Diethyl 2-[(2-benzyl-1-phenyl­sulfonyl-1H-indol-3-yl)methyl­ene]malonate

T Kavitha; M Thenmozhi; V Dhayalan; A K Mohanakrishnan; M N Ponnuswamy

doi:10.1107/S160053680804004X

. 2008 Dec 3;65(Pt 1):o12. doi: 10.1107/S160053680804004X

Diethyl 2-[(2-benzyl-1-phenylsulfonyl-1H-indol-3-yl)methylene]malonate

T Kavitha ^a, M Thenmozhi ^a, V Dhayalan ^b, A K Mohanakrishnan ^b, M N Ponnuswamy ^a,^*

PMCID: PMC2967933 PMID: 21581581

Abstract

In the title compound, C₂₉H₂₇NO₆S, the sulfonyl-bound phenyl ring is almost perpendicular to the indole ring system [dihedral angle = 87.96 (6)°], while the benzylphenyl ring is oriented at an angle of 76.8 (7)°. An intramolecular C—H⋯O hydrogen bond is observed. In the crystal structure, molecules are linked into a zigzag C(10) chain along the b axis by intermolecular C—H⋯O hydrogen bonds.

Related literature

For general background to indole derivatives and their biological activity, see: Andreani et al. (2001 ▶); Bassindale (1984 ▶); Quetin-Leclercq et al. (1995 ▶); Singh et al. (2000 ▶); Tsotinis et al. (1997 ▶); Wang & Ng (2002 ▶).

Experimental

Crystal data

C₂₉H₂₇NO₆S
M _r = 517.58
Monoclinic,
a = 10.8280 (9) Å
b = 13.7762 (11) Å
c = 17.6832 (16) Å
β = 91.341 (4)°
V = 2637.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 293 (2) K
0.30 × 0.25 × 0.16 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.952, T _max = 0.968
34168 measured reflections
7583 independent reflections
4683 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.142
S = 1.02
7583 reflections
334 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004 ▶); 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 and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680804004X/ci2729sup1.cif

e-65-00o12-sup1.cif^{(26.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680804004X/ci2729Isup2.hkl

e-65-00o12-Isup2.hkl^{(363.5KB, hkl)}

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O1	0.93	2.33	2.919 (2)	121
C7—H7⋯O5ⁱ	0.93	2.59	3.317 (2)	135

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Symmetry code: (i) Inline graphic .

Acknowledgments

TK thanks Dr Babu Varghese, SAIF, IIT-Madras, Chennai, India, for his help with the data collection. VD thanks UGC, India, for financial support.

supplementary crystallographic information

Comment

Indole derivatives have been found to exhibit antibacterial, antifungal (Wang & Ng, 2002; Singh et al., 2000; Tsotinis et al., 1997; Quetin-Leclercq et al., 1995) and antitumour activities (Andreani et al., 2001).

The longer C—N distances [N1—C2 = 1.417 (2) Å and N1—C5 = 1.421 (2) Å] are indicative of the electronic withdrawing character of the phenylsulfonyl group. Atom S1 has a distorted tetrahedral configuration. The widening of the O1—S1—O2 angle to 120.09 (8)°, and the resultant narrowing of the N1—S1—C10 to 104.99 (8)°, from the ideal tetrahedral values, are attributed to the Thorpe- Ingold effect (Bassindale, 1984). The indole ring system is planar. The sum of bond angles around N1 (358.0°) indicates that N1 is in sp² hybridization. The sulfonyl bound phenyl ring is almost perpendicular to the indole ring system, with a dihedral angle of 87.96 (6)°. The benzylphenyl ring is oriented at an angle of 76.69 (5)° with respect to the indole ring system. The ester groups attached to the indole ring system assume extended conformations [C3—C23—C24—C25 = 178.7 (2)°, C23—C24—C25—O4 = -176.8 (2)°, C24—C25—O4—C26 =179.4 (2)°, C25—O4—C26—C27 = 172.6 (2)°]. An intramolecular C6—H6···O1 hydrogen bond is observed.

In the crystal structure, the molecules are linked into a zigzag C(10) chain along the b axis by intermolecular C—H···O hydrogen bonds (Table 1 and Fig.2).

Experimental

To a solution of diethyl-2-((2-(bromomethyl)-1-(phenylsulfonyl)-1H-indol-3-yl)methylene)malonate (0.5 g, 0.96 mmol) in dry benzene (15 ml), ZnBr₂ (0.43 g, 1.90 mmol) was added. The reaction mixture was then refluxed for 5 h under N₂ atmosphere. It was then poured over ice-water (50 ml) containing 1 ml of concentrated HCl, extracted with chloroform (2 × 10 ml) and dried (Na₂SO₄). Removal of solvent followed by flash column chromatography (silica gel, 230–420 mesh, n-hexane/ethyl acetate 99:1) led to the isolation of diethyl-2-((2-benzyl-1-(phenylsulfonyl)-1H-indol-3-yl)methylene)malonate as a colourless solid. Single crystals were obtained by recrystallization from CDCl₃.