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Acta Cryst. (2009). E65, o90    [ doi:10.1107/S1600536808041469 ]

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

D. Zhang, X. Zhang and L. Guo

Abstract top

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.

Comment top

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.

Related literature top

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

Experimental top

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.

Refinement top

All H atoms were placed at calculated positions and refined using a riding model, with C—H = 0.93-0.97 Å, N—H = 0.86 Å and with Uiso(H) = 1.2 Ueq(C, N) or 1.5 Ueq(C) for methyl H atoms.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of The title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. Packing diagram of the title compound, viewed approximately along the a axis. Hydrogen bonds are shown as dashed lines.
(Z)-Ethyl 3-(4-chlorobenzamido)-2-cyano-3-(4-fluorophenyl)acrylate top
Crystal data top
C19H14ClFN2O3F(000) = 768
Mr = 372.77Dx = 1.337 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1253 reflections
a = 6.1429 (5) Åθ = 3.1–20.3°
b = 13.1555 (6) ŵ = 0.24 mm−1
c = 22.9263 (10) ÅT = 298 K
β = 92.280 (4)°Block, colourless
V = 1851.27 (19) Å30.40 × 0.20 × 0.10 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		2138 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.053
graphiteθmax = 25.0°, θmin = 1.8°
phi and ω scansh = −7→7
23332 measured reflectionsk = −15→15
3259 independent reflectionsl = −24→27
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0335P)2 + 1.3651P]
where P = (Fo2 + 2Fc2)/3
3259 reflections(Δ/σ)max = 0.001
236 parametersΔρmax = 0.25 e Å−3
0 restraintsΔρmin = −0.23 e Å−3
Crystal data top
C19H14ClFN2O3V = 1851.27 (19) Å3
Mr = 372.77Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.1429 (5) ŵ = 0.24 mm−1
b = 13.1555 (6) ÅT = 298 K
c = 22.9263 (10) Å0.40 × 0.20 × 0.10 mm
β = 92.280 (4)°
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		2138 reflections with I > 2σ(I)
23332 measured reflectionsRint = 0.053
3259 independent reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.065H-atom parameters constrained
wR(F2) = 0.140Δρmax = 0.25 e Å−3
S = 1.07Δρmin = −0.23 e Å−3
3259 reflectionsAbsolute structure: ?
236 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.4513 (5)0.4421 (2)0.11848 (12)0.0510 (7)
C20.4752 (5)0.3939 (2)0.17187 (14)0.0613 (9)
H20.37610.40640.20060.074*
C30.6452 (6)0.3273 (3)0.18272 (14)0.0670 (9)
H30.65990.29420.21850.080*
C40.7924 (5)0.3099 (2)0.14056 (15)0.0626 (9)
