3,5-Di­chloro-N-(2,4-di­chloro­phen­yl)benzene­sulfonamide

Shakuntala, K.; Lokanath, N.K.; Naveen, S.; Suchetan, P.A.

doi:10.1107/S2414314617003728

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 3| March 2017| x170372

https://doi.org/10.1107/S2414314617003728

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3,5-Dichloro-N-(2,4-dichlorophenyl)benzenesulfonamide

K. Shakuntala,^a N. K. Lokanath,^b S. Naveen ^c ^* and P. A. Suchetan ^d ^*

^aDepartment of Chemistry, Sri Bhuvanendra College, Karkala 574 104, India, ^bDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysuru-6, India, ^cInstitution of Excellence, University of Mysore, Manasagangotri, Mysuru-6, India, and ^dDepartment of Chemistry, University College of Science, Tumkur University, Tumkur 572 103, India
^*Correspondence e-mail: naveen@ioe.uni-mysore.ac.in, pasuchetan@yahoo.co.in

Edited by J. Simpson, University of Otago, New Zealand (Received 6 March 2017; accepted 8 March 2017; online 10 March 2017)

The molecule of the title compound, C₁₂H₇Cl₄NO₂S, is U-shaped, with the central C—S—N—C segment having a torsion angle of −58.7 (3)°. The dihedral angle between the benzene rings is 40.23 (2)°. Further, the ortho Cl atom on the aniline ring is syn to the N—H bond in the central –C—S(O₂)—NH—C– segment. In the crystal, molecules are linked by pairs of N—H⋯O hydrogen bonds, forming inversion dimers that enclose R₂²(8) loops. These dimers are linked by C—H⋯O hydrogen bonds that form a double C(7) chain propagating along the b-axis direction. These chains are further consolidated by Cl⋯Cl halogen bonds [3.4331 (2) Å]. π–π contacts [centroid–centroid distance = 3.6574 (19) Å] between the aniline rings link adjacent chains into a three-dimensional supramolecular network with molecules stacked along the b-axis direction.

Keywords: crystal structure; sulfonamides; N—H⋯O hydrogen bonds; C—H⋯O interactions; Cl⋯Cl contacts; π–π interactions.

CCDC reference: 1536597

Structure description

In recent years, extensive research has been carried out on the synthesis and evaluation of the pharmacological activities of molecules containing the sulfonamide moiety (Mohan et al., 2013 ). As part of our ongoing studies of sulfonamides (Shakuntala et al., 2017 ), we report herein the crystal structure of the title sulfonamide derivative.

The molecule of the title compound (Fig. 1) is U shaped with the central C1—S1—N1—C7 segment displaying a torsion angle of −58.7 (3)°. The dihedral angle between the benzene rings is 40.23 (2)°. Further, the ortho chlorine atom on the aniline ring is syn to the N—H bond in the central –C—S(O₂)-NH—C– segment of the molecule.

Figure 1
A view of the molecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

In the crystal, pairs of molecules are linked by N1—H1⋯O2ⁱ hydrogen bonds, forming inversion dimers that enclose R₂²(8) loops (Table 1 and Fig. 2). These dimers are joined through C9—H9⋯O1ⁱⁱ hydrogen bonds that form a double C(7) chain propagating along the b-axis direction. These chains are further consolidated by Cl3⋯Cl3ⁱⁱⁱ halogen bonds [3.4331 (2) Å; symmetry code: (iii) −x, −y + 1, −z + 1]. π–π contacts [centroid–centroid distance = 3.6574 (19) Å; symmetry code: 1 − x, 1 − y, 1 − z] between the C7–C12 rings, Fig. 3, link adjacent chains into a three-dimensional supramolecular network with molecules stacked along the b-axis direction.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.86	2.20	3.0026	155
C9—H9⋯O1ⁱⁱ	0.95	2.39	3.324 (4)	170
Symmetry codes: (i) -x, -y+2, -z+1; (ii) x, y-1, z.

Figure 2
Double-chain architecture displayed in the crystal structure of the title compound, propagating along the b axis and formed by N—H⋯O and C—H⋯O hydrogen bonds (see Table 1

). Cl⋯Cl contacts are also shown.

Figure 3
π_aryl–π_aryl contacts in the title compound viewed along a.

