1-{2-[(E)-2-(2-Nitro­phen­yl)ethen­yl]-1-phenyl­sulfonyl-1H-indol-3-yl}ethanone

S Karthikeyan; K Sethusankar; Velu Saravanan; Arasambattu K Mohanakrishnan

doi:10.1107/S1600536813022241

. 2013 Aug 14;69(Pt 9):o1422–o1423. doi: 10.1107/S1600536813022241

1-{2-[(E)-2-(2-Nitrophenyl)ethenyl]-1-phenylsulfonyl-1H-indol-3-yl}ethanone

S Karthikeyan ^a, K Sethusankar ^a,^*, Velu Saravanan ^b, Arasambattu K Mohanakrishnan ^b

PMCID: PMC3884461 PMID: 24427056

Abstract

In the title compound, C₂₄H₁₈N₂O₅S, the S atom has a distorted tetrahedral configuration, with bond angles varying from 105.11 (7) to 119.98 (8)°. As a result of the electron-withdrawing character of the phenylsulfonyl group, the N—Csp ² bond lengths [1.414 (2) and 1.413 (2) Å] are slightly longer than the reported value of 1.355 (14) Å for N atoms with a planar configuration. The indole moiety is essentially planar, with a maximum deviation of 0.0177 (14) Å for the N atom. The phenyl ring of the sulfonyl substituent makes a dihedral angle of 85.70 (7)° with the mean plane of the indole moiety. The molecular structure features intramolecular C—H⋯O hydrogen bonds, which generate S(6) and S(12) ring motifs. In the crystal, adjacent molecules are linked via C—H⋯O hydrogen bonds, forming infinite C(7) chains running along the a-axis direction. The crystal packing also features C—H⋯π interactions, which form a three-dimensional structure.

Related literature

For the biological activity of Indole derivatives, see: Rodriguez et al. (1985 ▶); Chai et al. (2006 ▶); Olgen & Coban (2003 ▶). For related crystal structures, see: Karthikeyan et al. (2011 ▶, 2012 ▶). For related bond distances and bond-angle geometries and distortions, see: Allen (1981 ▶); Allen et al. (1987 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶). For the Thorpe–Ingold effect, see: Bassindale (1984 ▶).

Experimental

Crystal data

C₂₄H₁₈N₂O₅S
M _r = 446.46
Monoclinic,
a = 8.2409 (8) Å
b = 16.1702 (15) Å
c = 15.3700 (15) Å
β = 95.775 (5)°
V = 2037.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 296 K
0.28 × 0.25 × 0.23 mm

Data collection

Bruker SMART APEXII CCD diffractometer
18837 measured reflections
4960 independent reflections
3893 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.118
S = 1.02
4960 reflections
290 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813022241/su2631sup1.cif

e-69-o1422-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813022241/su2631Isup2.hkl

e-69-o1422-Isup2.hkl^{(243KB, hkl)}

Click here for additional data file.^{(7.8KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813022241/su2631Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1, Cg2 and Cg3 are the centroids of the C17–C22, C11–C16 and C1–C6 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1	0.93	2.35	2.935 (2)	121
C18—H18⋯O3	0.93	2.46	3.108 (2)	127
C20—H20⋯O2ⁱ	0.93	2.68	3.319 (2)	126
C5—H5⋯Cg1ⁱⁱ	0.93	2.89	3.720 (2)	149
C22—H22⋯Cg2ⁱⁱⁱ	0.93	2.73	3.4618 (18)	137
C24—H24B⋯Cg3^iv	0.96	2.90	3.601 (3)	131

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

The authors thank Mr T. Srinivasan and Dr D. Velmurugan, The Head, CAS in Crystallography and Biophysics, University of Madras, Chennai, India, for the data collection.

supplementary crystallographic information

1. Comment

The indole ring system is present in a number of natural products, many of which are found to possess pharmacological properties like anti-microbial, anti-inflammatory and anti-implantation activities (Rodriguez et al., 1985). Indole derivatives are also known to exhibit anti-oxidant activities (Olgen & Coban, 2003) and antihepatitis B virus activities (Chai et al., 2006).

In the title compound, Fig. 1, the indole ring is essentially planar with a maximum deviation of 0.0177 (14) Å for atom N1. The indole moiety is perpendicular to the phenylsulfonyl ring with a dihedral angle 85.70 (7)°. The nitro-group is inclined at an angle of 7.59 (9)° to the benzene ring to which it is attached. The nitro-phenyl ring makes a dihedral angle of 76.41 (7)° with the indole moiety mean plane. Short intramolecular C2—H2···O1 and C18—H18···O3 hyrogen bonds result in S(6) and S(12) ring motifs (Table 1 and Fig. 1). The molecular dimensions in the title compound are in excellent agreement with those reported for a closely related compound (Karthikeyan et al., 2012).

The expansion of the ispo angles at C1, C3 and C4 [122.34 (16), 121.59 (18) and 121.13 (18)°, respectively] and contraction of the apical angles at C2, C5 and C6 [117.12 (19), 118.54 (18) and 119.28 (16)°, respectively] are caused by the fusion of the smaller pyrrole ring to the six-membered benzene ring and the strain is taken up by the angular distortion rather than by bond-length distortions (Allen, 1981). As a result of the electron withdrawing character of the phenylsulfonyl group, the N—Csp² bond lengths, viz, N1—C1 [1.414 (2) Å] and N1—C8 [1.413 (2) Å], are longer than the mean value of 1.355 (14) Å reported for N atoms with planar configurations (Allen et al., 1987).

Atom S1 has a distorted tetrahedral configuration. The widening of the angle O2═S1═O1 [119.98 (8)°] and the narrowing of the angle N1—S1—C17 [105.11 (7)°] from the ideal tetrahedral value are attributed to the Thorpe-Ingold effect (Bassindale, 1984). The widening of the angles may be due to the repulsive interactions between the two short S═O bonds, similar to what is observed in a related structure (Karthikeyan et al., 2011).

The crystal packing is stabilized by C—H···O hydrogen bonds (Fig. 2 and Table 1) resulting in C(7) infinite chains of molecules running along the a axis direction (Bernstein et al., 1995). The crystal packing is further stabilized by C—H···π interactions forming a three-dimensional structure (Table 1 and Fig. 3).

2. Experimental

A solution of the ylide, 1-[1-(phenylsulfonyl)-2-[(triphenyl-$1⁵-phosphanylidene)methyl]-1H-indol-3-yl]ethan-1-one (1 g, 1.745 mmol), and 2-nitrobenzaldehyde (0.29 g, 1.919 mmol) in dry DCM (20 ml) was refluxed for 8 h under N₂. Removal of solvent in vacuo followed by trituration of the crude product with cold methanol (5 ml) afforded the title compound as a yellow solid [Yield: 0.71 g (92%); M.p. 427-429 K]. Block-like yellow crystals were obtained by slow evaporation of a solution in CHCl₃.