(E)-2-[4-(2-Chloro­phen­yl)but-3-en-2-yl­idene]malononitrile

Tai-Ran Kang

doi:10.1107/S1600536811037159

. 2011 Sep 17;67(Pt 10):o2661. doi: 10.1107/S1600536811037159

(E)-2-[4-(2-Chlorophenyl)but-3-en-2-ylidene]malononitrile

Tai-Ran Kang ^a,^*

PMCID: PMC3201519 PMID: 22065812

Abstract

There are two independent but virtually identical molecules in the asymmetric unit of the title compound, C₁₃H₁₉ClN₂. Each molecular skeleton displays an approximately planar structure except for the methyl group [the r.m.s. deviations for all 16 non-H atoms are 0.039 (molecule 1) and 0.056 Å (molecule 2)]. An E configuration is found about each of the C=C bonds. The crystal packing is stabilized by C—H⋯N interactions that connect the independent molecules into supramolecular chains along the c-axis direction.

Related literature

For the use of malononitrile-containing compounds as building blocks in synthesis, see: Liu et al. (2002 ▶); Sepiol & Milart (1985 ▶); Zhang et al. (2003 ▶). For a related structure, see: Kang & Chen (2009 ▶).

Experimental

Crystal data

C₁₃H₉ClN₂
M _r = 228.67
Triclinic,
a = 7.7177 (2) Å
b = 11.0539 (5) Å
c = 14.7236 (5) Å
α = 91.260 (3)°
β = 103.992 (3)°
γ = 106.357 (3)°
V = 1163.99 (7) Å³
Z = 4
Cu Kα radiation
μ = 2.67 mm⁻¹
T = 291 K
0.35 × 0.32 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 Gemini ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.455, T _max = 0.502
9739 measured reflections
4135 independent reflections
3770 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.140
S = 1.04
4135 reflections
291 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811037159/tk2789sup1.cif

e-67-o2661-sup1.cif^{(20.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037159/tk2789Isup2.hkl

e-67-o2661-Isup2.hkl^{(198.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811037159/tk2789Isup3.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
C10—H10C⋯N3ⁱ	0.96	2.62	3.564 (3)	166 (1)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Testing Centre of Sichuan University for the diffraction measurements and are grateful for financial support from China West Normal University (No. 10ZB016).

supplementary crystallographic information

Comment

The chemistry of ylidene malononitrile has been studied extensively for ring closure reactions, with compounds containing newly formed five- or six-membered rings, such as indanes (Zhang et al., 2003), naphthalenes (Liu et al., 2002) and benzenes (Sepiol & Milart, 1985) being obtained. Some crystal structures involving ylidene malononitrile groups have been published, including a recent report from our laboratory (Kang & Chen, 2009). As a part of our interest in the synthesis of some complex ring systems, we investigated the title compound (I), which is a diene reagent in the Diels-Alder reaction. We report herein the crystal structure of (I).

Two independent molecules comprise the asymmetric unit of (I), Fig. 1. The molecular skeleton displays an approximately planar arrangement in each case. The chlorobenzene ring and 2-propylidenemalononitrile groups are located on opposite sides of the double bond to which they are attached, showing an E configuration. The crystal packing is stabilized by C—H···N interactions (Table 1).

Experimental

2-(Propan-2-ylidene)malononitrile (0.212 g, 2 mmol) and 2-chlorobenzaldehyde (0.28 g, 2 mmol) were dissolved in 2-propanol (2 ml). To the solution was added piperidine (0.017 g, 0.2 mmol). The solution was then stirred for 24 h at 343 K. The reaction mixture was cooled to room temperature and the solution was filtered to obtain a white solid. Recrystallization from hot ethanol afforded the pure compound. Single crystals of (I) were obtained by slow evaporation of its ethyl acetate solution.