Synthesis and crystallization

The title compound was prepared according to a literature method (Rodrigues et al., 2015 ). The purity of the compound was checked by determining its melting point. Prismatic single crystals suitable for X-ray diffraction study were obtained by slow evaporation of an ethanol solution of the compound at room temperature.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₇Cl₄NO₂S
M_r	371.05
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	8.1107 (4), 8.2615 (4), 11.2048 (5)
α, β, γ (°)	86.791 (2), 70.625 (2), 85.783 (2)
V (Å³)	705.96 (6)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	9.01
Crystal size (mm)	0.26 × 0.23 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.144, 0.165
No. of measured, independent and observed [I > 2σ(I)] reflections	6182, 2295, 2152
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.584

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.190, 1.08
No. of reflections	2295
No. of parameters	185
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.15, −1.04
Computer programs: APEX2, SAINT-Plus and XPREP (Bruker, 2009), SHELXT2016 (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1536597

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617003728/sj4094sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617003728/sj4094Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617003728/sj4094Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 and SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus and XPREP (Bruker, 2009); program(s) used to solve structure: SHELXT2016 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015b).

3,5-Dichloro-N-(2,4-dichlorophenyl)benzenesulfonamide top

Crystal data top

C₁₂H₇Cl₄NO₂S	Z = 2
M_r = 371.05	F(000) = 372
Triclinic, P1	prism
Hall symbol: -P 1	D_x = 1.746 Mg m⁻³
a = 8.1107 (4) Å	Cu Kα radiation, λ = 1.54178 Å
b = 8.2615 (4) Å	Cell parameters from 154 reflections
c = 11.2048 (5) Å	θ = 5.4–64.2°
α = 86.791 (2)°	µ = 9.01 mm⁻¹
β = 70.625 (2)°	T = 100 K
γ = 85.783 (2)°	Prism, colourless
V = 705.96 (6) Å³	0.26 × 0.23 × 0.20 mm

Data collection top

Bruker APEXII CCD area detector diffractometer	2295 independent reflections
Radiation source: fine-focus sealed tube	2152 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
φ and ω scans	θ_max = 64.2°, θ_min = 5.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
T_min = 0.144, T_max = 0.165	k = −9→9
6182 measured reflections	l = −12→13

