N,N′-[1,3-Phenylenebis(methyl­ene)]dibenzene­sulfonamide

Ejaz; Khan, I.U.; Ahmad, H.; Harrison, W.T.A.

doi:10.1107/S1600536811040694

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3037

doi:10.1107/S1600536811040694

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N,N′-[1,3-Phenylenebis(methylene)]dibenzenesulfonamide

Ejaz,^a Islam Ullah Khan,^a ^* Hira Ahmad ^a and William T. A. Harrison ^b

^aMaterials Chemistry Laboratry, Department of Chemistry, GC University, Lahore 54000, Pakistan, and ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: iuklodhi@yahoo.com

(Received 28 September 2011; accepted 3 October 2011; online 29 October 2011)

The complete molecule of the title compound, C₂₀H₂₀N₂O₄S₂, is generated by crystallographic twofold symmetry, with two C atoms lying on the rotation axis. The dihedral angle between the central benzene ring and the pendant ring is 68.42 (6)° and the dihedral angle between the pendant rings is 45.11 (5)°. The torsion angles for the C—S—N—C and S—N—C—C fragments are −73.22 (15) and −150.45 (13)°, respectively. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, generating corrugated (001) sheets. Aromatic π–π stacking [centroid–centroid separation = 3.8925 (12) and 3.9777 (12) Å] and weak C—H⋯O interactions also occur.

Related literature

For a related structure, see: Khan et al. (2011 ).

Experimental

Crystal data

C₂₀H₂₀N₂O₄S₂
M_r = 416.50
Monoclinic, C 2/c
a = 16.4319 (6) Å
b = 7.8024 (3) Å
c = 16.1217 (6) Å
β = 111.543 (2)°
V = 1922.54 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 296 K
0.15 × 0.11 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
8653 measured reflections
2346 independent reflections
1841 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.103
S = 1.07
2346 reflections
131 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.81 (2)	2.16 (2)	2.960 (2)	166 (2)
C5—H5⋯O1ⁱⁱ	0.93	2.55	3.461 (2)	166
C10—H10⋯O1ⁱⁱⁱ	0.93	2.57	3.379 (3)	146
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) x, y-1, 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 I, global. DOI: 10.1107/S1600536811040694/su2323sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811040694/su2323Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811040694/su2323Isup3.cml

checkCIF report

Comment top

As part of our ongoing structural studies of sulfonamides (Khan et al., 2011), the synthesis and structure of the title compound are described herein.

The complete molecule of the title compound is generated by crystallographic twofold symmetry (Fig. 1), with atoms C9 and C11 lying on the rotation axis. The diehdral angle between the central benzene ring and the pendant ring is 68.42 (6)°. The dihedral angle between the two pendant rings is 45.11 (5)°. The conformation of the C4—S1—N1—C7 fragment is approximately gauche [-73.22 (15)°] whereas the torsion angle for S1—N1—C8—C9 of -150.45 (13)° indicates a conformation between gauche and anti. The bond-angle sum for N1 of 350.6° seems to indicate a valence state close to sp² hybridization.

In the crystal, the molecules are linked by N—H···O hydrogen bonds (Table 1), to generate corrugated (010) sheets (Fig. 2). Weak aromatic π-π stacking [centroid-centroid separation = 3.8925 (12) and 3.9777 (12) Å] occurs between the layers and weak C—H···O interactions may help to consolidate the packing.

Related literature top

For a related structure, see: Khan et al. (2011).

Experimental top

The m-xylylenediamine (0.132 ml, 1.0 mmol) was mixed with 20 ml distilled water in a 50 ml round bottom flask. Benzene sulfonyl chloride (0.255 ml, 2.0 mmol) was added while maintaining the pH of the reaction mixture at ca. 9.0 using sodium carbonate solution (3%) and the mixture was stirred for five hours. The white precipitated product was filtered, washed, dried and crystallized from methanol to generate colourless blocks of the title compound.

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 the title molecule, showing the numbering cheme and 50% displacement ellipsoids [Symmetry code: (i) 1–x, y, 1/2 - z].

N,N'-[1,3-Phenylenebis(methylene)]dibenzenesulfonamide top

Crystal data top

C₂₀H₂₀N₂O₄S₂	F(000) = 872
M_r = 416.50	D_x = 1.439 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2346 reflections
a = 16.4319 (6) Å	θ = 2.9–28.3°
b = 7.8024 (3) Å	µ = 0.31 mm⁻¹
c = 16.1217 (6) Å	T = 296 K
β = 111.543 (2)°	Block, colourless
V = 1922.54 (12) Å³	0.15 × 0.11 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1841 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 28.3°, θ_min = 2.9°
ω scans	h = −21→21
8653 measured reflections	k = −9→10
2346 independent reflections	l = −21→21

