4-Chloro-N-(3,5-dichloro­phenyl)benzene­sulfonamide

Shakuntala, K.; Foro, S.; Gowda, B.T.

doi:10.1107/S160053681101470X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1219

doi:10.1107/S160053681101470X

Open

access

4-Chloro-N-(3,5-dichlorophenyl)benzenesulfonamide

K. Shakuntala,^a Sabine Foro ^b and B. Thimme Gowda ^a ^*

^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 16 April 2011; accepted 19 April 2011; online 29 April 2011)

In the title compound, C₁₂H₈Cl₃NO₂S, the dihedral angle between the aromatic rings is 87.9 (1)° and the C—S—N—C torsion angle is 77.8 (2)°. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds occur.

Related literature

For hydrogen-bonding preferences of sulfonamides, see; Adsmond & Grant (2001 ). For our study of the effect of substituents on the structures of N-(aryl)-amides, see: Gowda et al. (2004 ); on the structures of N-(aryl)arylsulfonamides, see: Shakuntala et al. (2011a ,b ); and on the oxidative strengths of N-chloro-N-arylsulfonamides, see: Gowda & Kumar (2003 ).

Experimental

Crystal data

C₁₂H₈Cl₃NO₂S
M_r = 336.60
Triclinic, $[P \overline 1]$
a = 4.935 (1) Å
b = 11.630 (2) Å
c = 13.115 (2) Å
α = 113.52 (2)°
β = 90.49 (1)°
γ = 96.50 (1)°
V = 684.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.82 mm⁻¹
T = 293 K
0.32 × 0.20 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.780, T_max = 0.923
4440 measured reflections
2785 independent reflections
2236 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.086
S = 1.03
2785 reflections
175 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2ⁱ	0.84 (2)	2.08 (2)	2.917 (2)	170 (2)
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; 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/S160053681101470X/bq2298sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681101470X/bq2298Isup2.hkl

checkCIF report

Comment top

The amide and sulfonamide moieties are important constituents of many biologically important compounds. As a part of studying the substituent effects on the structures and other aspects of this class of compounds (Gowda & Kumar, 2003; Gowda et al., 2004; Shakuntala et al., 2011a,b), in the present work, the crystal structure of 4-chloro-N-(3,5-dichlorophenyl)benzenesulfonamide (I) has been determined (Fig. 1). The molecule is twisted at the S atom with the C—SO₂—NH—C torsion angle of 77.8 (2)°, compared to the values of -58.4 (3)° in 4-chloro-N-(3-chlorophenyl)benzenesulfonamide (II) (Shakuntala et al., 2011b) and -56.7 (2)° in 4-chloro-N-(2,3-dichlorophenyl)-benzenesulfonamide (III) (Shakuntala et al., 2011a). The conformation of the N—H bond is anti to one of the meta-chloro group in the anilino benzene ring and syn to the other.

The sulfonyl and the anilino benzene rings in (I) are tilted relative to each other by 87.9 (1)°, compared to the values of 77.1 (1)° in (II) and 56.5 (1)° in (III).

Intermolecular N—H···O(S) hydrogen bonding interactions generate inversion related dimers which are further packed via van der Waals interactions in the crystal structure (Fig. 2).

Related literature top

For hydrogen-bonding preferences of sulfonamides, see; Adsmond & Grant (2001). For our study of the effect of substituents on the structures of N-(aryl)-amides, see: Gowda et al. (2004); on the structures of N-(aryl)arylsulfonamides, see: Shakuntala et al. (2011a,b); and on the oxidative strengths of N-chloro-N-arylsulfonamides, see: Gowda & Kumar (2003).

Experimental top

The solution of chlorobenzene (10 ml) in chloroform (40 ml) was added dropwise with chlorosulfonic acid (25 ml) 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 4-chlorobenzenesulfonylchloride was treated with 3,5-dichloroaniline in the stoichiometric ratio and boiled for 15 min. The reaction mixture was then cooled to room temperature and added to ice cold water (100 ml). The resultant 4-chloro-N-(3,5-dichlorophenyl)-benzenesulfonamide was filtered under suction and washed thoroughly with cold water. It was then recrystallized to constant melting point from dilute ethanol. The compound was characterized by FT–IR and NMR spectra.

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

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

	Fig. 1. Molecular structure of (I), showing the atom labeling scheme and displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Molecular packing of (I) with hydrogen bonding shown as dashed lines.

