(5S,6S,10R)-10-(2,4-Dichloro­phen­yl)-14-[(E)-(2,4-dichloro­phen­yl)methyl­idene]-3,9-diphenyl-12-[(R)-1-phenyl­ethyl]-1,4,7-trioxa-2,8,12-triaza­dispiro­[4.0.4.4]tetra­deca-2,8-diene

S Mahalakshmi; R Suresh Kumar; S Perumal; V Sivakumar; J Suresh

doi:10.1107/S1600536807063477

. 2007 Dec 6;64(Pt 1):o199–o200. doi: 10.1107/S1600536807063477

(5S,6S,10R)-10-(2,4-Dichlorophenyl)-14-[(E)-(2,4-dichlorophenyl)methylidene]-3,9-diphenyl-12-[(R)-1-phenylethyl]-1,4,7-trioxa-2,8,12-triazadispiro[4.0.4.4]tetradeca-2,8-diene

S Mahalakshmi ^a, R Suresh Kumar ^b, S Perumal ^b, V Sivakumar ^c, J Suresh ^c,^*

PMCID: PMC2915262 PMID: 21200764

Abstract

The asymmetric unit of the title compound, C₄₁H₃₁Cl₄N₃O₃, contains two independent molecules with almost identical geometries. The piperidine ring adopts a chair conformation in both molecules, and the dihydroisoxazole rings adopt envelope conformations. The crystal structure is stabilized by C—H⋯N hydrogen bonds and C—H⋯π interactions.

Related literature

For related literature, see: Curran (1983 ▶); De Amici et al. (1990 ▶); Diana et al. (1985 ▶); Faulkner (2001 ▶); Gothelf & Jorgensen (1998 ▶); Howe & Shelton (1990 ▶); Jager & Muller (1985 ▶); Kang et al. (2000 ▶); Konig et al. (1990 ▶); Kozikowski & Stein (1982 ▶); Lepage et al. (1992 ▶). Martin et al. (1989 ▶); Nair et al. (1999 ▶); Padwa (1984 ▶); Xue et al. (1998 ▶).

Experimental

Crystal data

C₄₁H₃₁Cl₄N₃O₃
M _r = 755.49
Monoclinic,
a = 13.302 (6) Å
b = 12.551 (9) Å
c = 22.650 (11) Å
β = 105.55 (4)°
V = 3643 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 293 (2) K
0.25 × 0.18 × 0.13 mm

Data collection

Nonius MACH-3 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.923, T _max = 0.953
7698 measured reflections
7370 independent reflections
3074 reflections with I > 2σ(I)
R _int = 0.052
2 standard reflections frequency: 60 min intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.096
S = 0.99
7370 reflections
921 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.22 e Å⁻³
Absolute structure: Flack (1983 ▶), 639 Friedel pairs
Flack parameter: 0.05 (7)

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, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807063477/ci2522sup1.cif

e-64-0o199-sup1.cif^{(51KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063477/ci2522Isup2.hkl

e-64-0o199-Isup2.hkl^{(353.3KB, 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
C10B—H10D⋯N2Bⁱ	0.96	2.61	3.560 (10)	173
C34B—H34B⋯Cg1ⁱⁱ	0.93	2.68	3.495 (10)	147
C74A—H74A⋯Cg2ⁱⁱⁱ	0.93	2.85	3.601 (10)	139

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1 is the centroid of the C91B–C96B ring. Cg2 is the centroid of the ring C12B–C17B ring.

Acknowledgments

SP thanks CSIR, New Delhi, for a Major Research Project.

supplementary crystallographic information

Comment

1,3-Dipolar cycloaddition reactions afford complex heterocycles with multiple stereocentres, which are useful in the construction of many natural products and pharmaceuticals (Kozikowski & Stein, 1982; Curran, 1983; Jager & Muller, 1985; Martin et al., 1989). 1,3-Dipolar cycloaddition of nitrile oxides to alkenes and α, β -unsaturated carbonyl compounds afford isoxazolines, spiroisoxazolines and dioxazoles (Padwa, 1984; Gothelf & Jorgensen, 1998; Nair et al., 1999). Isoxazolines exhibit antibacterial, antiplatelet, antiviral and anticonvulsant activities, while compounds incorporating spiroisoxazoline sub-structure have stimulated much interest in medicinal and biological chemistry, and hence the structure determination of these compounds is of paramount importance (Diana et al., 1985; De Amici et al., 1990; Howe & Shelton, 1990; Konig et al., 1990; Lepage et al., 1992; Xue et al., 1998; Kang et al., 2000; Faulkner, 2001).

The asymmetric unit of the title compound contains two independent molecules (A and B), with almost identical geometry (Fig.1 and Fig.2). The piperidine ring adopts a chair conformation in both molecules. The olefinic double bonds in molecule A and molecule B have an E configuration and the aryl rings are not coplanar with the adjacent olefinic double bond. The dioxazole ring is essentially planar in both molecules and it forms a dihedral angle of 5.1 (5)° with the attached C12—C17 phenyl ring in molecule A and the corresponding angle is 33.0 (4)° in molecule B. The dihydroisoxazole ring adopts an envelope conformation in both molecules. As a result of steric repulsions the C3—C31—C32 bond angle is widened to 128.5 (8)° in molecule A and 128.6 (8)° in B.

Crystal packing reveals that molecules B are linked by C10B—H10D···N2B (Table 1) hydrogen bonds, generating a C(9) chain along the b axis. In addition, weak C—H···π interactions are observed (Table 1).

Experimental

To a solution of 3,5-bis[(E)-(2,4-dichlorophenyl)methylidene]-1-[(R)-1-phenylethyl]-tetrahydro-4(1H)-pyridinone (0.30 g, 0.58 mmol)in benzene (20 ml), benzohydroximoyl chloride (0.316 g, 2.33 mmol) was added and the mixture stirred at room temperature. A solution of triethylamine (0.235 g, 2.33 mmol) in benzene (5 ml) was added dropwise to the above mixture and the stirring was continued for 10 h. The progress of the reaction was monitored by thin-layer chromatography (TLC) with petrolium ether-ethyl acetate (4:1 v/v) mixture as eluent. After completion of the reaction as evident from TLC, the resulting mixture was filtered to remove the triethylamine hydrochloride, the solvent evaporated in vacuo and the residue subjected to flash column chromatography on silica gel (petrolim ether-ethyl acetate, 10:1). The product was recrystallized from ethanol.