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0466P)² + 1.1784P] where P = (F_o² + 2F_c²)/3
2346 reflections	(Δ/σ)_max = 0.001
131 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₂₀H₂₀N₂O₄S₂	V = 1922.54 (12) Å³
M_r = 416.50	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.4319 (6) Å	µ = 0.31 mm⁻¹
b = 7.8024 (3) Å	T = 296 K
c = 16.1217 (6) Å	0.15 × 0.11 × 0.08 mm
β = 111.543 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1841 reflections with I > 2σ(I)
8653 measured reflections	R_int = 0.024
2346 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.29 e Å⁻³
2346 reflections	Δρ_min = −0.34 e Å⁻³
131 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	0.23478 (13)	0.4749 (3)	0.57485 (13)	0.0492 (5)
H1A	0.2133	0.4616	0.6204	0.059*
C2	0.18163 (12)	0.5397 (3)	0.49388 (14)	0.0493 (5)
H2	0.1239	0.5677	0.4846	0.059*
C3	0.21285 (11)	0.5637 (3)	0.42623 (12)	0.0405 (4)
H3	0.1766	0.6069	0.3713	0.049*
C4	0.29908 (10)	0.5225 (2)	0.44139 (10)	0.0313 (4)
C5	0.35276 (12)	0.4531 (2)	0.52240 (11)	0.0396 (4)
H5	0.4102	0.4230	0.5318	0.048*
C6	0.31953 (13)	0.4296 (3)	0.58870 (12)	0.0481 (5)
H6	0.3548	0.3828	0.6431	0.058*
C7	0.43547 (11)	0.2757 (2)	0.36899 (11)	0.0378 (4)
H7A	0.4162	0.1957	0.4041	0.045*
H7B	0.4827	0.3439	0.4096	0.045*
C8	0.46828 (10)	0.1780 (2)	0.30692 (11)	0.0332 (4)
C9	0.5000	0.2653 (3)	0.2500	0.0320 (5)
H9	0.5000	0.3845	0.2500	0.038*
C10	0.46821 (12)	0.0009 (3)	0.30605 (13)	0.0429 (4)
H10	0.4467	−0.0593	0.3434	0.052*
C11	0.5000	−0.0871 (4)	0.2500	0.0504 (7)
H11	0.5000	−0.2063	0.2500	0.061*
S1	0.34361 (3)	0.56500 (6)	0.35953 (3)	0.03403 (15)
N1	0.36255 (9)	0.3882 (2)	0.31843 (10)	0.0382 (4)
H1	0.3187 (13)	0.339 (3)	0.2865 (14)	0.046*
O1	0.42667 (8)	0.64544 (18)	0.40359 (9)	0.0459 (3)
O2	0.27803 (9)	0.65172 (19)	0.28749 (8)	0.0502 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0510 (11)	0.0624 (14)	0.0390 (10)	−0.0120 (10)	0.0223 (9)	−0.0015 (9)
C2	0.0371 (10)	0.0647 (14)	0.0507 (11)	−0.0021 (9)	0.0213 (9)	−0.0029 (10)
C3	0.0355 (9)	0.0490 (12)	0.0342 (9)	0.0017 (8)	0.0097 (7)	0.0017 (8)
C4	0.0330 (8)	0.0318 (9)	0.0282 (7)	−0.0021 (6)	0.0101 (6)	−0.0021 (6)
C5	0.0362 (9)	0.0459 (11)	0.0343 (8)	0.0004 (7)	0.0101 (7)	0.0019 (7)
C6	0.0526 (11)	0.0575 (13)	0.0307 (9)	−0.0038 (9)	0.0110 (8)	0.0074 (8)
C7	0.0364 (9)	0.0416 (11)	0.0367 (9)	0.0013 (7)	0.0151 (7)	0.0044 (8)
C8	0.0264 (7)	0.0335 (10)	0.0379 (8)	−0.0002 (6)	0.0098 (7)	0.0026 (7)
C9	0.0316 (11)	0.0233 (12)	0.0409 (12)	0.000	0.0131 (10)	0.000
C10	0.0406 (9)	0.0337 (10)	0.0530 (11)	−0.0052 (8)	0.0155 (9)	0.0091 (9)
C11	0.0536 (16)	0.0234 (14)	0.0696 (19)	0.000	0.0171 (15)	0.000
S1	0.0348 (2)	0.0367 (3)	0.0307 (2)	0.00170 (17)	0.01223 (17)	0.00359 (17)
N1	0.0313 (7)	0.0452 (10)	0.0358 (8)	0.0011 (6)	0.0095 (6)	−0.0079 (7)
O1	0.0439 (7)	0.0438 (8)	0.0516 (7)	−0.0117 (6)	0.0195 (6)	0.0002 (6)
O2	0.0544 (8)	0.0605 (10)	0.0357 (7)	0.0195 (7)	0.0165 (6)	0.0149 (6)

