Ethyl 2-[(N-meth­oxy-N-methyl­carbamo­yl)meth­yl]-1-(phenyl­sulfon­yl)-1H-indole-3-carboxyl­ate

G Chakkaravarthi; V Dhayalan; A K Mohanakrishnan; V Manivannan

doi:10.1107/S1600536808014979

. 2008 May 21;64(Pt 6):o1139. doi: 10.1107/S1600536808014979

Ethyl 2-[(N-methoxy-N-methylcarbamoyl)methyl]-1-(phenylsulfonyl)-1H-indole-3-carboxylate

G Chakkaravarthi ^a,^*, V Dhayalan ^b, A K Mohanakrishnan ^b, V Manivannan ^c

PMCID: PMC2961377 PMID: 21202648

Abstract

In the title compound, C₂₁H₂₂N₂O₆S, the phenyl ring forms a dihedral angle of 83.17 (7)° with the indole ring system. The methyl group of the ester unit is disordered over two positions with site occupancies of 0.635 (6) and 0.365 (6). In the crystal structure, weak intramolecular C—H⋯O interactions and intermolecular C—H⋯O, C—H⋯N and C—H⋯π interactions are observed.

Related literature

For biological activity, see: Merck (1973 ▶, 1974 ▶); Hendi & Basangoudar (1981 ▶); Kolocouris et al. (1994 ▶); Uchida et al. (1989 ▶); Shaaban et al. (1977 ▶). For the structures of closely related compounds, see: Chakkaravarthi et al. (2007 ▶, 2008 ▶).

Experimental

Crystal data

C₂₁H₂₂N₂O₆S
M _r = 430.47
Monoclinic,
a = 8.5827 (3) Å
b = 11.0783 (5) Å
c = 21.7433 (8) Å
β = 97.091 (2)°
V = 2051.58 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 295 (2) K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEX2 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.914, T _max = 0.961
29808 measured reflections
7666 independent reflections
3947 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.064
wR(F ²) = 0.238
S = 1.04
7666 reflections
285 parameters
20 restraints
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014979/is2294sup1.cif

e-64-o1139-sup1.cif^{(22.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808014979/is2294Isup2.hkl

e-64-o1139-Isup2.hkl^{(367.5KB, 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
C2—H2⋯O2	0.93	2.54	2.896 (3)	103
C6—H6⋯O3	0.93	2.37	3.218 (3)	152
C10—H10⋯O6	0.93	2.46	2.969 (4)	114
C13—H13⋯O2	0.93	2.51	3.039 (4)	117
C15—H15A⋯O5	0.97	2.39	2.844 (3)	108
C15—H15B⋯O1	0.97	2.17	2.847 (3)	126
C17—H17B⋯O5ⁱ	0.96	2.47	3.420 (3)	173
C20—H20C⋯N1ⁱⁱ	0.97	2.45	3.351 (4)	155
C20—H20C⋯O2ⁱⁱ	0.97	2.53	3.343 (4)	142
C21A—H21F⋯Cgⁱⁱⁱ	0.96	2.80	3.196 (13)	105

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg is the centroid of the C1–C6 phenyl ring.

Acknowledgments

The authors acknowledge the Sophisticated Analytical Instrument Facility, Indian Institute of Technology, Madras, for the data collection.

supplementary crystallographic information

Comment

In continuation of our studies of indole derivatives, which are found to possess antihypertensive (Merck, 1973), muscle-relaxant (Hendi & Basangoudar, 1981), antiviral (Kolocouris et al., 1994) antiulcer (Uchida et al., 1989) and analgesic (Shaaban et al., 1977) activities, we determined the crystal structure of the title compound, (I). The geometric parameters of the molecule of (I) (Fig. 1) agree well with those reported for similar structures (Chakkaravarthi et al., 2007, 2008).

The plane of phenyl ring forms 83.17 (7)° with the indole ring system. The plane of N1—S1—C1 forms the dihedral angles of 39.36 (9)° and 69.28 (9)°, respectively, with the phenyl ring and the indole ring. The carboxylate group and N-methoxy-N-methylcarbamide group are approximately orthogonal to each other [dihedral angle 88.45 (1)°] and makes the dihedral angles of 18.61 (14)° and 84.81 (7)°, respectively, with the indole ring. The sum of bond angles around N1 (359.69°) indicates that N1 is sp²-hybridized. The torsion angles O1—S1—N1—C7 and O2—S1—N1—C14 [-9.9 (2)° and 48.3 (2)°, respectively] indicate the syn conformation of the sulfonyl moiety.

The methyl C atom of the ester group is disordered over two positions with occupancies of 0.635 (6) and 0.365 (6). The molecular structure is stabilized by weak intramolecular C—H···O interactions and the crystal packing (Fig. 2) exhibits weak intermolecular C—H···O, C—H···N interactions and a C—H···π interaction involving the ring C1—C6 (centroid Cg) (Table 1).

Experimental

CO gas was passed through the stirred solution of Ethyl-1-phenylsulfonyl-2-bromomethylindole-3-carboxylate (5.0 g, 11.84 mmol) in CH₃CN (60 ml). To this, PdCl₂ (200 mg, 1.12 mmol) and an in situ prepared HN(OMe)Me solution [HCl.HN(OMe)Me (230 mg, 23.71 mmol) in CH₃CN (30 ml)], K₂CO₃ (3.27 g, 23.69 mmol) and H₂O (0.5 ml) were added, stirred for 1 h and filtered] were added. Usual work up followed by evaporation of solvent to give sticky product and the crude product was purified by column chromatography (silica gel) using hexane and ethyl acetate mixture (7:3). Crystals suitable for X-ray analysis were grown by slow evaporation of ethyl acetate solution.