1′,1′′-Dimethyl-4′-(naphthalen-1-yl)-1,2,3,4-tetra­hydro­naphthalene-2-spiro-3′-pyrrolidine-2′-spiro-3′′-indoline-1,2′′-dione

S Selvanayagam; K Ravikumar; P Saravanan; R Raghunathan

doi:10.1107/S1600536811007124

. 2011 Mar 2;67(Pt 4):o751. doi: 10.1107/S1600536811007124

1′,1′′-Dimethyl-4′-(naphthalen-1-yl)-1,2,3,4-tetrahydronaphthalene-2-spiro-3′-pyrrolidine-2′-spiro-3′′-indoline-1,2′′-dione

S Selvanayagam ^a,^*, K Ravikumar ^b, P Saravanan ^c, R Raghunathan ^c

PMCID: PMC3099991 PMID: 21754048

Abstract

In the title compound, C₃₂H₂₈N₂O₂, the pyrrolidine ring adopts an envelope conformation, whereas the cyclohexanone ring in the tetrahydronaphthalene fused-ring system adopts a half-chair conformation. The oxindole ring system is oriented at an angle of 48.2 (1)° with respect to the naphthyl ring system. An intramolecular C—H⋯O close contact is observed. In the crystal, molecules associate via two C—H⋯O hydrogen bonds, forming R ₂ ²(14) and R ₂ ²(10) dimers.

Related literature

For general background to pyrrolidine derivatives, see: Obniska et al. (2003 ▶); Peddi et al. (2004 ▶); Kaminski & Obniska (2008 ▶); Stylianakis et al. (2003 ▶). For related structures, see: Selvanayagam et al. (2011 ▶); Gans & Shalloway (2001 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶) and for asymmetry parameters, see: Nardelli (1983 ▶).

Experimental

Crystal data

C₃₂H₂₈N₂O₂
M _r = 472.56
Monoclinic,
a = 8.7529 (8) Å
b = 18.0411 (16) Å
c = 15.4489 (13) Å
β = 98.181 (2)°
V = 2414.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 292 K
0.24 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
27968 measured reflections
5745 independent reflections
4389 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.141
S = 1.04
5745 reflections
327 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97 and PLATON.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811007124/ng5125sup1.cif

e-67-0o751-sup1.cif^{(26.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811007124/ng5125Isup2.hkl

e-67-0o751-Isup2.hkl^{(281.3KB, 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
C12—H12A⋯O1	0.97	2.48	3.143 (2)	126
C13—H13B⋯O1ⁱ	0.97	2.58	3.482 (2)	156
C32—H32A⋯O1ⁱⁱ	0.96	2.59	3.364 (2)	138

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

Acknowledgments

SS acknowledges the Department of Science and Technology (DST), India, for providing computing facilities under the DST-Fast Track Scheme. SS also thanks the Vice Chancellor and management of Kalasalingam University, Krishnankoil, for their support and encouragement.

supplementary crystallographic information

Comment

Spiro-pyrrolidine derivatives are unique tetracyclic 5-HT(2A) receptor antagonist (Obniska et al., 2003; Peddi et al., 2004). These derivatives possess anticonvulsant (Kaminski & Obniska, 2008) and anti-influenza virus (Stylianakis et al., 2003) activities. In view of these importance and continuation of our work on the crystal structure analyis of spiro-pyrrolidine derivatives, we have undertaken the crystal structure determination of the title compound, and the results are presented here.

The X-ray study confirmed the molecular structure and atomic connectivity for (I), as illustrated in Fig. 1. The geometry of pyrrolidine, tetrahydro naphthalin and naphthyl group systems are comparable with the related reported structure (Selvanayagam et al., 2011). Fig. 2 shows a superposition of the pyrrolidine ring of (I) with this related reported structure, using Qmol (Gans & Shalloway, 2001); the r.m.s. deviation is 0.363 Å.

The sum of the angles at N1 of the pyrrolidine ring [334.8°] and N2 of the oxindole ring [359.9°] are in accordance with sp³ and sp² hybridizations. The short contacts H3···H23 (2.06 Å) and H4B···H30 (2 Å) result in substantial widening of the C21—C22—C23 and C21—C30—C29 bond angles [123.6 (2)° and 122.3 (2)°, respectively].

Pyrrolidine ring is in an envelope conformation, with puckering parameters q₂ = 0.409 (1) Å and φ = -175.1 (2) °, and with atom N1 deviating -0.603 (2) Å from the least-squares plane passing through the remaining four atoms (C1-C4) of that ring (Cremer & Pople, 1975). The cyclohexanone ring in the tetrahydro naphthalin ring system has a half-chair conformation with the lowest asymmetry parameters of ΔC₂(C2-C12) = 0.084 (1)° (Nardelli, 1983). The best plane of pyrrolidine ring system make a dihedral angles of 76.9 (1) and 68.9 (1)°, respectively with respect to the oxindole ring and naphtyl group systems.

The molecular structure is influenced by an intramolecular C—H···O close contacts. Atom O1 acts as a trifurcated acceptor for three intramolecular C—H···O contacts. In the molecular packing, C—H···O hydrogen bonds involving atoms C13 and O1 link inversion-related molecules to form R₂² (14) graph-set dimer (Fig. 3 and Table 1). In addition to this another graph-set dimer of R₂²(10) forms in the unit cell involving C32 and O1 atoms via C-H···O hydrogen bonds (Fig. 4).

Experimental

To a mixture of N-methyl isatin (1mmol), sarcosine (1mmol) and 2-napthalidene- 1,2,3,4-tetrahydronaphthalene-1-ones (1mmol) was added and heated under reflux in methanol (20ml) until the disappearance of the starting materials as evidenced by TLC. The solvent was removed under vacuo. The crude product was subjected to column chromatography using petroleum ether-ethyl acetate as eluent. Single crystals were grown by slow evaporation from methanol.