(Z)-Ethyl 3-(4-chloro­benzamido)-2-cyano-3-(4-fluoro­phen­yl)acrylate

Dehua Zhang; Xiaoyan Zhang; Lijuan Guo

doi:10.1107/S1600536808041469

. 2008 Dec 10;65(Pt 1):o90. doi: 10.1107/S1600536808041469

(Z)-Ethyl 3-(4-chlorobenzamido)-2-cyano-3-(4-fluorophenyl)acrylate

Dehua Zhang ^a,^*, Xiaoyan Zhang ^b, Lijuan Guo ^c

PMCID: PMC2967997 PMID: 21581728

Abstract

The title compound, C₁₉H₁₄ClFN₂O₃, was prepared by the reaction of ethyl (Z)-3-amino-2-cyano-3-(4-fluorophenyl)acrylate and 4-chlorobenzoyl chloride. The dihedral angle between the chlorobenzene and fluorobenzene rings is 66.18 (19)°. In addition to an intramolecular N—H⋯O hydrogen bond, there are intermolecular C—H⋯O and C—H⋯N hydrogen bonding interactions, which stabilize the crystal structure.

Related literature

For the agrochemical activity of the title compound, see: Heller et al. (2004 ▶); Ibers & Hamilton (1964 ▶).

Experimental

Crystal data

C₁₉H₁₄ClFN₂O₃
M _r = 372.77
Monoclinic,
a = 6.1429 (5) Å
b = 13.1555 (6) Å
c = 22.9263 (10) Å
β = 92.280 (4)°
V = 1851.27 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 298 (2) K
0.40 × 0.20 × 0.10 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: none
23332 measured reflections
3259 independent reflections
2138 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.140
S = 1.07
3259 reflections
236 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1999 ▶); 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/S1600536808041469/rz2277sup1.cif

e-65-00o90-sup1.cif^{(19.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808041469/rz2277Isup2.hkl

e-65-00o90-Isup2.hkl^{(159.9KB, 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
N1—H1⋯O2	0.86	2.00	2.668 (3)	134
C3—H3⋯N2ⁱ	0.93	2.53	3.314 (5)	143
C6—H6⋯O1ⁱⁱ	0.93	2.41	3.170 (4)	140
C14—H14⋯N2ⁱⁱⁱ	0.93	2.55	3.463 (5)	169

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

supplementary crystallographic information

Comment

Recently, 2-cyanoacrylates have been extensively used as agrochemicals because of their unique mechanism of action and good environmental profiles. The title compound is useful as an inhibitor of Pyricularia oryzae, Rhizoctonia solani, Botrytis cinerea and Gibberella zeae (Heller et al., 2004; Ibers & Hamilton, 1964).

In the title compound (Fig.1), all bond lengths and angles are unexcepional. The aromatic rings of the chlorobenzene and fluorobenzene groups form a dihedral angle of 66.18 (19)°. The molecular conformation is stabilized by an intramolecular N—H···O hydrogen bond (Table 1). The crystal packing is governed by C—H···O and C—H···N hydrogen interactions (Fig.2) resulting in a three-dimensional network.

Experimental

To a solution of ethyl (2Z)-3-amino-2-cyano-3-(4-fluorophenyl)acrylate (1.17 g, 0.0050 mol) in CH₂Cl₂ (18 ml), 4-chlorobenzoyl chloride (2.63 g, 0.015 mol) was added. Subsequently, Et₃N (1.52 g, 0.015 mol) was dropped into the solution under stirring. The reaction mixture was then heated to reflux, stirred for 4 h and cooled to room temperature. The reaction solution was filtered off and some white solid was separated. The organic phase was washed with water and then dried over Na₂SO₄. After removal of the solvent, a brown dope was obtained. The title compound was isolated by column chromatography using ethyl acetate/light petroleum (1:6 v/v) as eluent. Single crystals suitable for X-ray analysis were obtained by slow evaporation at room temperature of an ethyl acetate/petroleum ether (3:1 v/v) solution after 45 days.