N,N′-Bis(3-methylbut-2-enyl)-N,N′-(1,4-phenylene)dibenzenesulfonamide

Ejaz; Khan, I.U.; Sheikh, T.A.; Harrison, W.T.A.

doi:10.1107/S1600536811045661

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3281

https://doi.org/10.1107/S1600536811045661

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N,N′-Bis(3-methylbut-2-enyl)-N,N′-(1,4-phenylene)dibenzenesulfonamide

Ejaz,^a Islam Ullah Khan,^a ^* Tahir Ali Sheikh ^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 26 October 2011; accepted 31 October 2011; online 12 November 2011)

The complete molecule of the title compound, C₂₈H₃₂N₂O₄S₂, is generated by a crystallographic inversion centre. The dihedral angle between the central and pendant aromatic rings is 46.78 (7)°. The C_ar—S—N—C_ar (ar = aromatic) torsion angle is 73.64 (15)° and the bond-angle sum for the N atom is 350.4°. In the crystal, weak C—H⋯O interactions link the molecules, forming a two-dimensional network lying parallel to the bc plane.

Related literature

For related structures, see: Ejaz et al. (2011a ,b ).

Experimental

Crystal data

C₂₈H₃₂N₂O₄S₂
M_r = 524.68
Monoclinic, P 2₁ /c
a = 10.6574 (4) Å
b = 20.8073 (8) Å
c = 6.4015 (2) Å
β = 105.673 (2)°
V = 1366.76 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 296 K
0.50 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
11502 measured reflections
2667 independent reflections
1931 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.104
S = 1.03
2667 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2ⁱ	0.93	2.52	3.398 (3)	158
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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: https://doi.org/10.1107/S1600536811045661/su2338sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811045661/su2338Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811045661/su2338Isup3.cml

checkCIF report

Comment top

As part of our ongoing studies of symmetrical aryl sulfonamides (Ejaz et al., 2011a,b), the synthesis and structure of the title compound are described herein.

The complete molecule of the title compound is generated by a crystallographic inversion centre (Fig. 1). The dihedral angles between the central benzene ring (C12-C17) and the pendant (C1-C6) ring is 46.78 (7)°. Overall, an approximante H-shaped conformation arises. The C1—S1—N1—C12 torsion angle is 73.64 (15)°, indicating a gauche conformation for the sulfonamide bridge between the aromatic rings. The bond angle sum of 350.4° for the nitrogen atom, N1, is similar to the situation found for two related structures, N,N'-(benzene-1,3-diyldimethanediyl)dibenzenesulfonamide and N,N'-diethyl-(benzene-1,3-diyldimethanediyl) dibenzenesulfonamide, that we have reported on recently (Ejaz et al., 2011a,b).

In the crystal, weak C—H···O interactions link the molecules to form a two-dimensional network lieing parallel to the bc plane (Table 1). There is no aromatic π-π stacking in the crystal.

Related literature top

For related structures, see: Ejaz et al. (2011a,b).

Experimental top

A mixture of N,N'-benzene-1,4-diyldibenzenesulfonamide (0.194 g, 0.5 mmol), sodium hydride (0.24 g; 1.0 mmol) and N,N-dimethylformamide (10.0 ml) was stirred in a 100-ml round-bottom flask at room temperature for half an hour followed by the addition of 3,3-dimethylallyl bromide (0.116 ml; 1.0 mmol). The reaction mixture was stirred for five hours; reaction progress was monitored by TLC. After completion, the contents were poured over crushed ice. The precipitated product was isolated, washed and crystallized from methanol to yield brown block-like crystals of the title compound.

Structure description top

As part of our ongoing studies of symmetrical aryl sulfonamides (Ejaz et al., 2011a,b), the synthesis and structure of the title compound are described herein.

In the crystal, weak C—H···O interactions link the molecules to form a two-dimensional network lieing parallel to the bc plane (Table 1). There is no aromatic π-π stacking in the crystal.

For related structures, see: Ejaz et al. (2011a,b).

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 50% displacement ellipsoids and the atom numbering scheme [symmetry code: (i) -x+1, -y+1, -z+1].

