organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

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 Car—S—N—Car (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[Ejaz, Khan, I. U., Ahmad, A. & Harrison, W. T. A. (2011a). Acta Cryst. E67, o3037.],b[Ejaz, Khan, I. U., Ahmad, A., Harrison, W. T. A. & Sheikh, T. A. (2011b). Acta Cryst. E67, o3038.]).

[Scheme 1]

Experimental

Crystal data
  • C28H32N2O4S2

  • Mr = 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)

  • Rint = 0.031

Refinement
  • R[F2 > 2σ(F2)] = 0.039

  • wR(F2) = 0.104

  • S = 1.03

  • 2667 reflections

  • 165 parameters

  • H-atom parameters constrained

  • Δρmax = 0.23 e Å−3

  • Δρmin = −0.31 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97.

Supporting information


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.

Refinement top

The hydrogen atoms were placed in calculated positions (C—H = 0.93–0.96 Å) and refined as riding atoms with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The methyl groups were allowed to rotate, but not to tip, to best fit the electron density.

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.

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.

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
[Figure 1] 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
C28H32N2O4S2F(000) = 556
Mr = 524.68Dx = 1.275 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3403 reflections
a = 10.6574 (4) Åθ = 2.0–28.4°
b = 20.8073 (8) ŵ = 0.23 mm1
c = 6.4015 (2) ÅT = 296 K
β = 105.673 (2)°Block, brown
V = 1366.76 (8) Å30.50 × 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 tubeRint = 0.031
Graphite monochromatorθmax = 26.0°, θmin = 2.8°
ω scansh = 1313
11502 measured reflectionsk = 2525
2667 independent reflectionsl = 77
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0426P)2 + 0.3607P]
where P = (Fo2 + 2Fc2)/3
2667 reflections(Δ/σ)max = 0.001
165 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
C28H32N2O4S2V = 1366.76 (8) Å3
Mr = 524.68Z = 2
Monoclinic, P21/cMo Kα radiation
a = 10.6574 (4) ŵ = 0.23 mm1
b = 20.8073 (8) ÅT = 296 K
c = 6.4015 (2) Å0.50 × 0.20 × 0.15 mm
β = 105.673 (2)°
Data collection top
Bruker APEXII CCD
diffractometer
1931 reflections with I > 2σ(I)
11502 measured reflectionsRint = 0.031
2667 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.104H-atom parameters constrained
S = 1.03Δρmax = 0.23 e Å3
2667 reflectionsΔρmin = 0.31 e Å3
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
xyzUiso*/Ueq
C10.1596 (2)0.38177 (9)0.4486 (3)0.0504 (5)
C20.1301 (2)0.33079 (11)0.3050 (4)0.0653 (6)
H20.17350.29180.33860.078*
C30.0355 (3)0.33861 (14)0.1113 (4)0.0812 (8)
H30.01680.30500.01170.097*
C40.0307 (3)0.39525 (15)0.0648 (4)0.0864 (8)
H40.09530.39980.06500.104*
C50.0026 (3)0.44530 (13)0.2077 (4)0.0780 (7)