C50.7716 (6)0.3559 (3)0.08732 (15)0.0696 (9)
H50.87180.34310.05890.084*
C60.6006 (6)0.4213 (2)0.07632 (14)0.0673 (9)
H60.58480.45230.03990.081*
C70.2778 (5)0.5173 (2)0.10220 (14)0.0582 (8)
C8−0.0191 (5)0.6171 (2)0.14507 (13)0.0531 (8)
C9−0.0435 (5)0.6899 (2)0.09582 (13)0.0557 (8)
C10−0.2251 (6)0.6897 (3)0.05965 (16)0.0790 (11)
H10−0.33080.64000.06420.095*
C11−0.2547 (7)0.7618 (3)0.01659 (16)0.0873 (12)
H11−0.37790.7598−0.00830.105*
C12−0.1070 (8)0.8340 (3)0.01079 (16)0.0870 (13)
C130.0819 (9)0.8367 (3)0.04453 (19)0.1072 (16)
H130.18670.88630.03880.129*
C140.1124 (7)0.7635 (3)0.08740 (17)0.0879 (12)
H140.23950.76380.11080.106*
C15−0.1571 (5)0.6200 (2)0.18996 (13)0.0539 (8)
C16−0.3251 (6)0.6945 (3)0.18956 (14)0.0667 (9)
C17−0.1424 (5)0.5506 (2)0.24042 (13)0.0561 (8)
C18−0.3118 (6)0.4975 (3)0.32660 (15)0.0742 (10)
H18A−0.18400.51020.35180.089*
H18B−0.31260.42640.31550.089*
C19−0.5130 (7)0.5229 (4)0.35748 (17)0.1065 (15)
H19A−0.51140.59370.36770.160*
H19B−0.51930.48260.39230.160*
H19C−0.63830.50880.33240.160*
Cl11.00991 (17)0.22922 (8)0.15591 (5)0.0969 (4)
F1−0.1365 (6)0.90693 (18)−0.03083 (11)0.1356 (11)
N10.1499 (4)0.54859 (19)0.14698 (10)0.0595 (7)
H10.17990.52160.18050.071*
N2−0.4597 (6)0.7536 (3)0.19023 (14)0.0981 (12)
O10.2500 (5)0.5501 (2)0.05344 (10)0.0940 (9)
O20.0048 (4)0.49015 (17)0.24988 (10)0.0701 (6)
O3−0.3085 (4)0.56200 (16)0.27479 (9)0.0628 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0583 (19)0.0492 (16)0.0460 (17)−0.0001 (14)0.0068 (15)0.0007 (14)
C20.065 (2)0.064 (2)0.056 (2)0.0058 (17)0.0166 (17)0.0054 (16)
C30.076 (2)0.070 (2)0.055 (2)0.0070 (19)0.0057 (18)0.0142 (17)
C40.066 (2)0.0532 (18)0.069 (2)0.0047 (16)0.0076 (18)0.0025 (16)
C50.077 (2)0.073 (2)0.061 (2)0.0152 (19)0.0198 (18)0.0022 (18)
C60.085 (3)0.066 (2)0.0522 (19)0.0133 (19)0.0115 (18)0.0070 (16)
C70.069 (2)0.0603 (19)0.0460 (19)0.0017 (16)0.0124 (16)0.0019 (15)
C80.060 (2)0.0509 (17)0.0482 (18)0.0018 (15)−0.0006 (15)−0.0051 (14)
C90.064 (2)0.0523 (18)0.0514 (18)0.0036 (16)0.0030 (16)−0.0038 (15)
C100.083 (3)0.086 (3)0.067 (2)−0.013 (2)−0.011 (2)0.013 (2)
C110.093 (3)0.099 (3)0.067 (2)0.003 (3)−0.025 (2)0.008 (2)
C120.137 (4)0.056 (2)0.066 (2)0.008 (2)−0.021 (3)0.0120 (19)
C130.150 (4)0.066 (2)0.102 (3)−0.032 (3)−0.038 (3)0.026 (2)
C140.109 (3)0.069 (2)0.083 (3)−0.014 (2)−0.032 (2)0.012 (2)
C150.060 (2)0.0543 (17)0.0471 (18)0.0084 (15)0.0011 (15)−0.0003 (14)
C160.073 (2)0.077 (2)0.050 (2)0.019 (2)0.0033 (17)0.0008 (17)
C170.057 (2)0.0577 (19)0.0537 (19)0.0008 (16)0.0027 (16)−0.0077 (16)
C180.086 (3)0.076 (2)0.060 (2)−0.013 (2)0.0093 (19)0.0138 (18)
