2-Di­chloro­methyl-N-ethyl-5-(1-phenyl­silolan-1-yl)cyclo­pent-3-enecarboxamide

Han Xiao; Wan-Qiu Yang; Liang Shen

doi:10.1107/S160053681302446X

. 2013 Sep 12;69(Pt 10):o1530. doi: 10.1107/S160053681302446X

2-Dichloromethyl-N-ethyl-5-(1-phenylsilolan-1-yl)cyclopent-3-enecarboxamide

Han Xiao ^a,^*, Wan-Qiu Yang ^a, Liang Shen ^a

PMCID: PMC3790399 PMID: 24098218

Abstract

In the title compound, C₁₉H₂₅Cl₂NOSi, the NH group and the carbonyl O atom of the amide fragment are involved in an intermolecular N—H⋯O hydrogen bond forming chains of molecules. The plane of the benzene ring forms a dihedral angle of 50.5 (2)° with respect to the silolane ring and an angle of 49.74 (2)° with the cyclopentyl moiety.

Related literature

For biological activity of silicon-containing compounds, see: Tacke & Wannagat (1975 ▶, 1979 ▶); Voronkov (1979 ▶). For synthetic methods, see: Matthews et al. (2001 ▶, 2002 ▶); Benkeser et al. (1962 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₉H₂₅Cl₂NOSi
M _r = 382.39
Orthorhombic,
a = 42.892 (9) Å
b = 13.335 (3) Å
c = 14.234 (3) Å
V = 8141 (3) Å³
Z = 16
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 295 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.927, T _max = 0.963
3814 measured reflections
1925 independent reflections
1375 reflections with I > 2σ(I)
R _int = 0.045
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.106
S = 1.03
1925 reflections
219 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); 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: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, 1R. DOI: 10.1107/S160053681302446X/im2436sup1.cif

e-69-o1530-sup1.cif^{(28.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681302446X/im2436Isup2.hkl

e-69-o1530-Isup2.hkl^{(95KB, hkl)}

Click here for additional data file.^{(7KB, cml)}

Supplementary material file. DOI: 10.1107/S160053681302446X/im2436Isup3.cml

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
N1—H1⋯O1ⁱ	0.86	2.10	2.945 (5)	170

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by Yunnan Provincial Department of Science and Technology: Study on neuro-activities of gastrodin and helicid derivatives (grant No. 2013FZ102), Synthesis and Sturcture-Activity Relationship of Pulverolide and Its Analogues (grant No. 2013FZ101).

supplementary crystallographic information

1. Comment

It is well known that some silicon-containing compounds show extremely high biological activity, e.g. silatranes, which are much more toxic than strychnine (Tacke & Wannagat, 1975, 1979; Voronkov, 1979). In recent years, people have reported that the reaction of diphenyldichlorosilane with magnesium and butadiene yields silacyclopentenes, which are thought to be formed via a diphenylsilylene intermediate (Matthews et al., 2001, 2002). As part of this work, we synthesized the title compound derived from 1-(cyclopenta-2,4-dienyl)-1-phenylsilolane (CDP), and its structure is reported here..

The compound crystallized with a structural configuration in which the phenyl ring (C1~C6) forms a dihedral angle of 50.5 (2)° with respect to the silolane ring (C7,C8,C9,C10,Si1). The cyclopentene ring (C11~C15) is almost planar with the largest deviation being 0.074 Å for atom C15. The bond length of C12—C13 (1.294 (6) Å), agrees with the value characteristic of a double bond. in general bond lengths (Allen et al., 1987) and angles are within normal ranges. In the crystal structure, there one intermolecular hydrogen bond (N1—H1···O1) is observed.

2. Experimental

1-(cyclopenta-2,4-dienyl)-1-phenylsilolane (CDP) was synthesized according to the method reported by Benkeser et al. (1962). 0.5 mol of CDP was dissolved in 20 ml n-hexane and 20 ml triethylamine in a 200 ml round flask. At 0°C 0.6 mol of 2, 2-dichloroacetyl chloride was added to the flask in 30 min. After continually stirring for 1 h, the solvent was removed and the residue was fractionated on a Todd-column (yield: 31.7%). Colourless block-shaped and needlelike crystals were obtained by slow evaporation of the solution in methanol. Colourless block-shaped single crystals suitable for X-ray structure determination were picked up and determined while the needlelike crystals were too thin to perform an X-ray diffraction experiment. Acoording to elemental analysis, colourless block-shaped and needlelike crystals show an identical composition and are therefore considered to be diastereoisomeric forms of the title compound.