N,N'-Bis(3-methylbut-2-enyl)-N,N'-(1,4- phenylene)dibenzenesulfonamide top

Crystal data top

C₂₈H₃₂N₂O₄S₂	F(000) = 556
M_r = 524.68	D_x = 1.275 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3403 reflections
a = 10.6574 (4) Å	θ = 2.0–28.4°
b = 20.8073 (8) Å	µ = 0.23 mm⁻¹
c = 6.4015 (2) Å	T = 296 K
β = 105.673 (2)°	Block, brown
V = 1366.76 (8) Å³	0.50 × 0.20 × 0.15 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	1931 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 26.0°, θ_min = 2.8°
ω scans	h = −13→13
11502 measured reflections	k = −25→25
2667 independent reflections	l = −7→7

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0426P)² + 0.3607P] where P = (F_o² + 2F_c²)/3
2667 reflections	(Δ/σ)_max = 0.001
165 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₂₈H₃₂N₂O₄S₂	V = 1366.76 (8) Å³
M_r = 524.68	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.6574 (4) Å	µ = 0.23 mm⁻¹
b = 20.8073 (8) Å	T = 296 K
c = 6.4015 (2) Å	0.50 × 0.20 × 0.15 mm
β = 105.673 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1931 reflections with I > 2σ(I)
11502 measured reflections	R_int = 0.031
2667 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 1.03	Δρ_max = 0.23 e Å⁻³
2667 reflections	Δρ_min = −0.31 e Å⁻³
165 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	0.1596 (2)	0.38177 (9)	0.4486 (3)	0.0504 (5)
C2	0.1301 (2)	0.33079 (11)	0.3050 (4)	0.0653 (6)
H2	0.1735	0.2918	0.3386	0.078*
C3	0.0355 (3)	0.33861 (14)	0.1113 (4)	0.0812 (8)
H3	0.0168	0.3050	0.0117	0.097*
C4	−0.0307 (3)	0.39525 (15)	0.0648 (4)	0.0864 (8)
H4	−0.0953	0.3998	−0.0650	0.104*
C5	−0.0026 (3)	0.44530 (13)	0.2077 (4)	0.0780 (7)
H5	−0.0489	0.4836	0.1758	0.094*
C6	0.0940 (2)	0.43918 (11)	0.3987 (4)	0.0617 (6)
H6	0.1149	0.4737	0.4940	0.074*
C7	0.4581 (2)	0.32309 (9)	0.4971 (4)	0.0563 (5)
H7A	0.4214	0.2838	0.5369	0.068*
H7B	0.4229	0.3295	0.3422	0.068*
C8	0.6019 (2)	0.31741 (9)	0.5505 (3)	0.0536 (5)
H8	0.6433	0.3027	0.6892	0.064*
C9	0.6779 (2)	0.33075 (10)	0.4248 (3)	0.0549 (5)
C10	0.8227 (3)	0.32188 (14)	0.5036 (4)	0.0874 (8)
