1′-Methyl-2,2′′-dioxoindoline-3-spiro-2′-pyrrolidine-3′-spiro-3′′-indoline-4′,4′-di­carbonitrile

P Ramesh; S S Sundaresan; N Vidhya Lakshmi; Paramasivan T Perumal; M N Ponnuswamy

doi:10.1107/S1600536809028025

. 2009 Jul 22;65(Pt 8):o1945. doi: 10.1107/S1600536809028025

1′-Methyl-2,2′′-dioxoindoline-3-spiro-2′-pyrrolidine-3′-spiro-3′′-indoline-4′,4′-dicarbonitrile

P Ramesh ^a, S S Sundaresan ^a, N Vidhya Lakshmi ^b, Paramasivan T Perumal ^b, M N Ponnuswamy ^a,^*

PMCID: PMC2977508 PMID: 21583626

Abstract

In the title compound, C₂₁H₁₅N₅O₂, the pyrrolidine ring adopts a twist conformation. Both the oxindole rings are planar [maximum deviations of 0.076 (1) and 0.029 (1) Å in the two rings] and are oriented at a dihedral angle of 72.7 (1)°. The crystal structure is stabilized by C—H⋯O, N—H⋯O, N—H⋯N and C—H⋯π interactions.

Related literature

For the use of indole derivatives as bioactive drugs, see: Stevenson et al. (2000 ▶). They exibit anti-allergic, central nervous system depressant and muscle-relaxant properties, see: Harris & Uhle (1960 ▶); Ho et al. (1986 ▶). Indoles also exhibit high aldose reductase inhibitory activity, see: Rajeswaran et al. (1999 ▶). For puckering and asymmetry parameters, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶).

Experimental

Crystal data

C₂₁H₁₅N₅O₂
M _r = 369.38
Monoclinic,
a = 13.3173 (3) Å
b = 9.9480 (2) Å
c = 13.3950 (3) Å
β = 91.827 (1)°
V = 1773.67 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.972, T _max = 0.982
26314 measured reflections
6939 independent reflections
4820 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.142
S = 1.02
6939 reflections
263 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028025/bt2998sup1.cif

e-65-o1945-sup1.cif^{(23.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028025/bt2998Isup2.hkl

e-65-o1945-Isup2.hkl^{(332.7KB, 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
C5—H5⋯O2	0.93	2.49	3.1371 (15)	127
C17—H17⋯O1	0.93	2.47	3.1433 (16)	130
C20—H20B⋯O1	0.97	2.54	2.9986 (14)	109
C22—H22B⋯O2ⁱ	0.96	2.53	3.3713 (15)	147
N12—H12⋯O2ⁱⁱ	0.853 (17)	2.591 (17)	3.2114 (13)	130.5 (14)
N12—H12⋯N19ⁱⁱ	0.853 (17)	2.371 (17)	3.1613 (13)	154.4 (15)
C14—H14⋯O2ⁱⁱ	0.93	2.51	3.2305 (16)	135
N1—H1⋯N24ⁱⁱⁱ	0.913 (18)	2.174 (18)	3.0315 (15)	156.1 (16)
C7—H7⋯Cg5^iv	0.93	2.84	3.5366 (15)	156

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg5 is the centroid of the C13–C18 ring.

Acknowledgments

PR thanks Dr Babu Varghese, SAIF, IIT-Madras, India, for his help with the data collection.

supplementary crystallographic information

Comment

Indole derivatives are used as bioactive drugs (Stevenson et al., 2000) and they exibit anti-allergic, central nervous system depressant and muscle relaxant properties (Harris & Uhle 1960; Ho et al., 1986). Indoles have been proved to display high aldose reductase inhibitory activity (Rajeswaran et al., 1999). Against this background and to ascertain the molecular conformation, the structure determination of the title compound has been carried out.

The ORTEP plot of the molecule is shown in Fig. 1. The pyrrolidine ring adopts a twist conformation with the puckering parameters (Cremer & Pople, 1975) and the asymmetry parameters (Nardelli, 1983) for this ring q₂ = 0.399 (1)Å, π = 202.5 (2)° and Δ2(C21) = 3.0 (1)°. Both oxindole rings are planar and the keto atoms O1 and O3 deviate by 0.207 (1) and -0.093 (1)Å, respectively. The oxindole rings attached at 4 and 5 positions of the pyrrolidine ring are oriented at an angle of 72.7 (1)°. In the indole ring system, the endocyclic angles at C8 and C14 are contracted to 117.3 (1)° and 117.4 (1)°, while those at C9 and C13 are expanded to 122.2 (1)° and 122.5 (1)°, respectively. The cyano groups are almost linear which can be seen from the bond angles of 176.4 (1)° (C21-C23-N24) and 175.2 (1)° (C21-C25-N26). The sum of the bond angles around the hetero nitrogen atom in the oxindole ring systems are N1 [360.0°] and N12 [359.8°] and in accordance with the sp² hybridization. The sum of the bond angles at N19 (334.4°) in the pyrrolidine ring system is in accordance with the sp³ hybridization.

The packing of the molecules in the crystal structure is stabilized by C-H···O, N-H···O, N-H···N and C-H···π interactions. Atom C22 (x, y, z) donates a proton to O2 (1/2-x, 1/2+y, 1/2-z) and forms a zig-zag chain running along the b-axis. The intermolecular N1-H1···N24 hydrogen bond forms a one dimensional chain running along the ac diagonal axis. The indole ring interacts with the other indole moiety through an intermolecular C-H···π interaction involving atom C7, the separation between H7 and the centroid (Cg5) of the ring (C13/C14/C15/C16/C17/C18) being 2.666Å.

Experimental

A mixture of isatin, sarcosine and isatylidene malononitrile in methanol and a catalytic amount of silica gel (100–200 mesh) was added and refluxed for about 15 minutes. The precipitated solid was filtered, dried and purified by column chromatography to afford the pure product in 87% yield. The purified compound was recrystallized from ethanol by using slow evaporation method.