H50.04890.48360.17580.094*
C60.0940 (2)0.43918 (11)0.3987 (4)0.0617 (6)
H60.11490.47370.49400.074*
C70.4581 (2)0.32309 (9)0.4971 (4)0.0563 (5)
H7A0.42140.28380.53690.068*
H7B0.42290.32950.34220.068*
C80.6019 (2)0.31741 (9)0.5505 (3)0.0536 (5)
H80.64330.30270.68920.064*
C90.6779 (2)0.33075 (10)0.4248 (3)0.0549 (5)
C100.8227 (3)0.32188 (14)0.5036 (4)0.0874 (8)
H10A0.84450.30290.64560.131*
H10B0.86500.36290.51010.131*
H10C0.85130.29420.40570.131*
C110.6331 (3)0.35544 (14)0.1992 (4)0.0806 (8)
H11A0.53960.35480.15240.121*
H11B0.66720.32880.10510.121*
H11C0.66340.39870.19430.121*
C120.45972 (18)0.44109 (8)0.5560 (3)0.0407 (4)
C130.41589 (19)0.46298 (9)0.3456 (3)0.0475 (5)
H130.35910.43800.24120.057*
C140.54372 (19)0.47809 (9)0.7100 (3)0.0471 (5)
H140.57340.46330.85190.057*
S10.28630 (5)0.37450 (2)0.68836 (8)0.05203 (19)
N10.42238 (16)0.37861 (7)0.6175 (2)0.0466 (4)
O10.28181 (15)0.42921 (7)0.8196 (2)0.0655 (4)
O20.28035 (15)0.31145 (7)0.7724 (3)0.0727 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0536 (12)0.0418 (12)0.0643 (12)0.0040 (10)0.0305 (10)0.0043 (9)
C20.0595 (15)0.0542 (14)0.0857 (16)0.0051 (11)0.0258 (13)0.0142 (12)
C30.0786 (19)0.083 (2)0.0821 (17)0.0127 (16)0.0222 (15)0.0308 (15)
C40.0791 (19)0.106 (2)0.0718 (16)0.0036 (17)0.0157 (14)0.0058 (16)
C50.0846 (18)0.0751 (18)0.0774 (17)0.0202 (15)0.0273 (15)0.0130 (14)
C60.0752 (16)0.0511 (14)0.0636 (13)0.0042 (12)0.0272 (12)0.0042 (10)
C70.0658 (15)0.0336 (11)0.0745 (13)0.0052 (10)0.0277 (11)0.0031 (10)
C80.0649 (14)0.0450 (12)0.0524 (11)0.0090 (10)0.0182 (10)0.0054 (9)
C90.0607 (14)0.0512 (13)0.0535 (11)0.0067 (10)0.0167 (10)0.0007 (9)
C100.0680 (17)0.116 (2)0.0790 (16)0.0122 (16)0.0220 (14)0.0009 (15)
C110.0872 (19)0.096 (2)0.0641 (14)0.0167 (15)0.0301 (14)0.0185 (13)
C120.0507 (11)0.0296 (9)0.0451 (10)0.0018 (8)0.0185 (9)0.0006 (7)
C130.0579 (13)0.0392 (11)0.0440 (10)0.0108 (9)0.0111 (9)0.0051 (8)
C140.0608 (13)0.0413 (11)0.0386 (9)0.0039 (10)0.0123 (9)0.0044 (8)
S10.0631 (4)0.0435 (3)0.0564 (3)0.0048 (3)0.0282 (3)0.0049 (2)
N10.0558 (10)0.0311 (9)0.0573 (9)0.0037 (7)0.0225 (8)0.0026 (7)
O10.0823 (11)0.0655 (10)0.0571 (8)0.0043 (8)0.0330 (8)0.0125 (7)
O20.0808 (11)0.0557 (10)0.0903 (11)0.0069 (8)0.0380 (9)0.0261 (8)
Geometric parameters (Å, º) top
C1—C61.378 (3)C9—C111.485 (3)
C1—C21.383 (3)C9—C101.500 (3)
C1—S11.756 (2)C10—H10A0.9600
C2—C31.381 (3)C10—H10B0.9600
C2—H20.9300C10—H10C0.9600
C3—C41.364 (4)C11—H11A0.9600
C3—H30.9300C11—H11B0.9600
C4—C51.365 (4)C11—H11C0.9600
C4—H40.9300C12—C141.374 (2)
C5—C61.375 (3)C12—C131.379 (2)
C5—H50.9300C12—N11.445 (2)
C6—H60.9300C13—C14i1.378 (2)
C7—C81.482 (3)C13—H130.9300
C7—N11.494 (2)C14—C13i1.378 (2)
C7—H7A0.9700C14—H140.9300
C7—H7B0.9700S1—O11.4233 (14)
C8—C91.317 (3)S1—O21.4257 (14)
C8—H80.9300S1—N11.6345 (16)
C6—C1—C2120.1 (2)C9—C10—H10A109.5
C6—C1—S1120.00 (16)C9—C10—H10B109.5