H10A	0.8445	0.3029	0.6456	0.131*
H10B	0.8650	0.3629	0.5101	0.131*
H10C	0.8513	0.2942	0.4057	0.131*
C11	0.6331 (3)	0.35544 (14)	0.1992 (4)	0.0806 (8)
H11A	0.5396	0.3548	0.1524	0.121*
H11B	0.6672	0.3288	0.1051	0.121*
H11C	0.6634	0.3987	0.1943	0.121*
C12	0.45972 (18)	0.44109 (8)	0.5560 (3)	0.0407 (4)
C13	0.41589 (19)	0.46298 (9)	0.3456 (3)	0.0475 (5)
H13	0.3591	0.4380	0.2412	0.057*
C14	0.54372 (19)	0.47809 (9)	0.7100 (3)	0.0471 (5)
H14	0.5734	0.4633	0.8519	0.057*
S1	0.28630 (5)	0.37450 (2)	0.68836 (8)	0.05203 (19)
N1	0.42238 (16)	0.37861 (7)	0.6175 (2)	0.0466 (4)
O1	0.28181 (15)	0.42921 (7)	0.8196 (2)	0.0655 (4)
O2	0.28035 (15)	0.31145 (7)	0.7724 (3)	0.0727 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0536 (12)	0.0418 (12)	0.0643 (12)	−0.0040 (10)	0.0305 (10)	−0.0043 (9)
C2	0.0595 (15)	0.0542 (14)	0.0857 (16)	−0.0051 (11)	0.0258 (13)	−0.0142 (12)
C3	0.0786 (19)	0.083 (2)	0.0821 (17)	−0.0127 (16)	0.0222 (15)	−0.0308 (15)
C4	0.0791 (19)	0.106 (2)	0.0718 (16)	0.0036 (17)	0.0157 (14)	−0.0058 (16)
C5	0.0846 (18)	0.0751 (18)	0.0774 (17)	0.0202 (15)	0.0273 (15)	0.0130 (14)
C6	0.0752 (16)	0.0511 (14)	0.0636 (13)	0.0042 (12)	0.0272 (12)	−0.0042 (10)
C7	0.0658 (15)	0.0336 (11)	0.0745 (13)	−0.0052 (10)	0.0277 (11)	−0.0031 (10)
C8	0.0649 (14)	0.0450 (12)	0.0524 (11)	0.0090 (10)	0.0182 (10)	0.0054 (9)
C9	0.0607 (14)	0.0512 (13)	0.0535 (11)	0.0067 (10)	0.0167 (10)	0.0007 (9)
C10	0.0680 (17)	0.116 (2)	0.0790 (16)	0.0122 (16)	0.0220 (14)	0.0009 (15)
C11	0.0872 (19)	0.096 (2)	0.0641 (14)	0.0167 (15)	0.0301 (14)	0.0185 (13)
C12	0.0507 (11)	0.0296 (9)	0.0451 (10)	−0.0018 (8)	0.0185 (9)	0.0006 (7)
C13	0.0579 (13)	0.0392 (11)	0.0440 (10)	−0.0108 (9)	0.0111 (9)	−0.0051 (8)
C14	0.0608 (13)	0.0413 (11)	0.0386 (9)	−0.0039 (10)	0.0123 (9)	0.0044 (8)
S1	0.0631 (4)	0.0435 (3)	0.0564 (3)	−0.0048 (3)	0.0282 (3)	0.0049 (2)
N1	0.0558 (10)	0.0311 (9)	0.0573 (9)	−0.0037 (7)	0.0225 (8)	0.0026 (7)
O1	0.0823 (11)	0.0655 (10)	0.0571 (8)	−0.0043 (8)	0.0330 (8)	−0.0125 (7)
O2	0.0808 (11)	0.0557 (10)	0.0903 (11)	−0.0069 (8)	0.0380 (9)	0.0261 (8)