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.063	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.190	w = 1/[σ²(F_o²) + (0.153P)² + 0.3492P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2295 reflections	Δρ_max = 1.15 e Å⁻³
185 parameters	Δρ_min = −1.04 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	−0.0147 (4)	0.9271 (4)	0.7955 (3)	0.0146 (7)
C2	0.0650 (4)	0.8534 (4)	0.8789 (3)	0.0137 (7)
H2	0.185287	0.865134	0.866524	0.016*
C3	−0.0373 (5)	0.7626 (4)	0.9805 (3)	0.0169 (8)
C4	−0.2119 (5)	0.7464 (4)	1.0011 (3)	0.0202 (8)
H4	−0.279938	0.684198	1.071779	0.024*
C5	−0.2867 (5)	0.8225 (5)	0.9167 (4)	0.0208 (8)
C6	−0.1911 (5)	0.9131 (4)	0.8122 (3)	0.0183 (8)
H6	−0.243662	0.963513	0.754287	0.022*
C7	0.3233 (4)	0.7602 (4)	0.5954 (3)	0.0132 (7)
C8	0.2658 (4)	0.6040 (4)	0.6286 (3)	0.0123 (7)
C9	0.3685 (4)	0.4808 (4)	0.6637 (3)	0.0140 (7)
H9	0.329198	0.373986	0.683842	0.017*
C10	0.5287 (5)	0.5179 (4)	0.6686 (3)	0.0157 (8)
C11	0.5914 (5)	0.6721 (4)	0.6362 (3)	0.0160 (8)
H11	0.703132	0.694572	0.639253	0.019*
C12	0.4883 (4)	0.7922 (4)	0.5996 (3)	0.0154 (8)
H12	0.530101	0.897891	0.576927	0.018*
N1	0.2191 (4)	0.8860 (3)	0.5578 (3)	0.0142 (6)
O1	0.2543 (3)	1.0985 (3)	0.6941 (2)	0.0167 (6)
O2	0.0145 (3)	1.1270 (3)	0.6002 (2)	0.0198 (6)
S1	0.12158 (10)	1.02925 (9)	0.65887 (8)	0.0129 (3)
CL1	0.05978 (11)	0.66634 (11)	1.08447 (8)	0.0222 (3)
CL2	−0.50807 (12)	0.80140 (14)	0.94357 (9)	0.0313 (4)
CL3	0.06355 (10)	0.55785 (10)	0.62220 (8)	0.0180 (3)
CL4	0.65852 (11)	0.36568 (10)	0.71396 (8)	0.0215 (3)
H1	0.149 (4)	0.853 (5)	0.523 (4)	0.012 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0141 (17)	0.0164 (17)	0.0120 (17)	−0.0025 (13)	−0.0024 (13)	0.0005 (13)
C2	0.0123 (15)	0.0140 (17)	0.0142 (18)	−0.0004 (13)	−0.0032 (13)	−0.0038 (14)
C3	0.0211 (19)	0.0191 (19)	0.0114 (19)	−0.0003 (15)	−0.0068 (15)	0.0008 (15)
C4	0.0206 (19)	0.0231 (19)	0.0123 (18)	−0.0086 (15)	0.0022 (15)	0.0005 (15)
C5	0.0125 (17)	0.029 (2)	0.0195 (19)	−0.0047 (15)	−0.0029 (14)	−0.0018 (16)
C6	0.0179 (18)	0.023 (2)	0.0143 (18)	−0.0005 (14)	−0.0062 (15)	−0.0023 (14)
C7	0.0149 (17)	0.0174 (18)	0.0055 (16)	0.0002 (13)	−0.0014 (13)	−0.0006 (13)
C8	0.0094 (15)	0.0191 (18)	0.0077 (15)	−0.0042 (13)	−0.0012 (13)	−0.0008 (13)
C9	0.0176 (17)	0.0131 (17)	0.0098 (17)	−0.0018 (13)	−0.0025 (13)	0.0006 (13)
C10	0.0170 (17)	0.0192 (18)	0.0095 (17)	0.0017 (14)	−0.0036 (14)	0.0030 (14)
C11	0.0123 (16)	0.0219 (19)	0.0133 (18)	−0.0043 (14)	−0.0030 (13)	0.0005 (14)
C12	0.0135 (17)	0.0173 (18)	0.0128 (17)	−0.0046 (13)	−0.0008 (13)	0.0036 (13)
N1	0.0150 (14)	0.0159 (15)	0.0133 (15)	−0.0034 (11)	−0.0068 (12)	0.0024 (12)
O1	0.0172 (12)	0.0158 (12)	0.0172 (13)	−0.0052 (10)	−0.0052 (10)	0.0027 (10)
O2	0.0215 (13)	0.0180 (13)	0.0201 (14)	0.0022 (10)	−0.0084 (11)	0.0032 (10)
S1	0.0132 (5)	0.0127 (5)	0.0124 (5)	−0.0028 (4)	−0.0038 (4)	0.0030 (4)
CL1	0.0241 (5)	0.0271 (6)	0.0155 (5)	−0.0033 (4)	−0.0076 (4)	0.0072 (4)
CL2	0.0129 (5)	0.0571 (8)	0.0232 (6)	−0.0112 (4)	−0.0037 (4)	0.0027 (5)
CL3	0.0142 (5)	0.0201 (5)	0.0225 (6)	−0.0070 (4)	−0.0094 (4)	0.0045 (4)
CL4	0.0189 (5)	0.0227 (6)	0.0247 (6)	0.0014 (4)	−0.0110 (4)	0.0057 (4)

Geometric parameters (Å, º) top

C1—C6	1.393 (5)	C7—N1	1.424 (4)
C1—C2	1.393 (5)	C8—C9	1.391 (5)
C1—S1	1.774 (4)	C8—CL3	1.736 (3)
C2—C3	1.385 (5)	C9—C10	1.376 (5)
C2—H2	0.9500	C9—H9	0.9500
C3—C4	1.372 (5)	C10—C11	1.391 (5)
C3—CL1	1.738 (3)	C10—CL4	1.742 (3)
C4—C5	1.384 (6)	C11—C12	1.383 (5)
C4—H4	0.9500	C11—H11	0.9500
C5—C6	1.385 (5)	C12—H12	0.9500
C5—CL2	1.740 (4)	N1—S1	1.651 (3)
C6—H6	0.9500	N1—H1	0.858 (19)
C7—C8	1.393 (5)	O1—S1	1.428 (3)
C7—C12	1.400 (5)	O2—S1	1.433 (3)