C2—C1—S1119.85 (17)H10A—C10—H10B109.5
C3—C2—C1119.1 (2)C9—C10—H10C109.5
C3—C2—H2120.5H10A—C10—H10C109.5
C1—C2—H2120.5H10B—C10—H10C109.5
C4—C3—C2120.5 (2)C9—C11—H11A109.5
C4—C3—H3119.8C9—C11—H11B109.5
C2—C3—H3119.8H11A—C11—H11B109.5
C3—C4—C5120.4 (3)C9—C11—H11C109.5
C3—C4—H4119.8H11A—C11—H11C109.5
C5—C4—H4119.8H11B—C11—H11C109.5
C4—C5—C6120.1 (2)C14—C12—C13119.93 (16)
C4—C5—H5120.0C14—C12—N1118.85 (15)
C6—C5—H5120.0C13—C12—N1121.18 (16)
C5—C6—C1119.9 (2)C14i—C13—C12119.95 (17)
C5—C6—H6120.1C14i—C13—H13120.0
C1—C6—H6120.1C12—C13—H13120.0
C8—C7—N1109.54 (16)C12—C14—C13i120.12 (16)
C8—C7—H7A109.8C12—C14—H14119.9
N1—C7—H7A109.8C13i—C14—H14119.9
C8—C7—H7B109.8O1—S1—O2120.08 (9)
N1—C7—H7B109.8O1—S1—N1107.20 (9)
H7A—C7—H7B108.2O2—S1—N1106.63 (9)
C9—C8—C7127.64 (19)O1—S1—C1107.84 (9)
C9—C8—H8116.2O2—S1—C1107.89 (10)
C7—C8—H8116.2N1—S1—C1106.46 (8)
C8—C9—C11125.3 (2)C12—N1—C7115.31 (14)
C8—C9—C10121.0 (2)C12—N1—S1116.94 (12)
C11—C9—C10113.7 (2)C7—N1—S1118.15 (12)
C6—C1—C2—C30.7 (3)C6—C1—S1—O2143.23 (16)
S1—C1—C2—C3176.16 (17)C2—C1—S1—O239.90 (18)
C1—C2—C3—C41.9 (4)C6—C1—S1—N1102.63 (17)
C2—C3—C4—C51.1 (4)C2—C1—S1—N174.23 (17)
C3—C4—C5—C60.8 (4)C14—C12—N1—C7119.44 (19)
C4—C5—C6—C12.0 (4)C13—C12—N1—C758.5 (2)
C2—C1—C6—C51.2 (3)C14—C12—N1—S194.90 (18)
S1—C1—C6—C5178.08 (17)C13—C12—N1—S187.15 (19)
N1—C7—C8—C9108.2 (2)C8—C7—N1—C1265.6 (2)
C7—C8—C9—C110.7 (4)C8—C7—N1—S1149.18 (14)
C7—C8—C9—C10179.6 (2)O1—S1—N1—C1241.56 (15)
C14—C12—C13—C14i0.1 (3)O2—S1—N1—C12171.36 (13)
N1—C12—C13—C14i177.99 (17)C1—S1—N1—C1273.64 (15)
C13—C12—C14—C13i0.1 (3)O1—S1—N1—C7173.77 (14)
N1—C12—C14—C13i178.04 (17)O2—S1—N1—C743.97 (17)
C6—C1—S1—O112.14 (19)C1—S1—N1—C771.02 (16)
C2—C1—S1—O1170.99 (16)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O2ii0.932.523.398 (3)158
Symmetry code: (ii) x, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC28H32N2O4S2
Mr524.68
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)10.6574 (4), 20.8073 (8), 6.4015 (2)
β (°) 105.673 (2)
V3)1366.76 (8)
Z2
Radiation typeMo Kα
µ (mm1)0.23
Crystal size (mm)0.50 × 0.20 × 0.15
Data collection
DiffractometerBruker APEXII CCD
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
11502, 2667, 1931
Rint0.031
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.104, 1.03
No. of reflections2667
No. of parameters165
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
C2—H2···O2i0.932.523.398 (3)158
Symmetry code: (i) x, y+1/2, z1/2.
 

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

First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationEjaz, Khan, I. U., Ahmad, A. & Harrison, W. T. A. (2011a). Acta Cryst. E67, o3037.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationEjaz, Khan, I. U., Ahmad, A., Harrison, W. T. A. & Sheikh, T. A. (2011b). Acta Cryst. E67, o3038.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds