N,N′-(Ethane-1,2-di­yl)bis­(4-chloro­benzene­sulfonamide)

Al-Dajani, M.T.M.; Wahab, H.A.; Shamsuddin, S.; Hemamalini, M.; Fun, H.-K.

doi:10.1107/S1600536811028443

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2241

doi:10.1107/S1600536811028443

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N,N′-(Ethane-1,2-diyl)bis(4-chlorobenzenesulfonamide)

Mohammad T. M. Al-Dajani,^a Habibah A. Wahab,^a Shaharum Shamsuddin,^a Madhukar Hemamalini ^b and Hoong-Kun Fun ^b ^*‡

^aSchool of Pharmaceutical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 12 July 2011; accepted 15 July 2011; online 2 August 2011)

The title molecule, C₁₄H₁₄Cl₂N₂O₄S₂, lies on an inversion center. The molecule is twisted in the region of the sulfonamide group with a C—S—N—C torsion angle of −67.49 (16)°. In the crystal, molecules are connected via intermolecular N—H⋯O and weak C—H⋯O hydrogen bonds, forming layers parallel to (100).

Related literature

For details of the chemistry of sulfonamides, see: Gowda et al. (2003 , 2007 ). For related structures, see: O'Connor & Maslen (1965 ); Kumar et al. (1992 ); Shakuntala et al. (2011 ).

Experimental

Crystal data

C₁₄H₁₄Cl₂N₂O₄S₂
M_r = 409.29
Monoclinic, P 2₁ /c
a = 13.2640 (5) Å
b = 5.3390 (2) Å
c = 13.1792 (5) Å
β = 110.270 (1)°
V = 875.51 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.63 mm⁻¹
T = 296 K
0.86 × 0.42 × 0.13 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.613, T_max = 0.925
25142 measured reflections
3689 independent reflections
2869 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.175
S = 1.03
3689 reflections
114 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2ⁱ	0.79 (3)	2.13 (3)	2.903 (2)	167 (3)
C4—H4A⋯O1ⁱⁱ	0.93	2.50	3.157 (2)	127
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811028443/lh5285sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028443/lh5285Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811028443/lh5285Isup3.cml

checkCIF report

Comment top

The chemistry of sulfonamides is of interest as they show distinct physical, chemical and biological properties. Many arylsulfonamides and their N-halo compounds exhibit pharmacological, fungicidal and herbicidal activities due to their oxidizing action in aqueous, partial aqueous and non-aqueous media. 2-chlorobenzenesulfonamide has been used to explore the substituent effects on the solid state structures of sulfonamides and N-haloarylsulfonamides (Gowda et al., 2003, 2007). The crystal structures of 4-aminobenzenesulfonamide (O'Connor & Maslen, 1965) and 4-methylbenzenesulfonamide (Kumar et al., 1992) have been reported in the literature. In this paper, we present the X-ray single-crystal structure of N,N'-(ethane-1,2-diyl)bis(4-chlorobenzenesulfonamide) (I).

The asymmetric unit of the title compound, (I), consists of a half molecule of N,N'-(ethane-1,2-diyl)bis(4-chlorobenzenesulfonamide). The other half is generated by a crystallographic inversion center, as shown in Fig. 1. The molecule is twisted at the S atom with an C-S-N-C torsion angle of -67.49 (16)°. This value agrees with that previously reported for the crystal structure of 4-Chloro-N-(2,6-dimethylphenyl)benzene sulfonamide (Shakuntala et al., 2011). In the crystal, molecules are connected via N1—H1N1···O2ⁱⁱ and C4—H4A···O1ⁱⁱⁱ (Table 1) hydrogen bonds (Fig. 2) forming layers parallel to (100).

Related literature top

For details of the chemistry of sulfonamides, see: Gowda et al. (2003, 2007). For related structures, see: O'Connor & Maslen (1965); Kumar et al. (1992); Shakuntala et al. (2011).

Experimental top

In a round bottom flask, 25ml of toluene was mixed with 4-chlorobenzenesulfonyl chloride (0.02 mol, 3.5 g) with stirring. Drops of ethylenediamine (0.01mol, 0.5 g ) were added and the mixture was refluxed for 30 min. The yellow gum formed was dissolved in hot water and sodium bicarbonate was added. The yellow precipitate formed was dissolved in methanol at 333K, yielding colourless crystals.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids (symmetry code: (A) -x+1, -y+2, -z).
	Fig. 2. The crystal packing of (I) with dashed lines representing hydrogen bonds.

