1-Ethyl-4′-(1H-indol-3-ylcarbon­yl)-1′-methyl-2,2′′-dioxodi­spiro­[indoline-3,2′-pyrrolidine-3′,3′′-indoline]-4′-carbo­nitrile dimethyl sulfoxide monosolvate

S Antony Inglebert; Yuvaraj Arun; K Sethusankar; Paramasivam T Perumal

doi:10.1107/S1600536813020485

. 2013 Jul 27;69(Pt 8):o1328–o1329. doi: 10.1107/S1600536813020485

1-Ethyl-4′-(1H-indol-3-ylcarbonyl)-1′-methyl-2,2′′-dioxodispiro[indoline-3,2′-pyrrolidine-3′,3′′-indoline]-4′-carbonitrile dimethyl sulfoxide monosolvate

S Antony Inglebert ^a, Yuvaraj Arun ^b, K Sethusankar ^c,^*, Paramasivam T Perumal ^b

PMCID: PMC3793813 PMID: 24109400

Abstract

In the title compound, C₃₁H₂₅N₅O₃·C₂H₆OS, the three indole/indoline units are all essentially planar with maximum deviations of 0.0172 (3), 0.053 (2) and 0.07 (2) Å. The pyrrolidine ring adopts an envelope conformation with the C atoms bearing the 1-ethyl-2-oxoindole substituent (in which the five-membered ring adopts a twisted conformation) as the flap. The dimethyl sulfoxide solvent molecule is disordered over two positions, with an occupancy factor ratio of 0.871 (4):0.129 (4). The solvent components are linked to the heterocyclic molecule via C—H⋯O and C—H⋯S hydrogen bonds. In the crystal, the solvent components are linked to the heterocyclic molecule via C—H⋯O and C—H⋯S interactions, forming R ₂ ²(10) ring motifs. The molecules are further connected into a chain along the a-axis direction via N—H⋯O hydrogen bonds.

Related literature

For applications of indole derivatives, see: Barden (2011 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For bond-length data, see: Allen et al. (1987 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶). graphic file with name e-69-o1328-scheme1.jpg

Experimental

Crystal data

C₃₁H₂₅N₅O₃·C₂H₆OS
M _r = 593.70
Orthorhombic,
a = 14.078 (5) Å
b = 20.416 (5) Å
c = 20.789 (5) Å
V = 5975 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 295 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.955, T _max = 0.970
26724 measured reflections
5139 independent reflections
3447 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.120
S = 1.03
5139 reflections
431 parameters
48 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.27 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/S1600536813020485/rk2408sup1.cif

e-69-o1328-sup1.cif^{(39.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813020485/rk2408Isup2.hkl

e-69-o1328-Isup2.hkl^{(251.8KB, 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
N4—H4A⋯O4	0.84 (3)	1.89 (3)	2.714 (3)	166 (2)
N1—H1A⋯O2ⁱ	0.84 (3)	2.10 (3)	2.887 (3)	155 (2)
C22—H22⋯S1ⁱⁱ	0.93	2.85	3.717 (3)	157
C32—H32A⋯O3ⁱⁱⁱ	0.96	2.60	3.219 (4)	123

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

Acknowledgments

The authors gratefully acknowledge Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection.

supplementary crystallographic information

Comment

Indole containing compounds are best known for their medicinal properties in the pharmaceutical industry. In modern times, analogs based on indole are significant players in a diverse array of markets such as dyes, plastics, agriculture, vitamin supplements, over-the-counterdrugs, flavour enhancers and perfumery (Barden, 2011).

In the crystal structure of title compound, C₃₁H₂₅N₅O₃^.C₂H₆OS, (Fig. 1), there is a dispiro centers system, which consists of two oxindole rings, an indole ring and a pyrrolidine ring. In crystals organic heterocycles moiety and solvent molecules connected by two intermolecular C–H···S and C–H···O hydrogen bonds (Table 1). The dimethyl sulfoxide solvent molecule is disordered over two positions with site occupancy factors 0.871 (4) and 0.129 (4).

The pyrrolidine ring (N3/C12/C13/C14/C10) adopts an envelope conformation with puckering parameters, q₂ = 0.402 (2)Å, φ(2) = 331.4 (3)°, and with atom C13 deviating by 0.256 (2)Å from the mean plane passing through the rest of the ring atoms (Cremer & Pople, 1975). The carbonitrile group is nearly perpendicular to pyrrolidine ring, as indicated by the torsion angle C12-C10-C11-N2 = 87.4 (2)°. The indole system A makes dihedral angles of 53.13 (15)° and 86.11 (6)° with the oxindole ring systems B & C, respectively. It clearly shows that ring systems A and C are almost perpendicular to each other. Also the dihedral angle between oxindole B and C is 54.40 (5)°. The twisted conformation of the five membered pyrrole ring in oxindole ring system C is observed through the puckering analysis [q₂ = 0.074 (2) Å and φ(2) = 277.1 (18)°].

The indole and oxindole ring systems A, B and C are planar with maximum deviations of 0.0172 (3)Å, 0.053 (2)Å and 0.07 (2)Å for the atoms C4, C14 and C26 from the LS planes. The bond lengths of O2-C16, C16-N4 in oxindole unit B and O3-C23, C23-N5 in oxindole unit C show electron delocalization over atoms O2, C16, N4, O3, C23 and N5.

The cyano bond distance C11≡N2 agrees well with the reported value of 1.138 (7)Å (Allen et al., 1987). The sum of the angles around atom N5 (359.86°) is in accordance with sp² hybridization, whereas the sum of the angles around atom N3 (337.75°) is in accordance with sp³ one. The oxygen atoms attached to C16 and C23 are coplanar with the oxindole ring system B & C as indicated by the torsion angles O2-C16-N4-C18 = -177.3 (2)° and O3-C23-N5-C24 = -176.3 (2)°, respectively.

In the crystal structure, pairs of molecules are linked by intermolecular C–H···O and C–H···S hydrogen bonds to generate R²₂(10) ring motifs (Bernstein et al., 1995). The molecules are further connected into a chain along the a axis via N–H···O intermolecular hydrogen bonds. The packing view of the title compound is shown in Fig. 2. (Macrae et al., 2008).

Experimental

A mixture of 1-ethyl-isatin (1 mmol), sarcosine (1 mmol) and 3-(1H-indol-3-yl)-3-oxo-2-(2-oxoindoline-3-ylidene)propane nitrile (1 mmol) were refluxed in ethanol (10 ml). After completion of the reaction as evidenced by TLC analysis, the reaction mixture was poured into ice-water, the resulting solid was filtered off and purified by column chromatography using ethyl acetate : petroleum ether (6 : 4) as an eluent to afford pure spirooxiindoles in 82% yield.