4-Chloro-N-(3,5-dichlorophenyl)benzenesulfonamide top

Crystal data top

C₁₂H₈Cl₃NO₂S	Z = 2
M_r = 336.60	F(000) = 340
Triclinic, P1	D_x = 1.633 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.935 (1) Å	Cell parameters from 1578 reflections
b = 11.630 (2) Å	θ = 3.0–27.8°
c = 13.115 (2) Å	µ = 0.82 mm⁻¹
α = 113.52 (2)°	T = 293 K
β = 90.49 (1)°	Prism, colourless
γ = 96.50 (1)°	0.32 × 0.20 × 0.10 mm
V = 684.6 (2) Å³

Data collection top

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector	2785 independent reflections
Radiation source: fine-focus sealed tube	2236 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
Rotation method data acquisition using ω and ϕ scans	θ_max = 26.4°, θ_min = 3.0°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −6→4
T_min = 0.780, T_max = 0.923	k = −14→14
4440 measured reflections	l = −15→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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0393P)² + 0.3103P] where P = (F_o² + 2F_c²)/3
2785 reflections	(Δ/σ)_max = 0.005
175 parameters	Δρ_max = 0.36 e Å⁻³
1 restraint	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₂H₈Cl₃NO₂S	γ = 96.50 (1)°
M_r = 336.60	V = 684.6 (2) Å³
Triclinic, P1	Z = 2
a = 4.935 (1) Å	Mo Kα radiation
b = 11.630 (2) Å	µ = 0.82 mm⁻¹
c = 13.115 (2) Å	T = 293 K
α = 113.52 (2)°	0.32 × 0.20 × 0.10 mm
β = 90.49 (1)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector	2785 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	2236 reflections with I > 2σ(I)
T_min = 0.780, T_max = 0.923	R_int = 0.013
4440 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	1 restraint
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.36 e Å⁻³
2785 reflections	Δρ_min = −0.33 e Å⁻³
175 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.7071 (4)	0.7199 (2)	0.24024 (17)	0.0357 (5)
C2	0.8325 (5)	0.7573 (2)	0.34566 (19)	0.0443 (5)
H2	0.7746	0.7164	0.3913	0.053*
C3	1.0431 (5)	0.8552 (2)	0.3823 (2)	0.0506 (6)
H3	1.1295	0.8807	0.4525	0.061*
C4	1.1242 (5)	0.9149 (2)	0.3139 (2)	0.0466 (6)
C5	0.9996 (5)	0.8800 (2)	0.2095 (2)	0.0507 (6)
H5	1.0565	0.9221	0.1648	0.061*
C6	0.7896 (5)	0.7817 (2)	0.17258 (19)	0.0454 (5)
H6	0.7035	0.7569	0.1024	0.055*
C7	0.7357 (4)	0.39831 (19)	0.18639 (16)	0.0330 (4)