Geometric parameters (Å, º) top

C1—C2	1.373 (3)	C7—H7A	0.9700
C1—C6	1.373 (3)	C7—H7B	0.9700
C1—H1A	0.9300	C8—C10	1.382 (3)
C2—C3	1.378 (3)	C8—C9	1.389 (2)
C2—H2	0.9300	C9—C8ⁱ	1.389 (2)
C3—C4	1.385 (2)	C9—H9	0.9300
C3—H3	0.9300	C10—C11	1.381 (2)
C4—C5	1.390 (2)	C10—H10	0.9300
C4—S1	1.7596 (17)	C11—C10ⁱ	1.381 (2)
C5—C6	1.379 (3)	C11—H11	0.9300
C5—H5	0.9300	S1—O2	1.4314 (12)
C6—H6	0.9300	S1—O1	1.4315 (13)
C7—N1	1.467 (2)	S1—N1	1.6092 (16)
C7—C8	1.506 (2)	N1—H1	0.81 (2)

C2—C1—C6	120.16 (18)	H7A—C7—H7B	108.1
C2—C1—H1A	119.9	C10—C8—C9	118.86 (17)
C6—C1—H1A	119.9	C10—C8—C7	120.91 (16)
C1—C2—C3	120.73 (18)	C9—C8—C7	120.22 (17)
C1—C2—H2	119.6	C8ⁱ—C9—C8	121.3 (2)
C3—C2—H2	119.6	C8ⁱ—C9—H9	119.4
C2—C3—C4	118.88 (16)	C8—C9—H9	119.4
C2—C3—H3	120.6	C11—C10—C8	120.31 (19)
C4—C3—H3	120.6	C11—C10—H10	119.8
C3—C4—C5	120.78 (16)	C8—C10—H10	119.8
C3—C4—S1	120.29 (13)	C10—C11—C10ⁱ	120.4 (3)
C5—C4—S1	118.89 (13)	C10—C11—H11	119.8
C6—C5—C4	119.00 (17)	C10ⁱ—C11—H11	119.8
C6—C5—H5	120.5	O2—S1—O1	119.47 (9)
C4—C5—H5	120.5	O2—S1—N1	105.84 (8)
C1—C6—C5	120.41 (17)	O1—S1—N1	106.67 (8)
C1—C6—H6	119.8	O2—S1—C4	107.53 (8)
C5—C6—H6	119.8	O1—S1—C4	107.08 (8)
N1—C7—C8	110.62 (13)	N1—S1—C4	110.10 (8)
N1—C7—H7A	109.5	C7—N1—S1	121.73 (12)
C8—C7—H7A	109.5	C7—N1—H1	114.8 (15)
N1—C7—H7B	109.5	S1—N1—H1	114.1 (15)
C8—C7—H7B	109.5

C6—C1—C2—C3	−1.4 (3)	C7—C8—C10—C11	−178.78 (13)
C1—C2—C3—C4	−0.4 (3)	C8—C10—C11—C10ⁱ	−0.31 (11)
C2—C3—C4—C5	1.9 (3)	C3—C4—S1—O2	3.65 (17)
C2—C3—C4—S1	−175.61 (15)	C5—C4—S1—O2	−173.94 (14)
C3—C4—C5—C6	−1.6 (3)	C3—C4—S1—O1	133.19 (15)
S1—C4—C5—C6	175.99 (15)	C5—C4—S1—O1	−44.39 (17)
C2—C1—C6—C5	1.8 (3)	C3—C4—S1—N1	−111.21 (15)
C4—C5—C6—C1	−0.3 (3)	C5—C4—S1—N1	71.20 (16)
N1—C7—C8—C10	−121.05 (17)	C8—C7—N1—S1	−150.45 (13)
N1—C7—C8—C9	59.57 (18)	O2—S1—N1—C7	170.85 (14)
C10—C8—C9—C8ⁱ	−0.30 (11)	O1—S1—N1—C7	42.63 (16)
C7—C8—C9—C8ⁱ	179.09 (15)	C4—S1—N1—C7	−73.22 (15)
C9—C8—C10—C11	0.6 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱⁱ	0.81 (2)	2.16 (2)	2.960 (2)	166 (2)
C5—H5···O1ⁱⁱⁱ	0.93	2.55	3.461 (2)	166
C10—H10···O1^iv	0.93	2.57	3.379 (3)	146

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

Experimental details

Crystal data
Chemical formula	C₂₀H₂₀N₂O₄S₂
M_r	416.50
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	16.4319 (6), 7.8024 (3), 16.1217 (6)
β (°)	111.543 (2)
V (Å³)	1922.54 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.15 × 0.11 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8653, 2346, 1841
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.103, 1.07
No. of reflections	2346
No. of parameters	131
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.34

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···O2ⁱ	0.81 (2)	2.16 (2)	2.960 (2)	166 (2)
C5—H5···O1ⁱⁱ	0.93	2.55	3.461 (2)	166
C10—H10···O1ⁱⁱⁱ	0.93	2.57	3.379 (3)	146

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

Acknowledgements

IUK thanks the Higher Education Commission of Pakistan for its financial support under the project to strengthen the Materials Chemistry Laboratory at GCUL.

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
Khan, I. U., Sheikh, T. A., Ejaz & Harrison, W. T. A. (2011). Acta Cryst. E67, o2371. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar