5′′-(4-Meth­oxy­benzyl­idene)-1′-(4-meth­oxy­phen­yl)-1′′-methyl-1′,2′,3′,5′,6′,7′,8′,8a′-octa­hydro­dispiro­[acenaphthyl­ene-1,3′-indolizine-2′,3′′-piperidine]-2,4′′(1H)-dione

J Suresh; R A Nagalakshmi; S Sivakumar; R Ranjith Kumar; P L Nilantha Lakshman

doi:10.1107/S1600536813001177

. 2013 Jan 19;69(Pt 2):o256–o257. doi: 10.1107/S1600536813001177

5′′-(4-Methoxybenzylidene)-1′-(4-methoxyphenyl)-1′′-methyl-1′,2′,3′,5′,6′,7′,8′,8a′-octahydrodispiro[acenaphthylene-1,3′-indolizine-2′,3′′-piperidine]-2,4′′(1H)-dione

J Suresh ^a, R A Nagalakshmi ^a, S Sivakumar ^b, R Ranjith Kumar ^b, P L Nilantha Lakshman ^c,^*

PMCID: PMC3569788 PMID: 23424534

Abstract

In the title compound, C₃₉H₃₈N₂O₄, the pyridinone ring adopts a twisted half-chair conformation with the N atom deviating by 0.3304 (1) and with the methylene C atom adjacent to the octahydroindolizine unit deviating by 0.444 (3) Å from the mean plane defined by the other four atoms. In the octahydroindolizine system, the pyrrolidine ring exhibits an envelope conformation, with the fused methyne C atom deviating by 0.6315 (1) Å from the mean plane defined by the other four atoms, and the piperidine ring exhibits a distorted chair conformation, as reflected in the puckering parameters Q = 0.568 (4) Å, θ = 1.5 (4) and ϕ = 161 (16)°. In the crystal pairs of weak C—H⋯O interactions form centrosymmetric dimers, which are further connected by C—H⋯π interactions. The crystal studied was a non-merohedral twin, with a domain ratio of 0.91:0.09.

Related literature

For general properties of indolizines, see: Weidner et al. (1989 ▶); Katritzky et al. (1999 ▶); Asano et al. (2000 ▶); Gilchrist (2001 ▶); Sarkunam & Nallu (2005 ▶); Tielmann & Hoenke (2006 ▶); Oslund et al. (2008 ▶); Vemula et al. (2011 ▶); Singh & Mmatli (2011 ▶). For bond lengths and angles in a related structure, see: Suresh et al. (2011 ▶). For ring conformation analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₃₉H₃₈N₂O₄
M _r = 598.71
Monoclinic,
a = 8.379 (5) Å
b = 16.958 (5) Å
c = 22.063 (5) Å
β = 96.605 (5)°
V = 3114 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.21 × 0.19 × 0.18 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.967, T _max = 0.974
5537 measured reflections
5537 independent reflections
3900 reflections with I > 2σ(I)

Refinement

R[F ² > 2σ(F ²)] = 0.066
wR(F ²) = 0.183
S = 1.05
5537 reflections
407 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.23 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: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Click here for additional data file.^{(29.4KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813001177/bh2471sup1.cif

e-69-0o256-sup1.cif^{(29.4KB, cif)}

Click here for additional data file.^{(265.6KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813001177/bh2471Isup2.hkl

e-69-0o256-Isup2.hkl^{(265.6KB, hkl)}

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

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

Cg1 is the centroid of the benzene ring (C52–C57) in the phenylmethylidene group.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C77—H77A⋯O2ⁱ	0.96	2.54	3.418 (5)	152
C58—H58C⋯Cg1ⁱⁱ	0.96	2.93	3.822 (5)	156

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

Acknowledgments

JS and RAN thank the management of Madura College for their encouragement and support. RRK thanks the DST, New Delhi, for funds under the fast-track scheme (grant No. SR/FT/CS-073/2009).

supplementary crystallographic information

Comment

Indolizines are used as dyes (Weidner et al., 1989), pharmaceuticals (Singh & Mmatli, 2011), and spectroscopic sensitizers (Katritzky et al., 1999; Sarkunam & Nallu, 2005; Gilchrist, 2001; Vemula et al., 2011). Indolizines, both synthetic and natural, have also been ascribed with a number of useful biological activities (Asano et al., 2000; Tielmann & Hoenke, 2006; Oslund et al., 2008) such as antibacterial, antiviral, CNS depressants, anti-HIV, anti-cancer, and have been used for treating cardiovascular ailments. In view of its medicinal importance we report the crystal structure of the title compound.

In the title compound (Fig. 1), the central pyridinone ring with the methyl substituent in an equatorial position, adopts twisted half chair conformation with atoms N2 and C2 deviating by 0.3304 (1) and -0.444 (3) Å respectively, from the mean plane defined by other atoms C3/C4/C5/C6. The O1 atom is deviating by -0.4117 (1) Å from the above mean plane. The sum of bond angles around N2, 332 (9)°, indicates a pyramidal geometry. In the fused system, the pyrrolidine ring adopts the twisted envelope conformation with C8 atom at the flap deviating by -0.6315 (1) Å from the mean plane defined by other atoms C7/C3/C13/N1, and this orientation may be due to the inter-molecular C7— H7A···O2 interaction. In the fused system, the piperidine ring adopts a slightly distorted chair conformation as evident from the puckering parameters Q = 0.568 (4) Å, θ = 1.5 (4)° and φ = 161 (16)° (Cremer & Pople, 1975). The twist of the 4-methoxy benzene ring (C52 to C57) with respect to the spiro junction is denoted by the torsion angle C5—C51—C52—C57 = -46.4 (5)°. The dihedral angles between the mean plane of the pyridinone ring, defined by atoms C3/C4/C5/C6 and 4-methoxy benzene rings are 85.58 (1) and 61.91 (1)°. The carbonyl bond lengths, C4═O1 and C14═02 [1.217 (4) Å for both], are somewhat long, due to C—H···O contacts. Although atoms C8, C12, C13 attached to the atom N1, are all sp³ hybridized, their different environments cause differences in bond lengths [N1—C12: 1.466 (4) Å, N1—C8: 1.453 (4) Å, and N1—C13: 1.466 (4) Å] and in the bond angles [C12—N1—C13: 116.9 (3)°, C13—N1—C8: 107.7 (2)° and C12—N1—C8: 114.3 (3)°]. The methoxy groups substituted at the phenyl rings are nearly coplanar, as it can be seen from the torsion angles C77—O3—C74—C73 = 2.5 (6)° and C58—O4—C55—C54 = -3.9 (6)°. The C—C bond lengths and C—C—C angles in the acenaphthylene group compare with those of related structures (Suresh et al., 2011).

The structure features weak intra-molecular interactions and inter-molecular interactions. A weak inter-molecular interaction, viz C77—H77A···O2, generates a ring motif R²₂(25), forming centrosymmetric dimers, and these dimers are interconnected by C—H···π interactions (Fig. 2), involving the benzene ring C52···C57.

Experimental

A mixture of 1-methyl-3,5-bis[(E)-4-methoxyphenyl-methylidene]tetrahydro-4(1H)-pyridinone (1 mmol), acenaphthenequinone (1 mmol) and piperidine-2-carboxylic acid (1 mmol) was dissolved in isopropyl alcohol (15 ml) and refluxed for 60 min. After completion of the reaction (TLC), the mixture was poured into water (50 ml), the precipitated solid was filtered and washed with water (100 ml) to obtain pure yellow solid. Melting point: 520 K, yield: 94%.