5′′-(4-Chloro­benzyl­idene)-4′-(4-chloro­phen­yl)-5-fluoro-1′,1′′-dimethyl­indoline-3-spiro-2′-pyrrolidine-3′-spiro-3′′-piperidine-2,4′′-dione

J Kalyana Sundar; B Devi Bala; S Natarajan; J Suresh; P L Nilantha Lakshman

doi:10.1107/S1600536811007550

. 2011 Mar 5;67(Pt 4):o801–o802. doi: 10.1107/S1600536811007550

5′′-(4-Chlorobenzylidene)-4′-(4-chlorophenyl)-5-fluoro-1′,1′′-dimethylindoline-3-spiro-2′-pyrrolidine-3′-spiro-3′′-piperidine-2,4′′-dione

J Kalyana Sundar ^a, B Devi Bala ^b, S Natarajan ^a, J Suresh ^c, P L Nilantha Lakshman ^d,^*

PMCID: PMC3099878 PMID: 21754090

Abstract

The piperidine ring of the title compound, C₃₀H₂₆Cl₂FN₃O₂, adopts a twisted chair conformation. The pyrrolidine ring has a twisted envelope structure with the N atom at the flap [displaced by 0.592 (3) Å]. The fluorooxindole, chlorophenyl and chlorobenzylidene groups are planar with r.m.s. deviations of 0.0348, 0.0048 and 0.0048 Å, respectively. The structure is stabilized by intermolecular N—H⋯O hydrogen bonds.

Related literature

For biological applications of 1,4-dihydropyridine derivatives, see: Jerom & Spencer (1988 ▶); Perumal et al. (2001 ▶); Hagenbach & Gysin (1952 ▶); Mobio et al. (1989 ▶); Katritzky & Fan (1990 ▶); Ganellin & Spickett (1965 ▶); El-Subbagh et al. (2000 ▶). For their use as synthetic intermediates in the preparation of various pharmaceuticals, see: Wang & Wuorola (1992 ▶). For their ocurrence in natural products such as alkaloids, see: Angle & Breitenbucher (1995 ▶).

Experimental

Crystal data

C₃₀H₂₆Cl₂FN₃O₂
M _r = 550.44
Monoclinic,
a = 16.694 (3) Å
b = 8.705 (4) Å
c = 18.474 (3) Å
β = 103.27 (4)°
V = 2613.3 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 293 K
0.23 × 0.21 × 0.18 mm

Data collection

Nonius MACH3 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.936, T _max = 0.950
5427 measured reflections
4581 independent reflections
2891 reflections with I > 2σ(I)
R _int = 0.020
3 standard reflections every 60 min intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.104
S = 1.02
4581 reflections
349 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ▶); 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811007550/zj2003sup1.cif

e-67-0o801-sup1.cif^{(26.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811007550/zj2003Isup2.hkl

e-67-0o801-Isup2.hkl^{(224.4KB, 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
N3—H1N⋯O1ⁱ	0.84 (3)	2.50 (3)	3.288 (3)	157 (3)

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

JK thanks the UGC for an RFSMS fellowship. SN thanks the CSIR for funding under the Emeritus Scientist Scheme.

supplementary crystallographic information

Comment

In the family of heterocyclic compounds, nitrogen containing heterocycles especially substituted piperidin-4-ones have considerable importance due to their variety of biological properties such as analgesic (Jerom et al., 1988), local anaesthetic (Perumal et al., 2001; Hagenbach & Gysin, 1952), antimicrobial, bactericidal, fungicidal, herbicidal, anticancer, CNS stimulant and depressant activities (Mobio et al., 1989; Katritzky & Fan, 1990; Ganellin & Spickett, 1965) and antiviral, antitumour (El-Subbagh et al., 2000). Also they are important synthetic intermediates in the preparation of various pharmaceuticals (Wang & Wuorola, 1992) and widely prevalent in natural products such as alkaloids (Angle & Breitenbucher, 1995). Hence, the present X-ray crystallographic study of the title compound has been carried out to determine the conformation of the system.

The piperidine ring of the title compound, C₃₀H₂₆N₃O₂Cl₂F, adopts a twisted chair conformation (C8/C9/C10/C11/N1/C12). Pyrrolidine ring has the twisted envelope structure with N atom at the flap (0.592 (3)Å from the mean plane formed by the atoms C10/C14/C23/C24) and this orientation may be influenced by the intramolecular C23—H23A···O2 hydrogen bond (Table 1).

Fluorooxindole, the chlorophenyl and chlorophenylmethylidine groups are planar as confirmed by thevalues of the r.m.s. deviation (0.0348 Å, 0.0048Å and 0.0048 Å), respectively,from the mean planes of the above groups. Flurooxindole is inclined with the plane of chlorophenyl by 33.99 (2)° and 55.56 (2)° with the mean plane of chlorophenylmethilidine. The sum of the bond angles around N1 atom (334.22°) of the piperidine ring in the molecule is in accordance with the sp² hybridization. Further, the structure is stabilized by intermolecular N—H···O hydrogen bond and intramolecular C—H···O hydrogen bonds.

Experimental

A mixture of 1-methyl-3,5-bis[(E)-chlorobenzylidene]tetrahydro-4 (1H)-pyridin-ones (1 mmol), 5-fluoroisatin (1 mmol) and sarcosine in methanol (10 ml) was refluxed for 30 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 to obtain the pure product. The product was dissolved in methonol and allowed to evoporate at room temperature. Transparent, needle-shaped, colourless crystals of small sizes (8 x 2 x 2 mm³)were obtained in a period of about a week. Yield:94%; M.p:224 °C