0.0507 (13)	0.0732 (17)	0.0540 (14)	−0.0088 (13)	−0.0089 (11)	−0.0155 (14)
C8	0.0825 (19)	0.078 (2)	0.0458 (14)	0.0175 (15)	0.0057 (13)	−0.0104 (14)
C9	0.0351 (10)	0.0356 (11)	0.0296 (10)	−0.0050 (9)	0.0024 (8)	−0.0019 (9)
C10	0.0390 (10)	0.0374 (11)	0.0365 (11)	−0.0029 (9)	−0.0006 (8)	−0.0027 (9)
C11	0.0462 (12)	0.0483 (13)	0.0461 (13)	−0.0077 (11)	−0.0079 (10)	−0.0096 (11)
C12	0.0382 (11)	0.0592 (15)	0.0497 (14)	−0.0038 (11)	−0.0091 (10)	−0.0002 (12)
C13	0.0401 (11)	0.0439 (12)	0.0407 (12)	0.0038 (10)	0.0028 (9)	0.0077 (10)
C14	0.0412 (11)	0.0373 (11)	0.0384 (11)	−0.0036 (9)	0.0018 (9)	−0.0021 (9)
Cl1	0.0479 (3)	0.0399 (3)	0.0586 (4)	0.0005 (2)	−0.0035 (2)	−0.0150 (3)
Cl2	0.0558 (4)	0.0571 (4)	0.0760 (4)	0.0165 (3)	−0.0020 (3)	0.0082 (3)
S1	0.0320 (2)	0.0373 (3)	0.0374 (3)	−0.0063 (2)	0.0019 (2)	−0.0072 (2)
N1	0.0382 (9)	0.0360 (9)	0.0386 (9)	0.0041 (8)	0.0001 (7)	−0.0077 (8)
O1	0.0438 (8)	0.0374 (8)	0.0515 (9)	−0.0084 (7)	−0.0015 (7)	−0.0112 (7)
O2	0.0393 (8)	0.0595 (10)	0.0473 (9)	−0.0077 (7)	0.0115 (7)	−0.0117 (8)

Geometric parameters (Å, º) top

C1—C6	1.384 (3)	C8—H12C	0.9600
C1—C2	1.388 (3)	C9—C14	1.386 (3)
C1—N1	1.453 (3)	C9—C10	1.394 (3)
C2—C3	1.403 (3)	C9—S1	1.786 (2)
C2—C7	1.505 (3)	C10—C11	1.380 (3)
C3—C4	1.381 (3)	C10—Cl1	1.725 (2)
C3—C8	1.505 (3)	C11—C12	1.377 (3)
C4—C5	1.379 (4)	C11—H7	0.9300
C4—H1A	0.9300	C12—C13	1.372 (3)
C5—C6	1.372 (3)	C12—H8	0.9300
C5—H13	0.9300	C13—C14	1.377 (3)
C6—H14	0.9300	C13—Cl2	1.732 (2)
C7—H11A	0.9600	C14—H10	0.9300
C7—H11B	0.9600	S1—O2	1.4235 (14)
C7—H11C	0.9600	S1—O1	1.4323 (14)
C8—H12A	0.9600	S1—N1	1.6098 (18)
C8—H12B	0.9600	N1—H1	0.87 (2)