4-chloro-N-[2-(4-chlorobenzenesulfonamido)ethyl]benzenesulfonamide top

Crystal data top

C₁₄H₁₄Cl₂N₂O₄S₂	F(000) = 420
M_r = 409.29	D_x = 1.553 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9471 reflections
a = 13.2640 (5) Å	θ = 3.3–33.5°
b = 5.3390 (2) Å	µ = 0.63 mm⁻¹
c = 13.1792 (5) Å	T = 296 K
β = 110.270 (1)°	Plate, colourless
V = 875.51 (6) Å³	0.86 × 0.42 × 0.13 mm
Z = 2

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	3689 independent reflections
Radiation source: fine-focus sealed tube	2869 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ϕ and ω scans	θ_max = 34.5°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −21→21
T_min = 0.613, T_max = 0.925	k = −8→8
25142 measured reflections	l = −19→20

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)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.175	w = 1/[σ²(F_o²) + (0.0979P)² + 0.221P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3689 reflections	Δρ_max = 0.84 e Å⁻³
114 parameters	Δρ_min = −0.71 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.037 (6)

Crystal data top

C₁₄H₁₄Cl₂N₂O₄S₂	V = 875.51 (6) Å³
M_r = 409.29	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.2640 (5) Å	µ = 0.63 mm⁻¹
b = 5.3390 (2) Å	T = 296 K
c = 13.1792 (5) Å	0.86 × 0.42 × 0.13 mm
β = 110.270 (1)°

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	3689 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2869 reflections with I > 2σ(I)
T_min = 0.613, T_max = 0.925	R_int = 0.032
25142 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.175	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.84 e Å⁻³
3689 reflections	Δρ_min = −0.71 e Å⁻³
114 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Cl1	0.05348 (6)	1.46054 (14)	0.19657 (6)	0.0881 (2)
S1	0.35715 (3)	0.67863 (7)	0.09928 (3)	0.04701 (14)
O1	0.30882 (14)	0.5925 (3)	−0.00946 (11)	0.0722 (4)
O2	0.39055 (12)	0.5017 (2)	0.18611 (12)	0.0615 (3)
N1	0.46306 (13)	0.8326 (3)	0.10557 (14)	0.0537 (3)
C1	0.18737 (14)	1.0017 (4)	0.04025 (13)	0.0572 (4)
H1A	0.1784	0.9592	−0.0308	0.069*
C2	0.12110 (16)	1.1788 (4)	0.06200 (16)	0.0648 (5)
H2A	0.0680	1.2581	0.0056	0.078*
C3	0.13465 (14)	1.2362 (4)	0.16811 (17)	0.0564 (4)
C4	0.21201 (17)	1.1220 (4)	0.25315 (15)	0.0602 (4)
H4A	0.2191	1.1612	0.3240	0.072*
C5	0.27916 (15)	0.9482 (4)	0.23194 (12)	0.0543 (4)
H5A	0.3325	0.8707	0.2888	0.065*
C6	0.26714 (11)	0.8888 (3)	0.12547 (11)	0.0428 (3)
C7	0.45903 (17)	1.0240 (4)	0.02466 (18)	0.0635 (5)
H7A	0.4710	1.1877	0.0587	0.076*
H7B	0.3884	1.0241	−0.0311	0.076*
H1N1	0.496 (2)	0.868 (6)	0.166 (2)	0.076 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0889 (4)	0.0823 (4)	0.1081 (5)	0.0331 (3)	0.0532 (4)	0.0217 (3)
S1	0.0555 (2)	0.0437 (2)	0.03914 (19)	−0.00060 (14)	0.01292 (15)	−0.00090 (12)
O1	0.0873 (10)	0.0712 (9)	0.0468 (6)	0.0035 (8)	0.0090 (6)	−0.0168 (6)
O2	0.0717 (8)	0.0495 (7)	0.0620 (7)	0.0049 (6)	0.0214 (6)	0.0146 (5)
N1	0.0538 (7)	0.0590 (8)	0.0516 (7)	0.0028 (6)	0.0226 (6)	0.0065 (6)
C1	0.0508 (8)	0.0756 (12)	0.0390 (7)	0.0038 (7)	0.0079 (6)	0.0079 (7)
C2	0.0524 (9)	0.0799 (13)	0.0563 (9)	0.0152 (8)	0.0113 (7)	0.0193 (9)
C3	0.0522 (8)	0.0566 (9)	0.0653 (10)	0.0068 (7)	0.0265 (7)	0.0122 (8)
C4	0.0711 (11)	0.0637 (10)	0.0484 (8)	0.0112 (9)	0.0241 (8)	0.0060 (7)
C5	0.0620 (9)	0.0605 (9)	0.0374 (6)	0.0110 (7)	0.0135 (6)	0.0078 (6)
C6	0.0431 (6)	0.0460 (7)	0.0366 (5)	−0.0031 (5)	0.0104 (5)	0.0047 (5)
C7	0.0724 (11)	0.0577 (10)	0.0775 (12)	0.0207 (8)	0.0477 (10)	0.0202 (9)

