N-(3,5-Dichloro­phen­yl)benzene­sulfonamide

Gowda, B.T.; Foro, S.; Babitha, K.S.; Fuess, H.

doi:10.1107/S1600536808034351

organic compounds

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Volume 64| Part 11| November 2008| Page o2190

doi:10.1107/S1600536808034351

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N-(3,5-Dichlorophenyl)benzenesulfonamide

B. Thimme Gowda,^a ^* Sabine Foro,^b K. S. Babitha ^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 12 October 2008; accepted 21 October 2008; online 25 October 2008)

In the crystal structure of the title compound, C₁₂H₉Cl₂NO₂S, the aromatic rings are aligned at 57.0 (1)°. The molecules form chains via intermolecular N—H⋯O hydrogen bonds.

Related literature

For the structural systematics of 4,4′-disubstituted aryl benzenesulfonamides, see: Gelbrich et al. (2007 ). For mono- and di-substituted-aryl benzenesulfonamides, see: Gowda et al. (2008a ,b ); Tkachev et al. (2006 ). For the spectroscopic analysis of the title compound, see: Shetty & Gowda (2005 ).

Experimental

Crystal data

C₁₂H₉Cl₂NO₂S
M_r = 302.16
Monoclinic, P 2₁ /c
a = 8.299 (2) Å
b = 7.215 (1) Å
c = 21.954 (3) Å
β = 99.49 (1)°
V = 1296.6 (4) Å³
Z = 4
Cu Kα radiation
μ = 5.96 mm⁻¹
T = 299 (2) K
0.50 × 0.50 × 0.25 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.129, T_max = 0.229
2518 measured reflections
2311 independent reflections
2153 reflections with I > 2σ(I)
R_int = 0.050
3 standard reflections frequency: 120 min intensity decay: 1.0%

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.156
S = 1.10
2311 reflections
167 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.856 (10)	2.059 (11)	2.915 (3)	178 (3)
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808034351/ng2501sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808034351/ng2501Isup2.hkl

checkCIF report

Comment top

As part of a study of the substituent effects on the crystal structures of N-(aryl)-benzenesulfonamides (Gowda et al., 2008a,b), in the present work, the structure of N-(3,5-dichlorophenyl)- benzenesulfonamide (N35DCPBSA) has been determined. The conformations of the N—H and S═O bonds in N35DCPBSA are trans to each other (Fig.1), similar to that observed in N-(3-chlorophenyl)- benzenesulfonamide (N3CPBSA) (Gowda et al., 2008b). The two benzene rings in N35DCPBSA form a dihedral angle of 57.0 (1)°, compared with the value of 65.4 (1)° in N3CPBSA (Gowda et al., 2008b). The other bond parameters in N35DCPBSA are also similar to those observed in N3CPBSA and other N-(aryl)-benzenesulfonamides (Gelbrich et al., 2007; Gowda et al., 2008a,b; Tkachev et al., 2006). The packing diagram of N35DCPBSA showing the N—H···O hydrogen bonds (Table 1) is shown in Fig. 2.

Related literature top

For the structural systematics of 4,4'-disubstituted aryl benzenesulfonamides, see: Gelbrich et al. (2007). For mono- and di-substituted-aryl benzenesulfonamides, see: Gowda et al. (2008a,b); Tkachev et al. (2006). For the spectroscopic analysis of the title compound, see: Shetty & Gowda (2005).

Experimental top

The solution of benzene (10 cc) in chloroform (40 cc) was treated dropwise with chlorosulfonic acid (25 cc) 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 benzenesulfonylchloride was treated with 3,5-dichloroaniline in the stoichiometric ratio and boiled for ten minutes. The reaction mixture was then cooled to room temperature and added to ice cold water (100 cc). The resultant solid 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 purity of the compound was checked and characterized by recording its infrared and NMR spectra (Shetty & Gowda, 2005). The single crystals used in X-ray diffraction studies were grown in ethanolic solution by evaporating it 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, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, showing the atom labeling scheme. The displacement ellipsoids are drawn at the 50% probability level. The H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines.

N-(3,5-Dichlorophenyl)benzenesulfonamide top

Crystal data top

C₁₂H₉Cl₂NO₂S	F(000) = 616
M_r = 302.16	D_x = 1.548 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.299 (2) Å	θ = 5.4–19.4°
b = 7.215 (1) Å	µ = 5.96 mm⁻¹
c = 21.954 (3) Å	T = 299 K
β = 99.49 (1)°	Prism, colourless
V = 1296.6 (4) Å³	0.50 × 0.50 × 0.25 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	2153 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.050
Graphite monochromator	θ_max = 67.0°, θ_min = 4.1°
ω/2θ scans	h = −9→1
Absorption correction: ψ scan (North et al., 1968)	k = 0→8
T_min = 0.129, T_max = 0.229	l = −26→26
2518 measured reflections	3 standard reflections every 120 min
2311 independent reflections	intensity decay: 1.0%

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)] = 0.057	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.156	w = 1/[σ²(F_o²) + (0.0987P)² + 0.7373P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
2311 reflections	Δρ_max = 0.59 e Å⁻³
167 parameters	Δρ_min = −0.38 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0105 (11)

Crystal data top

C₁₂H₉Cl₂NO₂S	V = 1296.6 (4) Å³
M_r = 302.16	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 8.299 (2) Å	µ = 5.96 mm⁻¹
b = 7.215 (1) Å	T = 299 K
c = 21.954 (3) Å	0.50 × 0.50 × 0.25 mm
β = 99.49 (1)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2153 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.050
T_min = 0.129, T_max = 0.229	3 standard reflections every 120 min
2518 measured reflections	intensity decay: 1.0%
2311 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	1 restraint
wR(F²) = 0.156	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.59 e Å⁻³
2311 reflections	Δρ_min = −0.38 e Å⁻³
167 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	0.3043 (3)	0.1779 (4)	0.79280 (13)	0.0445 (6)
C2	0.4358 (4)	0.1697 (5)	0.84058 (17)	0.0604 (8)
H2	0.4201	0.1476	0.8809	0.072*
C3	0.5911 (4)	0.1953 (6)	0.8269 (2)	0.0783 (12)
H3	0.6811	0.1914	0.8584	0.094*
C4	0.6130 (4)	0.2267 (6)	0.7670 (2)	0.0773 (11)
H4	0.7180	0.2427	0.7582	0.093*
C5	0.4818 (5)	0.2344 (5)	0.7202 (2)	0.0746 (10)
H5	0.4980	0.2547	0.6798	0.090*
C6	0.3257 (4)	0.2121 (4)	0.73293 (15)	0.0562 (7)
