3-(6-Benz­yloxy-2,2-dimethyl­perhydro­furo[2,3-d][1,3]dioxolan-5-yl)-5-(4-chloro­phen­yl)-4-nitro-2-phenyl-2,3,4,5-tetra­hydro­isoxazole

M NizamMohideen; M Damodiran; A SubbiahPandi; P T Perumal

doi:10.1107/S1600536809034096

. 2009 Sep 5;65(Pt 10):o2305–o2306. doi: 10.1107/S1600536809034096

3-(6-Benzyloxy-2,2-dimethylperhydrofuro[2,3-d][1,3]dioxolan-5-yl)-5-(4-chlorophenyl)-4-nitro-2-phenyl-2,3,4,5-tetrahydroisoxazole

M NizamMohideen ^a, M Damodiran ^b, A SubbiahPandi ^c,^*, P T Perumal ^b

PMCID: PMC2970260 PMID: 21577778

Abstract

In the title compound, C₂₉H₂₉ClN₂O₇, the isoxazole and dioxolane rings adopt envelope conformations, and the furan ring adopts a twisted conformation. The crystal structure is stabilized by intermolecular C—H⋯π interactions between a benzyloxy methylene H atom and the 4-chlorophenyl ring of an adjacent molecule, and by weak non-classical intermolecular C—H⋯O hydrogen bonds. In addition, the crystal structure exhibits a Cl⋯O halogen bond of 3.111 (3) Å, with a nearly linear C—Cl⋯O angle of 160.7 (1)°.

Related literature

For general background to 1,3-dipolar cycloaddition reactions, see: Gothelf & Jorgensen (1998 ▶); Bernotas et al. (1996 ▶); Breuer (1982 ▶); Colombi et al. (1978 ▶); Hossain et al. (1993 ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶). For halogen bonds, see: Politzer et al. (2007 ▶).

Experimental

Crystal data

C₂₉H₂₉ClN₂O₇
M _r = 552.99
Orthorhombic,
a = 12.7862 (5) Å
b = 13.0160 (5) Å
c = 16.8232 (6) Å
V = 2799.80 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker 2004 ▶) T _min = 0.926, T _max = 0.964
17056 measured reflections
4764 independent reflections
3446 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.088
S = 1.02
4764 reflections
355 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.14 e Å⁻³
Absolute structure: Flack (1983 ▶), 1975 Friedel pairs
Flack parameter: −0.05 (8)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034096/lx2103sup1.cif

e-65-o2305-sup1.cif^{(26.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034096/lx2103Isup2.hkl

e-65-o2305-Isup2.hkl^{(233.4KB, 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
C13—H13⋯O2ⁱ	0.98	2.54	3.298 (3)	134
C17—H17B⋯O1ⁱⁱ	0.97	2.46	3.218 (3)	135
C21—H21⋯Cg1ⁱ	0.93	2.75	3.598 (1)	152

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 is the centroid of the C1–C6 ring.

Acknowledgments

MNM and ASP thank Dr J. Jothi Kumar, Principal of Presidency College (Autonomous), Chennai, India, for providing the computer and internet facilities. The authors thank Dr Babu Vargheese, SAIF, IIT, Madras, India, for his help with the X-ray data collection.

supplementary crystallographic information

Comment

The 1,3-dipolar cycloaddition of nitrones with olefinic dipolarophiles proceeds through a concerted mechanism yielding highly substituted isoxazolidines (Gothelf & Jorgensen, 1998). The cornerstone for cycloaddition reactions, nitrones, are excellent spin traping (Bernotas et al., 1996) and highly versatile synthetic intermediates (Breuer, 1982). Highly substituted spiro-isoxazolidines result from the 1,3-dipolar cycloaddition of exocylic olefins with nitrones and these spiro-isoxazolidines have also been transformed into complex heterocycles (Colombi et al., 1978, Hossain et al., 1993). Here we report the crystal structure of the title compound (Fig. 1).

The dihedral angle between the phenyl rings C1-C6 and C18-C23, C18-C23 and C24-C29, and, C1-C6 and C24-C29 are 8.4 (2), 83.9 (1) and 75.7 (1)°, respectively. The five membered tetrahydrofuran ring (C10-C13/O4) adopts a twisted conformation and the other five membered rings, isoxazole ring (C7-C9/O1/N1) and the dioxolan ring (C12-C14/O5/O6), adopt envelope conformations on C11 and C10, O1 and O5 with a pseudo-twofold axis passing through C12–C11, C9–C8 and C13–O6 bonds. The puckering parameters (Cremer & Pople, 1975) and the lowest displacement asymmetry parameters (Nardelli, 1983)as follows: for the tetrahydrofuran ring q₂ = 0.365 (1) Å, φ = 304.9 (1)°, Δ_S (C10) is 12.8 (1)° and Δ₂ (C13) is 1.8 (1)°, for the isoxazolidine ring q₂ = 0.377 (1) Å, φ = 359.7 (1)°, Δ_S (O1) is 1.0 (1)° and Δ₂(C8) is 19.6 (1)° and for the dioxolone ring q₂ = 0.248 (1) Å, φ = 181.2 (1)°, Δ_S (O5) is 0.3 (1)° and Δ₂ (C13) is 13.3 (1)°.

The molecular packing is stabilized by weak non-classical intermolecular C–H···O hydrogen bonds (Table 1 and Fig. 2; symmetry code as in Fig. 2). Additionally, the crystal structure exhibits a Cl···O halogen bond (Politzer et al., 2007) between the chlorine atom and the oxygen of a neighbouring NO₂ group, with a Cl1···O2^iv distance of 3.111 (3) Å (symmetry code as in Fig. 2). The molecular packing (Fig. 3) is further stabilized by an intermolecular C–H···π interactions between the methylene H atom of benzyloxy substituent and the 4-chlorophenyl ring of an adjacent molecule, with a C21–H21···Cg1ⁱⁱⁱ separation of 2.75 Å (Table 1, Cg1 is the centroid of C1-C6 benzene ring).

Experimental

A mixture of D-glucose derived nitrone (0.5 mmol) and β-nitrostyrene (0.5 mmol) was refluxed in dry toluene (10 ml) until completion of the reaction as evidenced by TLC analysis. The solvent was evaporated under reduced pressure. The crude was purified by column chromatography on silica gel (Merck, 100-200 mesh, ethylacetate-petroleum ether (10 : 90) to afford pure isoxazolidine. Single crystals of the title compound suitable for X-ray diffraction was recrystallized from ethanol.