C6—C1—C2	121.9 (2)	H12B—C8—H12C	109.5
C6—C1—N1	118.21 (19)	C14—C9—C10	119.30 (18)
C2—C1—N1	119.86 (18)	C14—C9—S1	117.77 (15)
C1—C2—C3	117.6 (2)	C10—C9—S1	122.90 (15)
C1—C2—C7	122.27 (19)	C11—C10—C9	120.01 (19)
C3—C2—C7	120.1 (2)	C11—C10—Cl1	118.46 (16)
C4—C3—C2	119.9 (2)	C9—C10—Cl1	121.52 (15)
C4—C3—C8	119.5 (2)	C12—C11—C10	120.4 (2)
C2—C3—C8	120.6 (2)	C12—C11—H7	119.8
C5—C4—C3	121.4 (2)	C10—C11—H7	119.8
C5—C4—H1A	119.3	C13—C12—C11	119.42 (19)
C3—C4—H1A	119.3	C13—C12—H8	120.3
C6—C5—C4	119.4 (2)	C11—C12—H8	120.3
C6—C5—H13	120.3	C12—C13—C14	121.2 (2)
C4—C5—H13	120.3	C12—C13—Cl2	119.53 (17)
C5—C6—C1	119.7 (2)	C14—C13—Cl2	119.27 (18)
C5—C6—H14	120.1	C13—C14—C9	119.7 (2)
C1—C6—H14	120.1	C13—C14—H10	120.2
C2—C7—H11A	109.5	C9—C14—H10	120.2
C2—C7—H11B	109.5	O2—S1—O1	119.69 (9)
H11A—C7—H11B	109.5	O2—S1—N1	106.47 (9)
C2—C7—H11C	109.5	O1—S1—N1	107.85 (9)
H11A—C7—H11C	109.5	O2—S1—C9	108.78 (9)
H11B—C7—H11C	109.5	O1—S1—C9	104.91 (9)
C3—C8—H12A	109.5	N1—S1—C9	108.81 (9)
C3—C8—H12B	109.5	C1—N1—S1	120.16 (14)
H12A—C8—H12B	109.5	C1—N1—H1	113.4 (15)
C3—C8—H12C	109.5	S1—N1—H1	115.5 (15)
H12A—C8—H12C	109.5

C6—C1—C2—C3	3.8 (3)	Cl1—C10—C11—C12	−179.43 (18)
N1—C1—C2—C3	−177.39 (18)	C10—C11—C12—C13	0.6 (3)
C6—C1—C2—C7	−175.2 (2)	C11—C12—C13—C14	−0.1 (3)
N1—C1—C2—C7	3.6 (3)	C11—C12—C13—Cl2	−179.36 (17)
C1—C2—C3—C4	−2.0 (3)	C12—C13—C14—C9	−0.8 (3)
C7—C2—C3—C4	177.0 (2)	Cl2—C13—C14—C9	178.45 (15)
C1—C2—C3—C8	179.5 (2)	C10—C9—C14—C13	1.2 (3)
C7—C2—C3—C8	−1.5 (3)	S1—C9—C14—C13	−176.79 (16)
C2—C3—C4—C5	−1.5 (4)	C14—C9—S1—O2	127.48 (16)
C8—C3—C4—C5	177.1 (2)	C10—C9—S1—O2	−50.46 (19)
C3—C4—C5—C6	3.3 (4)	C14—C9—S1—O1	−1.71 (18)
C4—C5—C6—C1	−1.5 (4)	C10—C9—S1—O1	−179.65 (16)
C2—C1—C6—C5	−2.0 (3)	C14—C9—S1—N1	−116.91 (16)
N1—C1—C6—C5	179.1 (2)	C10—C9—S1—N1	65.14 (18)
C14—C9—C10—C11	−0.7 (3)	C6—C1—N1—S1	−93.2 (2)
S1—C9—C10—C11	177.17 (16)	C2—C1—N1—S1	87.9 (2)
C14—C9—C10—Cl1	178.49 (15)	O2—S1—N1—C1	177.30 (15)
S1—C9—C10—Cl1	−3.6 (2)	O1—S1—N1—C1	−53.06 (17)
C9—C10—C11—C12	−0.2 (3)	C9—S1—N1—C1	60.22 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.87 (2)	2.14 (2)	2.975 (2)	162.9 (19)

Symmetry code: (i) −x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₃Cl₂NO₂S
M_r	330.21
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	13.0069 (11), 10.0775 (9), 22.408 (2)
V (Å³)	2937.2 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.58
Crystal size (mm)	0.30 × 0.20 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	23820, 3260, 2377
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.643

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.090, 0.98
No. of reflections	3260
No. of parameters	186
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.31

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	0.87 (2)	2.14 (2)	2.975 (2)	162.9 (19)

Symmetry code: (i) −x+1/2, y+1/2, z.

Acknowledgements

The authors are grateful to the Higher Education Commission (HEC), Pakistan, for providing funds for the single-crystal XRD facilities at GC University Lahore.

References

Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Mughal, S. Y., Khan, I. U., Harrison, W. T. A., Khan, M. H. & Arshad, M. N. (2012a). Acta Cryst. E68, o2433. CSD CrossRef IUCr Journals Google Scholar
Mughal, S. Y., Khan, I. U., Harrison, W. T. A., Khan, M. H. & Arshad, M. N. (2012b). Acta Cryst. E68, o2476. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar