Diethyl 1-acetyl-4′-(4-chloro­phen­yl)-5′-(4-nitro­phen­yl)-2-oxospiro­[indoline-3,3′-pyrrolidine]-2′,2′-dicarboxyl­ate

Long He

doi:10.1107/S160053680903551X

. 2009 Sep 9;65(Pt 10):o2388. doi: 10.1107/S160053680903551X

Diethyl 1-acetyl-4′-(4-chlorophenyl)-5′-(4-nitrophenyl)-2-oxospiro[indoline-3,3′-pyrrolidine]-2′,2′-dicarboxylate

Long He ^a,^*

PMCID: PMC2970347 PMID: 21577852

Abstract

In the title compound, C₃₁H₂₈ClN₃O₈, the pyrrolidine ring exhibits an envelope conformation, with the spiro C atom located at the flap position. A spiro junction links the oxindole ring system and the pyrrolidine ring. The planar oxindole ring system is twisted with respect to the nitrobenzene and chlorobenzene rings, with dihedral angles of 62.34 (11) and 75.93 (9)°, respectively. In the crystal, a weak C—H⋯O interaction links the molecules into chains and two intramolecular C—H⋯O close contacts are seen.

Related literature

For general background to the spirooxindole–pyrrolidine ring system, see: Garnick & Lequesne (1978 ▶); Jossang et al. (1991 ▶). For the biological activity of pyrrolidine-containing compounds and their use in catalysis, see: Grigg (1995 ▶); Kravchenko et al. (2005 ▶); Witherup et al. (1995 ▶). For the biological activity of oxindole derivatives, see: Glover et al. (1998 ▶); Bhattacharya et al. (1982 ▶).

Experimental

Crystal data

C₃₁H₂₈ClN₃O₈
M _r = 606.01
Orthorhombic,
a = 9.780 (2) Å
b = 14.859 (3) Å
c = 20.466 (5) Å
V = 2974.1 (11) Å³
Z = 4
Cu Kα radiation
μ = 1.61 mm⁻¹
T = 293 K
0.40 × 0.38 × 0.32 mm

Data collection

Oxford Diffraction Gemini S Ultra diffractometer
Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009 ▶) T _min = 0.565, T _max = 0.626
27366 measured reflections
4732 independent reflections
4456 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.066
S = 1.00
4732 reflections
403 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.15 e Å⁻³
Absolute structure: Flack (1983 ▶), with 2017 Friedel pairs
Flack parameter: 0.020 (15)

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis Pro; data reduction: CrysAlis Pro ; 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903551X/xu2602sup1.cif

e-65-o2388-sup1.cif^{(28.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680903551X/xu2602Isup2.hkl

e-65-o2388-Isup2.hkl^{(227.1KB, 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
C10—H10C⋯O8ⁱ	0.96	2.51	3.387 (4)	152
C11—H11⋯O3	0.98	2.54	3.200 (3)	125
C21—H21⋯O3	0.93	2.44	3.181 (3)	136

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Symmetry code: (i) Inline graphic .

Acknowledgments

The diffraction data were collected at the Centre for Test and Analysis, Chengdu Branch, Chinese Academy of Sciences. The author acknowledges financial support from China West Normal University.

supplementary crystallographic information

Comment

The spirooxindole-pyrrolidine unit is a privileged heterocyclic motif that forms the core of a large family of alkaloid natural products with strong bioactivity profiles and interesting structural properties such as alstonia muelleriana and horsfiline (Garnick & Lequesne, 1978; Jossang et al., 1991). Pyrrolidine-containing compounds are of significant importance because of their biological activities and widespread employment in catalysis (Grigg et al., 1995; Witherup et al., 1995; Kravchenko et al., 2005). Oxindole derivatives are of importance in the total synthesis of indole and oxindole alkaloids such as potent inhibitors of monoamine oxidase (MAO) in human urine and rat tissues (Glover et al., 1998) and atrial natriuretic peptide-stimulated guanylate cyclase and a potent antagonist of in vitro receptor binding by atrial natriuretic peptide besides possessing a wide range of central nervous system activities (Bhattacharya et al., 1982). We report herein the crystal structure of the title compound.

The molecular structure of (I) is shown in Fig. 1. In the molecule, the pyrrolidine ring exhibits an envelope conformation. The oxyindole ring forms dihedral angles of 62.34 (11)°, 75.93 (9)° with nitrophenyl and chlorophenyl rings, respectively. The crystal packing is stabilized by C—H···O hydrogen bonding (Table 1).

Experimental

1-acetyl-3-(4-chlorobenzylidene)indolin-2-one (0.09 g, 0.3 mmol), diethyl 2-aminomalonate (0.035 g, 0.2 mmol) and 4-nitrobenzaldehyde (0.036 g, 0.24 mmol) were dissolved in dichloromethane (2 ml). To the stirred mixture, acetic acid (0.006 g, 0.1 mmol) was added. After the mixture had been stirred at 273 K for 24 h, the reaction was quenched with a saturated solution of sodium bicarbonate (5 ml). The mixture was extracted with diethyl ether, removal of solvent under reduced pressure, the residue was purified through column chromatography on silica gel to give target compound. Colourless single crystals suitable for X-ray diffraction were obtained by recrystallization from ethanol.