1′-Methyl-4′-(1-naphth­yl)-1′′,2′′,3′′,4′′-tetra­hydro­indane-2-spiro-2′-pyrrolidine-3′-spiro-2′′-naphthalene-1,3,1′′-trione

S Selvanayagam; B Sridhar; K Ravikumar; P Saravanan; R Raghunathan

doi:10.1107/S1600536811004880

. 2011 Feb 12;67(Pt 3):o629. doi: 10.1107/S1600536811004880

1′-Methyl-4′-(1-naphthyl)-1′′,2′′,3′′,4′′-tetrahydroindane-2-spiro-2′-pyrrolidine-3′-spiro-2′′-naphthalene-1,3,1′′-trione

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

PMCID: PMC3052033 PMID: 21522383

Abstract

In the title compound, C₃₂H₂₅NO₃, the pyrrolidine ring adopts an envelope conformation, whereas the cyclohexanone ring in the tetrahydronaphthalene fused-ring system adopts a half-chair conformation. The indanedione unit is oriented at an angle of 58.9 (1)° with respect to the naphthyl ring system. Three intramolecular C—H⋯O close contacts and an intramolecular C—H⋯π interaction are observed. In the crystal, molecules associate via C—H⋯O hydrogen bonds, forming a helical chain with a C(10) motif along the b axis.

Related literature

For general background to pyrrolidine derivatives, see: Bello et al. (2010 ▶); Pettersson et al. (2011 ▶). For related structures, see: Abdul Ajees et al. (2002 ▶); Selvanayagam et al. (2005 ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶).

Experimental

Crystal data

C₃₂H₂₅NO₃
M _r = 471.53
Orthorhombic,
a = 10.8442 (9) Å
b = 11.431 (1) Å
c = 19.2701 (16) Å
V = 2388.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 292 K
0.24 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
28122 measured reflections
3233 independent reflections
2941 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.112
S = 1.10
3233 reflections
326 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.16 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/S1600536811004880/ng5116sup1.cif

e-67-0o629-sup1.cif^{(26.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811004880/ng5116Isup2.hkl

e-67-0o629-Isup2.hkl^{(158.6KB, hkl)}

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

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

Cg1 is centroid of the C1/C5/C6/C11/C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O3	0.98	2.23	2.772 (2)	114
C4—H4A⋯O1	0.97	2.53	3.072 (3)	115
C13—H13B⋯O1	0.97	2.59	3.246 (3)	125
C29—H29⋯O2ⁱ	0.93	2.40	3.218 (2)	146
C17—H17⋯O1ⁱⁱ	0.93	2.55	3.442 (3)	163
C14—H14B⋯Cg1	0.97	2.51	3.146 (2)	123

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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 and also thanks the Vice Chancellor and management of Kalasalingam University, Krishnankoil, for their support and encouragement.

supplementary crystallographic information

Comment

Pyrrolidine derivatives are used as norepinephrine reuptake inhibitors and 5-HT(1A) partial agonists for treating neuropsychiatric disorders including depression and anxiety (Pettersson et al., 2011). These derivatives are used as alpha-mannosidase inhibitors and with antitumor activities against hematological and solid malignancies (Bello et al., 2010). In view of these importance, we have undertaken the crystal structure determination of the title compound, a pyrrolidine derivative, and the results are presented here.

The molecular structure of (I) is illustrated in Fig. 1. The C—C bond lengths in the pyrrolidine ring are somewhat longer in particular at two spiro junctions C1 and C2 and the C—N bond lengths are somewhat shorter than normal values. This may be due to steric forces of the bulky substituents at atoms C1 and C2 of the pyrrolidine ring (Abdul Ajees et al., 2002; Selvanayagam et al., 2005).

The sum of the angles at N1 of the pyrrolidine ring [336.3°] is in accordance with sp³ hybridization. The short contacts H3···H24 (2.12 Å) and H4A···H31 (1.96 Å) result in substantial widening of the C24—C23—C22 and C31—C22—C3 bond angles [123.8 (2)° and 122.4 (2)°, respectively].

The indanedione moiety is planar with a maximum deviation of 0.051 (3) Å for atom C9. The keto O atoms O1 and O2 deviate from this system by 0.115 (2) and 0.177 (2) Å, respectively. The naphthyl group is also planar with a maximum deviation of 0.013 (2) Å for atom C30. This group is oriented at an angle of 58.9° with respect to the indanedione moiety.

Pyrrolidine ring is in an envelope conformation, with puckering parameters q₂ = 0.406 (2) Å and φ = 5.3 (2) °, and with atom N1 deviating 0.601 (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-C13) = 0.070 (1)° (Nardelli, 1983).

The molecular structure is influenced by an intramolecular C—H···O hydrogen bonds and weak C—H···π interactions. In the molecular packing, C—H···O hydrogen bonds involving atoms C17 and O1 link symmetry related molecules to form a helical shape arrangement in the unit cell (Fig. 2 and Table 1). In addition to this another C—H···O hydrogen bonds form a C(10) chain motif in the unit cell.

Experimental

To a mixture of ninhydrin (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.