rac-5′′-(4-Fluoro­benzyl­idene)-1′-(4-fluoro­phen­yl)-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/S1600536812051094

. 2012 Dec 22;69(Pt 1):o140–o141. doi: 10.1107/S1600536812051094

rac-5′′-(4-Fluorobenzylidene)-1′-(4-fluorophenyl)-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: PMC3588349 PMID: 23476397

Abstract

In the title E isomer of the racemic compound, C₃₇H₃₂F₂N₂O₂, the pyridinone ring adopts a twisted half-chair conformation with the N atom deviating by −0.355 (3) Å and with the methylene C atom next to octahydroindolizine moiety deviating by 0.415 (3) Å from the mean plane defined by other four atoms. In the octahydroindolizine system, the pyrrolidine ring exhibits an envelope conformation with the fused methyne C atom deviating by 0.6496 (1) Å from the mean plane defined by four other atoms, and the piperidine ring exhibits a distorted chair conformation as evident from the puckering parameters Q = 0.568 (2) Å, θ = 1.0 (2) and Φ = 256 (11)°. In the crystal, C—H⋯O interactions connect the molecules into chains along [101].

Related literature

For general properties of indolizines, see: Malonne et al. (1998 ▶); Medda et al. (2003 ▶); Pearson & Guo (2001 ▶). For related structures, see: Sussman & Wodak (1973 ▶); Wodak (1975 ▶). For ring conformation analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₃₇H₃₂F₂N₂O₂
M _r = 574.65
Monoclinic,
a = 10.2716 (4) Å
b = 20.0353 (7) Å
c = 14.3790 (6) Å
β = 97.047 (1)°
V = 2936.8 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 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
33177 measured reflections
7519 independent reflections
4823 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.126
S = 1.01
7519 reflections
388 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.21 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.^{(29.6KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812051094/ld2088sup1.cif

e-69-0o140-sup1.cif^{(29.6KB, cif)}

Click here for additional data file.^{(360.5KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812051094/ld2088Isup2.hkl

e-69-0o140-Isup2.hkl^{(360.5KB, 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
C11—H11A⋯O1ⁱ	0.97	2.49	3.352 (2)	148

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Symmetry code: (i) Inline graphic .

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

Indolizine derivatives have been found to possess a variety of biological activities such as anti-inflammatory (Malonne et al., 1998), antiviral (Medda et al., 2003) and anti-tumor (Pearson & Guo, 2001) activities. In view of its medicinal importance and in conjunction with our research interests, we synthesized the title compound and report here its X-ray structure.

In the title compound (Fig.1), the pyridinone ring adopts twisted half chair conformation with atoms N2 and C2 deviating by -0.355 (3)Å and 0.415 (3)Å respectively, from the mean plane defined by other atoms C3/C4/C5/C6. The sum of bond angles around N2 (332.65 (1) °) indicates a pyramidal geometry. Although the atoms C1, C2, C6 attached to the atom N2, are all in Sp² hybridization, their different environments cause differences in bond lengths (N2-C2 (1.4467 (19) Å) and N2-C6 (1.457 (2) Å)) and in the bond angles (C1-N2-C2 (112.35 (13) °), C1-N2-C6 (111.00 (14) °) and C2-N2-C6 (109.31 (12) °)). The methyl group at position 1 of the pyridinone ring is in equatorial orientation, denoted by the torsion angle C1-N2-C6-C5 (177.38 (1) °). In the fused system , the pyrrolidine ring adopts the twisted envelope conformation with C8 atom at the flap deviating by 0.6496 (1) Å from the mean plane defined by other atoms C7/C3/C13/N1 and this orientation may be due to the intra-molecular C7—H7···O1 interaction. In the fused system the piperidine ring adopts a slightly distorted chair conformation as evident from the puckering parameters Q = 0.568 (2) Å, θ = 1.0 (2)° and Φ = 256 (11)° (Cremer & Pople, 1975). The twist of the 4-fluorobenzene ring (C52-C57) with respect to the spiro junction is denoted by the torsion angle C5-C51-C52-C57 (-49.1 (2) °). The dihedral angle between the mean plane of the pyridinone ring, defined by the atoms C2/C4/C5/C6 with the two 4-fluorobenzene rings are 87.70 (1) ° and 63.20 (1)°. The carbonyl bond length, i.e C4=O1 (1.214 (2) Å), is somewhat longer, due to C—H···O contacts. The C8—N1 bond length (1.456 (2) Å) is comparable with the CSp²—NSp² distance found in similar structures (Sussman & Wodak, 1973; Wodak, 1975).

The structure is stabilized by intermolecular C11—H11A···O1 interactions generating chains along [101] (Fig. 2).

Experimental

A mixture of 1-methyl-3,5-bis[(E)-4-fluromethylidene]tetrahydro-4(1H)- pyridinone (1 mmol), acenaphthenequinone (1 mmol) and piperidine-2- carboxylic acid (1 mmol) was dissolved in isopropyl alcohol (15 ml) and heated to reflux for 60 min. 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 yellow solid. Melting point:498 K, Yield: 93%