C8	0.6937 (4)	0.4095 (2)	0.29448 (17)	0.0388 (5)
H8	0.5776	0.4644	0.3387	0.047*
C9	0.8290 (5)	0.3369 (2)	0.33442 (18)	0.0416 (5)
C10	1.0005 (5)	0.2536 (2)	0.27211 (19)	0.0463 (6)
H10	1.0892	0.2057	0.3010	0.056*
C11	1.0357 (4)	0.2439 (2)	0.16442 (19)	0.0400 (5)
C12	0.9083 (4)	0.3151 (2)	0.12094 (18)	0.0365 (5)
H12	0.9373	0.3077	0.0487	0.044*
N1	0.5991 (4)	0.46264 (17)	0.13400 (14)	0.0382 (4)
H1N	0.645 (5)	0.452 (2)	0.0694 (15)	0.046*
O1	0.3111 (3)	0.58358 (15)	0.28347 (12)	0.0442 (4)
O2	0.2996 (3)	0.59558 (15)	0.09918 (12)	0.0442 (4)
Cl1	1.39180 (14)	1.03860 (7)	0.36017 (7)	0.0681 (2)
Cl2	0.77531 (16)	0.35067 (7)	0.46970 (5)	0.0603 (2)
Cl3	1.24838 (13)	0.13818 (6)	0.08193 (6)	0.05370 (18)
S1	0.45009 (11)	0.58943 (5)	0.19092 (4)	0.03502 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0393 (11)	0.0375 (11)	0.0312 (10)	0.0088 (9)	0.0033 (9)	0.0137 (9)
C2	0.0567 (14)	0.0441 (13)	0.0365 (12)	0.0058 (11)	−0.0029 (10)	0.0210 (10)
C3	0.0594 (15)	0.0460 (13)	0.0460 (14)	0.0057 (11)	−0.0123 (11)	0.0187 (11)
C4	0.0438 (13)	0.0368 (12)	0.0563 (15)	0.0068 (10)	−0.0006 (11)	0.0154 (11)
C5	0.0588 (15)	0.0504 (14)	0.0501 (14)	0.0054 (12)	0.0082 (12)	0.0279 (12)
C6	0.0553 (14)	0.0514 (14)	0.0321 (11)	0.0054 (11)	0.0030 (10)	0.0197 (10)
C7	0.0362 (11)	0.0341 (11)	0.0301 (10)	−0.0015 (8)	−0.0025 (8)	0.0159 (8)
C8	0.0454 (12)	0.0407 (12)	0.0311 (11)	0.0013 (9)	0.0002 (9)	0.0164 (9)
C9	0.0505 (13)	0.0444 (12)	0.0329 (11)	−0.0039 (10)	−0.0028 (10)	0.0212 (10)
C10	0.0528 (14)	0.0444 (13)	0.0480 (14)	0.0032 (11)	−0.0076 (11)	0.0263 (11)
C11	0.0390 (12)	0.0362 (11)	0.0423 (12)	0.0001 (9)	−0.0002 (9)	0.0145 (10)
C12	0.0388 (11)	0.0382 (11)	0.0327 (11)	−0.0005 (9)	0.0000 (9)	0.0160 (9)
N1	0.0495 (11)	0.0440 (10)	0.0249 (9)	0.0105 (8)	0.0057 (8)	0.0166 (8)
O1	0.0453 (9)	0.0560 (10)	0.0342 (8)	0.0078 (7)	0.0101 (7)	0.0206 (7)
O2	0.0448 (9)	0.0574 (10)	0.0330 (8)	0.0125 (7)	−0.0027 (7)	0.0194 (7)
Cl1	0.0579 (4)	0.0520 (4)	0.0911 (6)	−0.0058 (3)	−0.0129 (4)	0.0292 (4)
Cl2	0.0874 (5)	0.0668 (4)	0.0378 (3)	0.0071 (3)	0.0023 (3)	0.0333 (3)
Cl3	0.0543 (4)	0.0469 (3)	0.0610 (4)	0.0135 (3)	0.0063 (3)	0.0209 (3)
S1	0.0375 (3)	0.0434 (3)	0.0262 (3)	0.0081 (2)	0.0021 (2)	0.0154 (2)