C6—C1—C2	122.3 (3)	C7—C8—CL3	119.9 (3)
C6—C1—S1	120.4 (3)	C10—C9—C8	118.1 (3)
C2—C1—S1	117.2 (3)	C10—C9—H9	120.9
C3—C2—C1	117.6 (3)	C8—C9—H9	120.9
C3—C2—H2	121.2	C9—C10—C11	122.0 (3)
C1—C2—H2	121.2	C9—C10—CL4	118.9 (3)
C4—C3—C2	122.0 (3)	C11—C10—CL4	119.1 (3)
C4—C3—CL1	119.4 (3)	C12—C11—C10	118.9 (3)
C2—C3—CL1	118.6 (3)	C12—C11—H11	120.6
C3—C4—C5	118.7 (3)	C10—C11—H11	120.6
C3—C4—H4	120.7	C11—C12—C7	120.9 (3)
C5—C4—H4	120.7	C11—C12—H12	119.6
C4—C5—C6	122.2 (3)	C7—C12—H12	119.6
C4—C5—CL2	118.3 (3)	C7—N1—S1	118.4 (2)
C6—C5—CL2	119.4 (3)	C7—N1—H1	115 (3)
C5—C6—C1	117.1 (3)	S1—N1—H1	111 (3)
C5—C6—H6	121.4	O1—S1—O2	121.08 (15)
C1—C6—H6	121.4	O1—S1—N1	107.18 (15)
C8—C7—C12	118.3 (3)	O2—S1—N1	105.43 (15)
C8—C7—N1	121.8 (3)	O1—S1—C1	107.19 (15)
C12—C7—N1	119.9 (3)	O2—S1—C1	109.28 (16)
C9—C8—C7	121.8 (3)	N1—S1—C1	105.69 (15)
C9—C8—CL3	118.3 (3)

C6—C1—C2—C3	0.6 (5)	C8—C9—C10—C11	−1.8 (5)
S1—C1—C2—C3	−175.0 (3)	C8—C9—C10—CL4	179.4 (3)
C1—C2—C3—C4	−1.0 (5)	C9—C10—C11—C12	0.8 (5)
C1—C2—C3—CL1	178.8 (3)	CL4—C10—C11—C12	179.6 (3)
C2—C3—C4—C5	0.5 (6)	C10—C11—C12—C7	0.3 (5)
CL1—C3—C4—C5	−179.4 (3)	C8—C7—C12—C11	−0.3 (5)
C3—C4—C5—C6	0.5 (6)	N1—C7—C12—C11	179.7 (3)
C3—C4—C5—CL2	−180.0 (3)	C8—C7—N1—S1	105.4 (3)
C4—C5—C6—C1	−0.9 (6)	C12—C7—N1—S1	−74.6 (4)
CL2—C5—C6—C1	179.6 (3)	C7—N1—S1—O1	55.4 (3)
C2—C1—C6—C5	0.3 (6)	C7—N1—S1—O2	−174.4 (2)
S1—C1—C6—C5	175.8 (3)	C7—N1—S1—C1	−58.7 (3)
C12—C7—C8—C9	−0.8 (5)	C6—C1—S1—O1	150.1 (3)
N1—C7—C8—C9	179.2 (3)	C2—C1—S1—O1	−34.1 (3)
C12—C7—C8—CL3	−178.9 (3)	C6—C1—S1—O2	17.2 (4)
N1—C7—C8—CL3	1.1 (5)	C2—C1—S1—O2	−167.0 (3)
C7—C8—C9—C10	1.8 (5)	C6—C1—S1—N1	−95.8 (3)
CL3—C8—C9—C10	180.0 (3)	C2—C1—S1—N1	79.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.20	3.0026	155
C9—H9···O1ⁱⁱ	0.95	2.39	3.324 (4)	170

Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y−1, z.

Acknowledgements

The authors are thankful to the Institution of Excellence, Vijnana Bhavana, University of Mysore, Mysore, for providing the single-crystal X-ray diffraction data. KS is thankful to the University Grants Commission (UGC), New Delhi for the financial assistance under its MRP scheme.

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