H6	0.2360	0.2200	0.7015	0.067*
C7	0.1252 (3)	0.3838 (4)	0.90059 (11)	0.0400 (6)
C8	0.2051 (4)	0.5522 (4)	0.90920 (13)	0.0484 (6)
H8	0.2132	0.6288	0.8758	0.058*
C9	0.2725 (4)	0.6041 (4)	0.96827 (15)	0.0558 (7)
C10	0.2645 (4)	0.4935 (4)	1.01861 (14)	0.0590 (8)
H10	0.3122	0.5293	1.0582	0.071*
C11	0.1830 (4)	0.3278 (4)	1.00819 (13)	0.0534 (7)
C12	0.1118 (3)	0.2699 (4)	0.95062 (12)	0.0480 (6)
H12	0.0561	0.1577	0.9451	0.058*
N1	0.0494 (3)	0.3297 (3)	0.84009 (10)	0.0441 (5)
H1N	0.038 (4)	0.418 (3)	0.8138 (12)	0.053*
O1	−0.0021 (3)	0.1298 (3)	0.74998 (9)	0.0527 (5)
O2	0.1112 (3)	−0.0066 (3)	0.85135 (10)	0.0574 (6)
Cl1	0.37237 (16)	0.81541 (13)	0.97944 (5)	0.0927 (4)
Cl2	0.16462 (15)	0.18752 (15)	1.07089 (4)	0.0834 (4)
S1	0.10584 (7)	0.14095 (9)	0.80800 (3)	0.0412 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0475 (14)	0.0400 (13)	0.0467 (15)	0.0019 (11)	0.0101 (11)	0.0007 (11)
C2	0.0571 (17)	0.0615 (19)	0.0589 (19)	0.0079 (14)	−0.0009 (14)	−0.0049 (15)
C3	0.0517 (18)	0.065 (2)	0.111 (3)	0.0057 (15)	−0.0071 (19)	−0.014 (2)
C4	0.0560 (19)	0.063 (2)	0.117 (4)	0.0031 (16)	0.029 (2)	0.001 (2)
C5	0.079 (2)	0.064 (2)	0.091 (3)	−0.0014 (18)	0.044 (2)	0.0114 (19)
C6	0.0619 (17)	0.0556 (17)	0.0535 (17)	0.0004 (14)	0.0161 (13)	0.0070 (13)
C7	0.0447 (13)	0.0413 (13)	0.0349 (12)	0.0025 (10)	0.0088 (10)	−0.0039 (10)
C8	0.0581 (15)	0.0404 (14)	0.0465 (14)	0.0000 (12)	0.0079 (12)	0.0033 (12)
C9	0.0631 (17)	0.0424 (15)	0.0585 (17)	−0.0015 (13)	0.0001 (13)	−0.0043 (13)
C10	0.078 (2)	0.0531 (17)	0.0426 (15)	0.0025 (15)	0.0004 (14)	−0.0087 (13)
C11	0.0701 (18)	0.0540 (16)	0.0379 (14)	0.0049 (14)	0.0141 (13)	0.0020 (12)
C12	0.0593 (16)	0.0466 (15)	0.0405 (14)	−0.0057 (12)	0.0157 (12)	−0.0028 (11)
N1	0.0547 (13)	0.0423 (12)	0.0350 (12)	0.0020 (10)	0.0064 (9)	−0.0004 (9)
O1	0.0548 (11)	0.0586 (12)	0.0427 (11)	−0.0059 (9)	0.0021 (8)	−0.0107 (9)
O2	0.0838 (15)	0.0415 (11)	0.0499 (11)	−0.0053 (10)	0.0199 (10)	0.0058 (8)
Cl1	0.1209 (9)	0.0518 (5)	0.0915 (8)	−0.0250 (5)	−0.0236 (6)	−0.0022 (4)
Cl2	0.1333 (9)	0.0798 (7)	0.0393 (5)	−0.0122 (6)	0.0204 (5)	0.0085 (4)
S1	0.0495 (4)	0.0384 (4)	0.0359 (4)	−0.0042 (2)	0.0076 (3)	−0.0018 (2)

Geometric parameters (Å, º) top

C1—C6	1.377 (4)	C7—N1	1.427 (3)
C1—C2	1.385 (4)	C8—C9	1.377 (4)
C1—S1	1.754 (3)	C8—H8	0.9300
C2—C3	1.383 (5)	C9—C10	1.374 (5)
C2—H2	0.9300	C9—Cl1	1.734 (3)
C3—C4	1.376 (6)	C10—C11	1.374 (5)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.370 (6)	C11—C12	1.369 (4)
C4—H4	0.9300	C11—Cl2	1.736 (3)
C5—C6	1.379 (5)	C12—H12	0.9300
C5—H5	0.9300	N1—S1	1.637 (2)
C6—H6	0.9300	N1—H1N	0.856 (10)
C7—C8	1.382 (4)	O1—S1	1.433 (2)
C7—C12	1.391 (4)	O2—S1	1.424 (2)

C6—C1—C2	121.4 (3)	C7—C8—H8	120.7
C6—C1—S1	118.8 (2)	C10—C9—C8	122.3 (3)
C2—C1—S1	119.8 (2)	C10—C9—Cl1	118.9 (2)
C3—C2—C1	118.5 (4)	C8—C9—Cl1	118.9 (2)
C3—C2—H2	120.8	C11—C10—C9	117.3 (3)
C1—C2—H2	120.8	C11—C10—H10	121.3
C4—C3—C2	120.3 (4)	C9—C10—H10	121.3
C4—C3—H3	119.9	C12—C11—C10	123.0 (3)
C2—C3—H3	119.9	C12—C11—Cl2	118.2 (2)
C5—C4—C3	120.6 (3)	C10—C11—Cl2	118.7 (2)
C5—C4—H4	119.7	C11—C12—C7	118.0 (3)
C3—C4—H4	119.7	C11—C12—H12	121.0
C4—C5—C6	120.0 (4)	C7—C12—H12	121.0
C4—C5—H5	120.0	C7—N1—S1	120.98 (18)
C6—C5—H5	120.0	C7—N1—H1N	114 (2)
C1—C6—C5	119.2 (3)	S1—N1—H1N	110 (2)
C1—C6—H6	120.4	O2—S1—O1	119.87 (14)
C5—C6—H6	120.4	O2—S1—N1	108.29 (12)
C8—C7—C12	120.7 (2)	O1—S1—N1	104.34 (12)
C8—C7—N1	119.7 (2)	O2—S1—C1	108.30 (14)
C12—C7—N1	119.5 (2)	O1—S1—C1	107.97 (13)
C9—C8—C7	118.6 (3)	N1—S1—C1	107.45 (13)
C9—C8—H8	120.7

C6—C1—C2—C3	−0.5 (5)	C10—C11—C12—C7	1.0 (5)
S1—C1—C2—C3	178.6 (3)	Cl2—C11—C12—C7	179.2 (2)
C1—C2—C3—C4	−0.5 (5)	C8—C7—C12—C11	−1.4 (4)
C2—C3—C4—C5	0.5 (6)	N1—C7—C12—C11	−178.6 (3)
C3—C4—C5—C6	0.5 (6)	C8—C7—N1—S1	119.8 (2)
C2—C1—C6—C5	1.5 (5)	C12—C7—N1—S1	−62.9 (3)
S1—C1—C6—C5	−177.6 (3)	C7—N1—S1—O2	48.5 (2)
C4—C5—C6—C1	−1.5 (5)	C7—N1—S1—O1	177.3 (2)
C12—C7—C8—C9	0.6 (4)	C7—N1—S1—C1	−68.3 (2)
N1—C7—C8—C9	177.8 (3)	C6—C1—S1—O2	138.8 (2)
C7—C8—C9—C10	0.7 (5)	C2—C1—S1—O2	−40.3 (3)
C7—C8—C9—Cl1	−179.8 (2)	C6—C1—S1—O1	7.6 (3)
C8—C9—C10—C11	−1.2 (5)	C2—C1—S1—O1	−171.5 (2)
Cl1—C9—C10—C11	179.4 (3)	C6—C1—S1—N1	−104.5 (2)
C9—C10—C11—C12	0.3 (5)	C2—C1—S1—N1	76.5 (3)
C9—C10—C11—Cl2	−178.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.86 (1)	2.06 (1)	2.915 (3)	178 (3)

Symmetry code: (i) −x, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₉Cl₂NO₂S
M_r	302.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	299
a, b, c (Å)	8.299 (2), 7.215 (1), 21.954 (3)
β (°)	99.49 (1)
V (Å³)	1296.6 (4)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	5.96
Crystal size (mm)	0.50 × 0.50 × 0.25

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.129, 0.229
No. of measured, independent and observed [I > 2σ(I)] reflections	2518, 2311, 2153
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.156, 1.10
No. of reflections	2311
No. of parameters	167
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)	0.59, −0.38

Computer programs: CAD-4-PC (Enraf–Nonius, 1996), REDU4 (Stoe & Cie, 1987), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.856 (10)	2.059 (11)	2.915 (3)	178 (3)

Symmetry code: (i) −x, y+1/2, −z+3/2.

Acknowledgements

BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany, for extensions of his research fellowship.

References

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