Geometric parameters (Å, º) top

C1—C6	1.385 (3)	C7—N1	1.415 (3)
C1—C2	1.389 (3)	C8—C9	1.381 (3)
C1—S1	1.760 (2)	C8—H8	0.9300
C2—C3	1.376 (3)	C9—C10	1.375 (3)
C2—H2	0.9300	C9—Cl2	1.742 (2)
C3—C4	1.373 (4)	C10—C11	1.385 (3)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.379 (3)	C11—C12	1.377 (3)
C4—Cl1	1.744 (2)	C11—Cl3	1.742 (2)
C5—C6	1.376 (3)	C12—H12	0.9300
C5—H5	0.9300	N1—S1	1.6274 (19)
C6—H6	0.9300	N1—H1N	0.844 (16)
C7—C12	1.391 (3)	O1—S1	1.4207 (16)
C7—C8	1.390 (3)	O2—S1	1.4387 (15)

C6—C1—C2	120.5 (2)	C7—C8—H8	120.9
C6—C1—S1	120.01 (17)	C10—C9—C8	123.1 (2)
C2—C1—S1	119.48 (17)	C10—C9—Cl2	118.69 (17)
C3—C2—C1	119.6 (2)	C8—C9—Cl2	118.17 (19)
C3—C2—H2	120.2	C9—C10—C11	117.1 (2)
C1—C2—H2	120.2	C9—C10—H10	121.4
C2—C3—C4	119.2 (2)	C11—C10—H10	121.4
C2—C3—H3	120.4	C12—C11—C10	122.1 (2)
C4—C3—H3	120.4	C12—C11—Cl3	119.20 (18)
C3—C4—C5	121.8 (2)	C10—C11—Cl3	118.70 (18)
C3—C4—Cl1	119.2 (2)	C11—C12—C7	119.2 (2)
C5—C4—Cl1	119.0 (2)	C11—C12—H12	120.4
C6—C5—C4	119.0 (2)	C7—C12—H12	120.4
C6—C5—H5	120.5	C7—N1—S1	128.77 (14)
C4—C5—H5	120.5	C7—N1—H1N	116.4 (17)
C5—C6—C1	119.8 (2)	S1—N1—H1N	111.1 (17)
C5—C6—H6	120.1	O1—S1—O2	120.01 (10)
C1—C6—H6	120.1	O1—S1—N1	108.60 (10)
C12—C7—C8	120.25 (19)	O2—S1—N1	104.03 (9)
C12—C7—N1	116.01 (18)	O1—S1—C1	108.36 (10)
C8—C7—N1	123.65 (19)	O2—S1—C1	107.64 (10)
C9—C8—C7	118.2 (2)	N1—S1—C1	107.59 (10)
C9—C8—H8	120.9

C6—C1—C2—C3	−1.0 (3)	C9—C10—C11—Cl3	−179.32 (18)
S1—C1—C2—C3	176.71 (18)	C10—C11—C12—C7	−0.9 (3)
C1—C2—C3—C4	0.5 (4)	Cl3—C11—C12—C7	179.18 (16)
C2—C3—C4—C5	0.4 (4)	C8—C7—C12—C11	0.3 (3)
C2—C3—C4—Cl1	−179.78 (18)	N1—C7—C12—C11	−176.30 (19)
C3—C4—C5—C6	−0.6 (4)	C12—C7—N1—S1	−162.46 (16)
Cl1—C4—C5—C6	179.53 (18)	C8—C7—N1—S1	21.1 (3)
C4—C5—C6—C1	0.0 (4)	C7—N1—S1—O1	−39.3 (2)
C2—C1—C6—C5	0.8 (3)	C7—N1—S1—O2	−168.24 (18)
S1—C1—C6—C5	−176.95 (18)	C7—N1—S1—C1	77.8 (2)
C12—C7—C8—C9	0.5 (3)	C6—C1—S1—O1	−151.25 (18)
N1—C7—C8—C9	176.8 (2)	C2—C1—S1—O1	31.0 (2)
C7—C8—C9—C10	−0.6 (3)	C6—C1—S1—O2	−20.1 (2)
C7—C8—C9—Cl2	−179.79 (16)	C2—C1—S1—O2	162.20 (17)
C8—C9—C10—C11	0.0 (4)	C6—C1—S1—N1	91.51 (19)
Cl2—C9—C10—C11	179.18 (17)	C2—C1—S1—N1	−86.23 (19)
C9—C10—C11—C12	0.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.84 (2)	2.08 (2)	2.917 (2)	170 (2)

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₂H₈Cl₃NO₂S
M_r	336.60
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	4.935 (1), 11.630 (2), 13.115 (2)
α, β, γ (°)	113.52 (2), 90.49 (1), 96.50 (1)
V (Å³)	684.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.82
Crystal size (mm)	0.32 × 0.20 × 0.10

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)
T_min, T_max	0.780, 0.923
No. of measured, independent and observed [I > 2σ(I)] reflections	4440, 2785, 2236
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.086, 1.03
No. of reflections	2785
No. of parameters	175
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)	0.36, −0.33

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), 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	0.844 (16)	2.082 (17)	2.917 (2)	170 (2)

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

KS thanks the University Grants Commission, Government of India, New Delhi, for the award of a research fellowship under its faculty improvement programme.

References

Adsmond, D. A. & Grant, D. J. W. (2001). J. Pharm. Sci. 90, 2058–2077. Web of Science CrossRef PubMed CAS Google Scholar
Gowda, B. T. & Kumar, B. H. A. (2003). Oxid. Commun. 26, 403–425. CAS Google Scholar
Gowda, B. T., Svoboda, I. & Fuess, H. (2004). Z. Naturforsch. Teil A, 55, 845–852. Google Scholar
Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England. Google Scholar
Shakuntala, K., Foro, S. & Gowda, B. T. (2011a). Acta Cryst. E67, o232. Web of Science CSD CrossRef IUCr Journals Google Scholar
Shakuntala, K., Foro, S. & Gowda, B. T. (2011b). Acta Cryst. E67, o1017. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar