Crystal structure of 1,7,8,9-tetra­chloro-4-(3,5-di­chloro­benz­yl)-10,10-dimeth­oxy-4-aza­tri­cyclo­[5.2.1.02,6]dec-8-ene-3,5-dione

He Liu; Jia-liang Zhong; Wen-xia Sun; Yan-qing Gong; Li-hong Liu

doi:10.1107/S2056989014025961

. 2015 Jan 1;71(Pt 1):o14–o15. doi: 10.1107/S2056989014025961

Crystal structure of 1,7,8,9-tetrachloro-4-(3,5-dichlorobenzyl)-10,10-dimethoxy-4-azatricyclo[5.2.1.0^2,6]dec-8-ene-3,5-dione

He Liu ^a, Jia-liang Zhong ^b,^*, Wen-xia Sun ^b, Yan-qing Gong ^c, Li-hong Liu ^a

PMCID: PMC4331899 PMID: 25705480

Abstract

In the title compound, C₁₇H₁₁Cl₆NO₄, the configuration of the cycloalkene skeleton is endo,cis. The benzene ring is twisted by 58.94 (8)° from the attached pyrrolidine ring. Two carbonyl groups play a key role in the crystal packing. A short intermolecular C⋯O distance of 3.017 (3) Å reveals that one carbonyl group is involved in dipole–dipole interactions, which link two adjacent enantiomers into an inversion dimer. Another carbonyl group provides an acceptor for the weak intermolecular C—H⋯O hydrogen bonds which link these dimers into layers parallel to (011).

Keywords: crystal structure; tricyclo[5.2.1.0^2,6]dec-8-ene-3,5-dione; biological activity; cycloalkene skeleton; dipole–dipole interactions; hydrogen bonding

Related literature

For related crystal structures, see: Shan et al. (2012 ▸); Kossakowski et al. (2009 ▸). For the biological activity of related compounds, see: Kossakowski et al. (2006 ▸, 2008 ▸); Struga et al. (2007 ▸). graphic file with name e-71-00o14-scheme1.jpg

Experimental

Crystal data

C₁₇H₁₁Cl₆NO₄
M _r = 505.97
Triclinic,
a = 8.9905 (18) Å
b = 11.351 (2) Å
c = 11.482 (2) Å
α = 119.52 (3)°
β = 94.51 (3)°
γ = 90.23 (3)°
V = 1015.2 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.87 mm⁻¹
T = 296 K
0.25 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
10037 measured reflections
4611 independent reflections
3865 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.111
S = 1.05
4611 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); 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 datablock(s) I, global. DOI: 10.1107/S2056989014025961/cv5477sup1.cif

e-71-00o14-sup1.cif^{(21.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014025961/cv5477Isup2.hkl

e-71-00o14-Isup2.hkl^{(225.9KB, hkl)}

Click here for additional data file.^{(7.1KB, cml)}

Supporting information file. DOI: 10.1107/S2056989014025961/cv5477Isup3.cml

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989014025961/cv5477fig1.tif

View of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.^{(1.8MB, tif)}

. DOI: 10.1107/S2056989014025961/cv5477fig2.tif

A portion of the crystal packing viewed approximately along [01-1]. The dipole-dipole and intermolecular C—H⋯O interactions are shown by dashed lines. H atoms not involved in C—H⋯O interactions are omitted for clarity.

CCDC reference: 1036270

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C14H14AO2ⁱ	0.93	2.57	3.265(4)	132
C18H18AO2ⁱⁱ	0.96	2.45	3.260(4)	141

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

Acknowledgments

We gratefully acknowledge financial support from the National Natural Sciencce Foundation of China (No. 81072530).

supplementary crystallographic information

S1. Comment

The title compound, (I) (Fig. 1), was synthesized from N-(3',5'-dichlorobenzyl)maleimide and 5,5-dimethoxy-1,2,3,4-tetrachlorocydopentadiene. The fused pyrrolidine ring systems are frequently encountered structural units in many synthetically challenging and biologically active alkaloids. The interest of constructing skeletons of this type was further enlightened by the recent disclosure that the rigid arylcyclo analogues having azatricyclo ring systems show anti-HIV-1, anti-cancer, antiviral, and antibacterial activities (Kossakowski et al., 2006).

In (I), the configuration of the cycloalkene skeleton is endo, cis. The dihedral angle of pyrrolidine ring and benzene ring is 58.94 (8)°. Two carbonyl groups play a key role in the crystal packing (Fig. 2). One carbonyl group is involved in dipole-dipole interactions, with C3···O1(-x+2, -y+2, -z) distance of 3.017 (3) Å, which link two adjacent enantiomers into inversion dimers. The other carbonyl group provides an acceptor for two weak intermolecular C—H···O hydrogen bonds (Table 1). These intermoleclular interactions link these dimers into layers parallel to (011).

S2. Experimental

N-(3,5-Dichlorobenzyl)maleimide (2.44 g, 10 mmol) and 5,5-dimethoxy-1,2,3,4-tetrachlorocydopentadiene (2.63 g, 10 mmol) were dissolved in anhydrous toluene (100 ml). Then, the solution was refluxed for 8 h. After the solvent was removed under reduced pressure, the residue was dissolved in ether (150 ml), washed with water and brine, dried over anhydrous sodium sulfate, and concentrated to dryness. The product was purified by flash-chromatography (petroleum ether/ethyl acetate, 6:1) and the title compound was isolated as a white solid (4.16 g, 82%), with melting point between 104 and 106°C.

The crystals appropriate for X-ray data collection were obtained from acetone solution at room temperature after four days.