5′′-Benzyl­idene-5-chloro-1′,1′′-dimethyl-4′-phenyl­dispiro­[indoline-3,2′-pyrrolidine-3′,3′′-piperidine]-2,4′′-dione

I S Ahmed Farag; Adel S Girgis; A A Ramadan; A M Moustafa; Edward R T Tiekink

doi:10.1107/S1600536813032765

. 2013 Dec 7;70(Pt 1):o22–o23. doi: 10.1107/S1600536813032765

5′′-Benzylidene-5-chloro-1′,1′′-dimethyl-4′-phenyldispiro[indoline-3,2′-pyrrolidine-3′,3′′-piperidine]-2,4′′-dione

I S Ahmed Farag ^a,^‡, Adel S Girgis ^b, A A Ramadan ^c, A M Moustafa ^a, Edward R T Tiekink ^d,^*

PMCID: PMC4029213 PMID: 24855467

Abstract

The title compound, C₃₀H₂₈ClN₃O₂, features two spiro links, one connecting the piperidine and pyrrolidine rings, and the other connecting the pyrrolidine ring and indole residue. The configuration about the ethene bond is E. The piperidine ring adopts a half-chair conformation where the C atom connected to the spiro-C atom lies 0.713 (3) Å out of the plane of the remaining five atoms (r.m.s. deviation = 0.086 Å). The pyrrolidine ring has an envelope conformation with the flap atom being the methylene C atom. Centrosymmetric eight-membered {⋯HNCO}₂ amide synthons feature in the crystal packing. These are consolidated into a three-dimensional architecture by phenyl–pyrrolidine C—H⋯N and chlorobenzene–pyrrolidine-bound phenyl C—H⋯π interactions.

Related literature

For the biological activity of related spiropyrrolidine analogues, see: Girgis et al. (2012 ▶); Kumar et al. (2008 ▶). For related structural studies, see: Moustafa et al. (2012 ▶). For the synthesis of the precursor molecule, see: Al-Omary et al. (2012 ▶). graphic file with name e-70-00o22-scheme1.jpg

Experimental

Crystal data

C₃₀H₂₈ClN₃O₂
M _r = 498.00
Monoclinic,
a = 10.5028 (3) Å
b = 20.4117 (6) Å
c = 11.9951 (4) Å
β = 94.877 (1)°
V = 2562.20 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 293 K
0.52 × 0.22 × 0.15 mm

Data collection

Nonius 590 KappaCCD diffractometer
10395 measured reflections
5842 independent reflections
2547 reflections with I > 2σ(I)
R _int = 0.066

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.137
S = 0.94
5842 reflections
327 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) general, I. DOI: 10.1107/S1600536813032765/hg5367sup1.cif

e-70-00o22-sup1.cif^{(26.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813032765/hg5367Isup2.hkl

e-70-00o22-Isup2.hkl^{(280.2KB, hkl)}

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

Cg1 is the centroid of the C25–C30 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3n⋯O2ⁱ	0.86	2.01	2.854 (3)	165
C14—H14⋯N2ⁱⁱ	0.93	2.58	3.480 (4)	163
C20—H20⋯Cg1ⁱⁱⁱ	0.93	2.70	3.268 (3)	121

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

Acknowledgments

This study was supported financially by the Science and Technology Development Fund (STDF), Egypt (grant No. 1133).

supplementary crystallographic information

1. Introduction

2. Experimental

2.1. Synthesis and crystallization

A mixture of equimolar amounts of 3E,5E-1-methyl-3,5-bis(phenylmethylidene)-4-piperidone (5 mmol), prepared by a literature procedure (Al-Omary et al., 2012), 5-chloroisatin and sarcosine in absolute ethanol (25 ml) was boiled under reflux (TLC monitoring). The separated solid was collected and crystallized from n-butanol affording (I). Reaction time 9 h. Colourless crystals. M.pt: 512–514 K. Yield 88%. Anal. Calcd. for C₃₀H₂₈ClN₃O₂ (498.03): C, 72.35; H, 5.67; N, 8.44. Found: C, 72.56; H, 5.81; N, 8.67. IR: ν_max/cm^-1: 3168 (N—H); 1688 (C═O); 1597, 1457 (C═C).

2.2. Refinement

The C-bound H atoms were geometrically placed (C—H = 0.93–0.98 Å) and refined as riding with U_iso(H) = 1.2–1.5U_eq(C). The N-bound H-atoms were treated similarly with N—H = 0.86 Å, and with U_iso(H) = 1.2U_eq(N).

3. Results and discussion

In connection with on-going studies of spiropyrrolidine derivatives (Girgis et al. 2012; Moustafa et al. 2012), the title compound, (I), was synthesised and characterised crystallographically. These compounds have biological activity and the structure of the skeltal structure is well established (Kumar et al. 2008).

There are two spiro links in the molecule, Fig. 1, i) where the piperidine and pyrrolidine rings are connected at C1, and ii) where the pyrrolidine ring and indole residue are connected at C6. The phenylmethylidene functional group is connected to the piperidine ring at position C4 while the pyrrolidine-bound aryl ring is attached at C8. The conformation about the C4═C11 double bond is E. The sum of the angles around the piperidine-N1 atom is approximately 333° confirming its sp³ character. The piperidine ring adopts a half-chair conformation where the C2 atom lies 0.713 (3) Å out of the plane of the remaining five atoms (r.m.s. deviation = 0.086 Å). The C6 and C8 atoms occupy axial and equatorial positions with respect to the piperidine ring, the phenylmethylidene residue occupies an equatorial position, and the N-bound methyl substituent is equatorial. The pyrrolidine ring has an envelope conformation with the flap atom being the C7 atom which lies 0.648 (3) Å out of the plane of the remaining four atoms (r.m.s. deviation = 0.026 Å). Finally, the indole fused ring system is planar with a r.m.s. deviation = 0.051 Å.

The most prominent feature of the crystal packing of is the formation of centrosymmetric eight-membered {···HNCO}₂ synthons owing to the self-association of molecules via hydrogen bonding between amide groups, Table 1. The dimers are connected into a supramolecular chain parallel to the b axis by phenyl-C–H···N (pyrrolidine) interactions and these are consolidated into a three-dimensional architecture by (chlorobenzene)C—H···π (pyrrolidine-bound phenyl), edge-to-face, interactions; a view of the unit cell contents is shown in Fig. 2.