1′-Methyl-4′-(1-naphth­yl)-3′′-(1-naphthyl­methyl­ene)acenaphthene-1-spiro-2′-pyrrolidine-3′-spiro-1′′-cyclo­hexane-2,2′′-dione

S Athimoolam; V Anu Radha; S Asath Bahadur; R Ranjith Kumar; S Perumal

doi:10.1107/S1600536807061387

. 2007 Dec 6;64(Pt 1):o95–o96. doi: 10.1107/S1600536807061387

1′-Methyl-4′-(1-naphthyl)-3′′-(1-naphthylmethylene)acenaphthene-1-spiro-2′-pyrrolidine-3′-spiro-1′′-cyclohexane-2,2′′-dione

S Athimoolam ^a,^*, V Anu Radha ^a, S Asath Bahadur ^a, R Ranjith Kumar ^b, S Perumal ^b

PMCID: PMC2915050 PMID: 21200972

Abstract

In the title compound, C₄₂H₃₃NO₂, the six-membered cyclohexanone ring adopts a slightly distorted chair conformation and the five-membered pyrrolidine ring is in an envelope conformation. The molecular structure features four intramolecular C—H⋯O interactions and an intramolecular C—H⋯π interaction. Furthermore, the crystal packing is stabilized by an intermolecular C—H⋯O and three intermolecular C—H⋯π interactions.

Related literature

For the biological importance of pyran derivatives, see: Babu & Raghunathan (2007 ▶); Chande et al. (2005 ▶); De March et al. (2002 ▶); Escolano & Jones (2000 ▶); Fejes et al. (2001 ▶); Poornachandran & Raghunathan (2006 ▶); Raj & Raghunathan (2001 ▶); Raj et al. (2003 ▶); Pinna et al. (2002 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶). For hydrogen-bonding interactions, see: Desiraju & Steiner (1999 ▶).

Experimental

Crystal data

C₄₂H₃₃NO₂
M _r = 583.69
Monoclinic,
a = 12.4398 (8) Å
b = 17.3501 (11) Å
c = 14.4685 (9) Å
β = 90.728 (17)°
V = 3122.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 (2) K
0.22 × 0.18 × 0.16 mm

Data collection

Nonius MACH3 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.943, T _max = 0.986
6169 measured reflections
5489 independent reflections
3098 reflections with I > 2σ(I)
R _int = 0.022
3 standard reflections frequency: 60 min intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.164
S = 1.02
5489 reflections
407 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 Express; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXTL/PC (Bruker, 2000 ▶); program(s) used to refine structure: SHELXTL/PC; molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXTL/PC.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807061387/sj2436sup1.cif

e-64-00o95-sup1.cif^{(24.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807061387/sj2436Isup2.hkl

e-64-00o95-Isup2.hkl^{(263.3KB, hkl)}

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

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

Cg1, Cg2, Cg3 and Cg4 are the centroids of the C7/C70–72/C80, C95–C100, C26–C31 and C72–76/80 rings.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5B⋯O1	0.97	2.37	3.084 (3)	130
C8—H8A⋯O1	0.97	2.51	3.078 (4)	117
C9—H9⋯O2	0.98	2.26	2.803 (3)	114
C21—H21⋯O2	0.93	2.42	2.750 (3)	101
C73—H73⋯O1ⁱ	0.93	2.50	3.231 (4)	136
C4—H4A⋯Cg1	0.97	2.64	3.337 (3)	129
C75—H75⋯Cg2ⁱⁱ	0.93	2.74	3.646 (3)	164
C78—H78⋯Cg3ⁱⁱⁱ	0.93	2.82	3.622 (4)	145
C96—H96⋯Cg4^iv	0.93	2.96	3.742 (4)	142

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

Acknowledgments

SA and SAB sincerely thank the Vice Chancellor and management of the Kalasalingam University, Anand Nagar, Krishnan Koil, for their support and encouragement.

supplementary crystallographic information

Comment

1,3-Dipolar cycloaddition of azomethine ylides to alkenes affords pyrrolidines with high selectivities. Azomethine ylides are reactive and versatile 1,3-dipoles, which react readily with diverse dipolarophiles affording pyrrolizines, pyrrolidines and pyrazolidines (Fejes et al., 2001; De March et al., 2002). Pyrrolidine derivatives are widely used as organic catalysts and also serve as important structural units in biologically active molecules. Pyrrolidine derivatives, apart from displaying important biological activities (Pinna et al., 2002; Escolano & Jones, 2000), are present in natural products such as cephalotoxin, kainic acid, domoic acid and quinocarcin. The cycloaddition of azomethine ylides to dipolarophiles with exocyclic double bonds affords spiro-pyrrolidines (Raj & Raghunathan, 2001; Poornachandran & Raghunathan, 2006), which display important biological activities (Raj et al., 2003). Synthesis of spiro compounds has drawn considerable attention from chemists, in view of their very good antimycobacterial activity (Chande et al., 2005). Acenaphthenequinone is a versatile precursor for azomethine ylide cycloaddition as it reacts with various α-amino acids generating reactive 1,3-dipoles (Babu & Raghunathan, 2007).

In the title compound (I), Fig. 1, the six-membered cyclohexanone ring adopts a slightly distorted chair conformation [q₂=0.283 (3) Å, π₂=202.3 (5)° and q₃=0.419 (3) Å; Cremer & Pople, 1975] and the five-membered pyrrolidine ring is in envelope conformation [q₂=0.401 (3) Å and π₂=351.5 (4)°; Cremer & Pople, 1975] (Fig. 1). The dihedral angles between the acenaphthene group and the planes through the naphthyl rings are observed to be 78.7 (1) and 33.2 (1)°. Planes through the naphthyl units themselves are oriented at a dihedral angle of 68.3 (1)°.

The molecular structure features four C—H···O and a C—H···π intramolecular interactions (Desiraju & Steiner, 1999) and the crystal packing is further stabilized by a C—H···O and three C—H···π intermolecular interactions (Fig 2; Table 1). The centroids in detailed in Table 1 are identified as follows: Cg1 - ring C7/C70–72/C80; Cg2 - ring C95–100; Cg3 - ring C26–31; Cg4 - ring C72–76/80.

Experimental

A mixture of 2,6-bis[(E)-1-naphthylmethylidene] cyclohexanone (1 mmol), acenaphthenequinone (1 mmol) and sarcosine (1 mmol) was dissolved in methanol (10 ml) and refluxed for 1 h. After completion of the reaction as evident from TLC, the mixture was poured into water (50 ml), the precipitated solid was filtered and washed with water (100 ml) to obtain pure 1-methyl-4-(1-naphthyl)-pyrrolo-(spiro-[2.2"]-acenaphthene-1'-one) -spiro[3.3']-6'-(1-naphthyl)methylidenecyclohexanone as yellow solid. The compound was recrystallized from a 1:1 mixture of methanol:ethyl acetate and a yellow solid is obtained, Yield 98%