rac-(1R,2S,6R,7R)-4-{[(1E)-(2-Chloro­phen­yl)methyl­idene]amino}-1-isopropyl-7-methyl-4-aza­tricyclo­[5.2.2.02,6]undec-8-ene-3,5-dione

Jian-Xin Huang; Wen-Gui Duan; Xian-Li Ma; Qi-Jin Mo; Yin-Hua Liang

doi:10.1107/S1600536811013468

. 2011 Apr 29;67(Pt 5):o1251. doi: 10.1107/S1600536811013468

rac-(1R,2S,6R,7R)-4-{[(1E)-(2-Chlorophenyl)methylidene]amino}-1-isopropyl-7-methyl-4-azatricyclo[5.2.2.0^2,6]undec-8-ene-3,5-dione

Jian-Xin Huang ^a, Wen-Gui Duan ^a,^*, Xian-Li Ma ^b, Qi-Jin Mo ^a, Yin-Hua Liang ^a

PMCID: PMC3089279 PMID: 21754542

Abstract

The title compound, C₂₁H₂₃ClN₂O₂, was synthesized from N-amino-α-terpinene maleimide and 2-chlorobenzaldehyde. There are two independent molecules in the asymmetric unit which are linked via an intermolecular C—H⋯O hydrogen bond. The crystal studied was found to be a partial merohedral twin, with a 0.74 (7):0.26 (7) domain ratio.

Related literature

For the synthesis of the starting α-terpinene-maleic anhydride adduct, see: Luo et al. (2006 ▶). For the synthesis of N-amino-α-terpinene maleimide, see: Maurya & Verma (1986 ▶). For related structures, see: Struga et al. (2007 ▶, 2009 ▶); Devarajegowda et al. (2010 ▶); Duan et al. (2007 ▶). For standard bond lengths, see: Orpen et al. (1989 ▶).

Experimental

Crystal data

C₂₁H₂₃ClN₂O₂
M _r = 370.86
Orthorhombic,
a = 18.505 (9) Å
b = 27.012 (13) Å
c = 7.630 (4) Å
V = 3814 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 296 K
0.35 × 0.28 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.929, T _max = 0.947
26001 measured reflections
8499 independent reflections
4632 reflections with I > 2σ(I)
R _int = 0.092

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.129
S = 0.99
8499 reflections
470 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ▶), 3824 Friedel pairs
Flack parameter: 0.26 (7)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811013468/ld2006sup1.cif

e-67-o1251-sup1.cif^{(34.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013468/ld2006Isup2.hkl

e-67-o1251-Isup2.hkl^{(415.7KB, 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
C2B—H2BB⋯O1Aⁱ	0.98	2.40	3.213 (4)	139

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Natural Science Foundation of Guangxi Province of China (No. 2010GXNSFB013016) and The National Innovation Plan for Undergraduates in Guangxi University (No. 200924).

supplementary crystallographic information

Comment

Turpentine is an abundant and green resource in China. α-Pinene, the main component of turpentine, can be isomerized to α-terpinene which reacts with maleic anhydride to yield the α-terpinene-maleic anhydride adduct (Luo et al., 2006). In order to search for novel bioactive compounds (Duan et al., 2007), a series of α-pinene derivatives was synthesized and their respective crystal structures were detected.

Herein, we report the crystal structure of the title compound. The structure presents racemate crystallizing in a polar space group with Flack parameter 0.26 (7). The asymmetric unit of the title compound is shown in Fig. 1. There are two independent molecules [A and B] with all bond lengths and angles within normal ranges (Orpen et al., 1989). The C = N double bond in both molecules adopts E configuration. The dihedral angles between benzene rings [C16—C21 and C37—C42] and hydrazone moieties [N1A—N2A—C15A—C16A and N1B—N2B—C15B—C16B] are 4.1 (3)° and 1.7 (3)°, respectively. In the crystal, molecules A and B are linked together via weak intermolecular C—H···O hydrogen bond between tertiary carbon atom and carbonyl group.

Experimental

A mixture of 3.042 g (0.015 mol) of N-amino-α-terpinene maleimide, 1.41 g (0.01 mol) of 2-chlorobenzaldehyde and 35 ml of ethanol was placed in a 50 ml two-necked flask. When the reaction temperature reached 84 °C, 3 ml of acetic acid was successively added to the solution as a catalyst in 15 minutes. The reaction was monitored by TLC. After complete disappearance of 2-chlorobenzaldehyde, the solvent was evaporated under reduced pressure. The residue was washed with distilled water. The crude product was purified by column chromatography and recrystallized from ethanol. Single crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of an ethanol solution.