Geometric parameters (Å, º) top

C1—C6	1.378 (3)	C9—C11	1.485 (3)
C1—C2	1.383 (3)	C9—C10	1.500 (3)
C1—S1	1.756 (2)	C10—H10A	0.9600
C2—C3	1.381 (3)	C10—H10B	0.9600
C2—H2	0.9300	C10—H10C	0.9600
C3—C4	1.364 (4)	C11—H11A	0.9600
C3—H3	0.9300	C11—H11B	0.9600
C4—C5	1.365 (4)	C11—H11C	0.9600
C4—H4	0.9300	C12—C14	1.374 (2)
C5—C6	1.375 (3)	C12—C13	1.379 (2)
C5—H5	0.9300	C12—N1	1.445 (2)
C6—H6	0.9300	C13—C14ⁱ	1.378 (2)
C7—C8	1.482 (3)	C13—H13	0.9300
C7—N1	1.494 (2)	C14—C13ⁱ	1.378 (2)
C7—H7A	0.9700	C14—H14	0.9300
C7—H7B	0.9700	S1—O1	1.4233 (14)
C8—C9	1.317 (3)	S1—O2	1.4257 (14)
C8—H8	0.9300	S1—N1	1.6345 (16)

C6—C1—C2	120.1 (2)	C9—C10—H10A	109.5
C6—C1—S1	120.00 (16)	C9—C10—H10B	109.5
C2—C1—S1	119.85 (17)	H10A—C10—H10B	109.5
C3—C2—C1	119.1 (2)	C9—C10—H10C	109.5
C3—C2—H2	120.5	H10A—C10—H10C	109.5
C1—C2—H2	120.5	H10B—C10—H10C	109.5
C4—C3—C2	120.5 (2)	C9—C11—H11A	109.5
C4—C3—H3	119.8	C9—C11—H11B	109.5
C2—C3—H3	119.8	H11A—C11—H11B	109.5
C3—C4—C5	120.4 (3)	C9—C11—H11C	109.5
C3—C4—H4	119.8	H11A—C11—H11C	109.5
C5—C4—H4	119.8	H11B—C11—H11C	109.5
C4—C5—C6	120.1 (2)	C14—C12—C13	119.93 (16)
C4—C5—H5	120.0	C14—C12—N1	118.85 (15)
C6—C5—H5	120.0	C13—C12—N1	121.18 (16)
C5—C6—C1	119.9 (2)	C14ⁱ—C13—C12	119.95 (17)
C5—C6—H6	120.1	C14ⁱ—C13—H13	120.0
C1—C6—H6	120.1	C12—C13—H13	120.0
C8—C7—N1	109.54 (16)	C12—C14—C13ⁱ	120.12 (16)
C8—C7—H7A	109.8	C12—C14—H14	119.9
N1—C7—H7A	109.8	C13ⁱ—C14—H14	119.9
C8—C7—H7B	109.8	O1—S1—O2	120.08 (9)
N1—C7—H7B	109.8	O1—S1—N1	107.20 (9)
H7A—C7—H7B	108.2	O2—S1—N1	106.63 (9)
C9—C8—C7	127.64 (19)	O1—S1—C1	107.84 (9)
C9—C8—H8	116.2	O2—S1—C1	107.89 (10)
C7—C8—H8	116.2	N1—S1—C1	106.46 (8)
C8—C9—C11	125.3 (2)	C12—N1—C7	115.31 (14)
C8—C9—C10	121.0 (2)	C12—N1—S1	116.94 (12)
C11—C9—C10	113.7 (2)	C7—N1—S1	118.15 (12)

C6—C1—C2—C3	0.7 (3)	C6—C1—S1—O2	143.23 (16)
S1—C1—C2—C3	−176.16 (17)	C2—C1—S1—O2	−39.90 (18)
C1—C2—C3—C4	−1.9 (4)	C6—C1—S1—N1	−102.63 (17)
C2—C3—C4—C5	1.1 (4)	C2—C1—S1—N1	74.23 (17)
C3—C4—C5—C6	0.8 (4)	C14—C12—N1—C7	−119.44 (19)
C4—C5—C6—C1	−2.0 (4)	C13—C12—N1—C7	58.5 (2)
C2—C1—C6—C5	1.2 (3)	C14—C12—N1—S1	94.90 (18)
S1—C1—C6—C5	178.08 (17)	C13—C12—N1—S1	−87.15 (19)
N1—C7—C8—C9	−108.2 (2)	C8—C7—N1—C12	65.6 (2)
C7—C8—C9—C11	0.7 (4)	C8—C7—N1—S1	−149.18 (14)
C7—C8—C9—C10	−179.6 (2)	O1—S1—N1—C12	−41.56 (15)
C14—C12—C13—C14ⁱ	−0.1 (3)	O2—S1—N1—C12	−171.36 (13)
N1—C12—C13—C14ⁱ	−177.99 (17)	C1—S1—N1—C12	73.64 (15)
C13—C12—C14—C13ⁱ	0.1 (3)	O1—S1—N1—C7	173.77 (14)
N1—C12—C14—C13ⁱ	178.04 (17)	O2—S1—N1—C7	43.97 (17)
C6—C1—S1—O1	12.14 (19)	C1—S1—N1—C7	−71.02 (16)
C2—C1—S1—O1	−170.99 (16)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱⁱ	0.93	2.52	3.398 (3)	158

Symmetry code: (ii) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₈H₃₂N₂O₄S₂
M_r	524.68
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	10.6574 (4), 20.8073 (8), 6.4015 (2)
β (°)	105.673 (2)
V (Å³)	1366.76 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.50 × 0.20 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11502, 2667, 1931
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.104, 1.03
No. of reflections	2667
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.31

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
C2—H2···O2ⁱ	0.93	2.52	3.398 (3)	158

Symmetry code: (i) x, −y+1/2, z−1/2.

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

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