Geometric parameters (Å, º) top

Cl1—C3	1.7359 (19)	C2—C3	1.381 (3)
S1—O1	1.4282 (14)	C2—H2A	0.9300
S1—O2	1.4308 (13)	C3—C4	1.373 (3)
S1—N1	1.6048 (16)	C4—C5	1.380 (3)
S1—C6	1.7574 (16)	C4—H4A	0.9300
N1—C7	1.465 (2)	C5—C6	1.393 (2)
N1—H1N1	0.78 (3)	C5—H5A	0.9300
C1—C6	1.386 (2)	C7—C7ⁱ	1.469 (3)
C1—C2	1.387 (3)	C7—H7A	0.9700
C1—H1A	0.9300	C7—H7B	0.9700

O1—S1—O2	119.79 (10)	C2—C3—Cl1	119.94 (14)
O1—S1—N1	107.30 (10)	C3—C4—C5	119.05 (17)
O2—S1—N1	105.90 (9)	C3—C4—H4A	120.5
O1—S1—C6	107.66 (8)	C5—C4—H4A	120.5
O2—S1—C6	107.92 (8)	C4—C5—C6	120.03 (15)
N1—S1—C6	107.76 (8)	C4—C5—H5A	120.0
C7—N1—S1	120.62 (14)	C6—C5—H5A	120.0
C7—N1—H1N1	116 (2)	C1—C6—C5	120.40 (16)
S1—N1—H1N1	110 (2)	C1—C6—S1	119.90 (12)
C6—C1—C2	119.32 (16)	C5—C6—S1	119.66 (11)
C6—C1—H1A	120.3	N1—C7—C7ⁱ	110.75 (19)
C2—C1—H1A	120.3	N1—C7—H7A	109.5
C3—C2—C1	119.42 (16)	C7ⁱ—C7—H7A	109.5
C3—C2—H2A	120.3	N1—C7—H7B	109.5
C1—C2—H2A	120.3	C7ⁱ—C7—H7B	109.5
C4—C3—C2	121.75 (18)	H7A—C7—H7B	108.1
C4—C3—Cl1	118.31 (16)

O1—S1—N1—C7	48.19 (17)	C2—C1—C6—S1	−176.04 (15)
O2—S1—N1—C7	177.22 (15)	C4—C5—C6—C1	−0.5 (3)
C6—S1—N1—C7	−67.49 (16)	C4—C5—C6—S1	176.93 (15)
C6—C1—C2—C3	−1.0 (3)	O1—S1—C6—C1	−20.18 (17)
C1—C2—C3—C4	−0.2 (3)	O2—S1—C6—C1	−150.79 (14)
C1—C2—C3—Cl1	179.13 (16)	N1—S1—C6—C1	95.26 (15)
C2—C3—C4—C5	1.1 (3)	O1—S1—C6—C5	162.35 (16)
Cl1—C3—C4—C5	−178.26 (16)	O2—S1—C6—C5	31.74 (16)
C3—C4—C5—C6	−0.7 (3)	N1—S1—C6—C5	−82.21 (15)
C2—C1—C6—C5	1.4 (3)	S1—N1—C7—C7ⁱ	−126.2 (2)

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2ⁱⁱ	0.79 (3)	2.13 (3)	2.903 (2)	167 (3)
C4—H4A···O1ⁱⁱⁱ	0.93	2.50	3.157 (2)	127

Symmetry codes: (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄Cl₂N₂O₄S₂
M_r	409.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	13.2640 (5), 5.3390 (2), 13.1792 (5)
β (°)	110.270 (1)
V (Å³)	875.51 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.63
Crystal size (mm)	0.86 × 0.42 × 0.13

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.613, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	25142, 3689, 2869
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.796

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.175, 1.03
No. of reflections	3689
No. of parameters	114
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.84, −0.71

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2ⁱ	0.79 (3)	2.13 (3)	2.903 (2)	167 (3)
C4—H4A···O1ⁱⁱ	0.93	2.50	3.157 (2)	127

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+3/2, z+1/2.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

SS and HAW gratefully acknowledge funding from the Ministry of Science, Technology and Innovation and Universiti Sains Malaysia (USM) under the University Research Grant (Nos. 09-05-lfn-meb-004 and 304/PPSK/6150107/I 121, respectively). HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

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