C190.095 (3)0.155 (4)0.072 (3)0.002 (3)0.028 (2)0.021 (3)
Cl10.0849 (7)0.0965 (7)0.1095 (8)0.0329 (6)0.0085 (6)0.0214 (6)
F10.226 (3)0.0791 (16)0.0970 (18)0.0063 (18)−0.0458 (19)0.0293 (14)
N10.0694 (18)0.0653 (16)0.0443 (14)0.0139 (14)0.0072 (13)0.0055 (12)
N20.105 (3)0.122 (3)0.068 (2)0.053 (2)0.0133 (19)0.0078 (19)
O10.110 (2)0.119 (2)0.0542 (15)0.0513 (17)0.0204 (14)0.0236 (15)
O20.0746 (16)0.0726 (14)0.0636 (14)0.0142 (13)0.0100 (12)0.0111 (12)
O30.0666 (14)0.0682 (13)0.0543 (13)0.0006 (11)0.0105 (11)0.0010 (11)
Geometric parameters (Å, °) top
C1—C21.381 (4)C11—C121.324 (5)
C1—C61.386 (4)C11—H110.9300
C1—C71.491 (4)C12—F11.361 (4)
C2—C31.378 (4)C12—C131.369 (6)
C2—H20.9300C13—C141.383 (5)
C3—C41.369 (4)C13—H130.9300
C3—H30.9300C14—H140.9300
C4—C51.364 (4)C15—C161.423 (5)
C4—Cl11.732 (3)C15—C171.473 (4)
C5—C61.374 (4)C16—N21.135 (4)
C5—H50.9300C17—O21.217 (4)
C6—H60.9300C17—O31.322 (4)
C7—O11.204 (4)C18—O31.461 (4)
C7—N11.380 (4)C18—C191.487 (5)
C8—C151.360 (4)C18—H18A0.9700
C8—N11.374 (4)C18—H18B0.9700
C8—C91.484 (4)C19—H19A0.9600
C9—C101.363 (4)C19—H19B0.9600
C9—C141.381 (5)C19—H19C0.9600
C10—C111.376 (5)N1—H10.8600
C10—H100.9300
C2—C1—C6118.5 (3)C11—C12—F1120.2 (4)
C2—C1—C7125.2 (3)C11—C12—C13122.1 (4)
C6—C1—C7116.3 (3)F1—C12—C13117.7 (4)
C3—C2—C1120.4 (3)C12—C13—C14118.1 (4)
C3—C2—H2119.8C12—C13—H13121.0
C1—C2—H2119.8C14—C13—H13121.0
C4—C3—C2119.7 (3)C9—C14—C13120.8 (4)
C4—C3—H3120.2C9—C14—H14119.6
C2—C3—H3120.2C13—C14—H14119.6
C5—C4—C3121.2 (3)C8—C15—C16119.2 (3)
C5—C4—Cl1119.9 (3)C8—C15—C17123.8 (3)
C3—C4—Cl1119.0 (3)C16—C15—C17117.0 (3)
C4—C5—C6119.1 (3)N2—C16—C15178.8 (4)
C4—C5—H5120.5O2—C17—O3123.6 (3)
C6—C5—H5120.5O2—C17—C15124.5 (3)
C5—C6—C1121.2 (3)O3—C17—C15111.9 (3)
C5—C6—H6119.4O3—C18—C19107.2 (3)
C1—C6—H6119.4O3—C18—H18A110.3
O1—C7—N1121.3 (3)C19—C18—H18A110.3
O1—C7—C1122.9 (3)O3—C18—H18B110.3
N1—C7—C1115.7 (3)C19—C18—H18B110.3
C15—C8—N1119.2 (3)H18A—C18—H18B108.5
C15—C8—C9120.7 (3)C18—C19—H19A109.5
N1—C8—C9120.1 (3)C18—C19—H19B109.5
C10—C9—C14118.1 (3)H19A—C19—H19B109.5
C10—C9—C8121.1 (3)C18—C19—H19C109.5
C14—C9—C8120.6 (3)H19A—C19—H19C109.5
C9—C10—C11121.1 (4)H19B—C19—H19C109.5
C9—C10—H10119.4C8—N1—C7128.6 (3)
C11—C10—H10119.4C8—N1—H1115.7
C12—C11—C10119.7 (4)C7—N1—H1115.7
C12—C11—H11120.2C17—O3—C18117.1 (3)
C10—C11—H11120.2
C6—C1—C2—C30.5 (5)C10—C11—C12—C133.4 (7)
C7—C1—C2—C3−178.5 (3)C11—C12—C13—C14−2.7 (7)
C1—C2—C3—C40.8 (5)F1—C12—C13—C14179.3 (4)
C2—C3—C4—C5−1.3 (5)C10—C9—C14—C131.9 (6)
C2—C3—C4—Cl1177.9 (3)C8—C9—C14—C13−174.7 (4)
C3—C4—C5—C60.6 (5)C12—C13—C14—C90.0 (7)
Cl1—C4—C5—C6−178.6 (3)N1—C8—C15—C16176.6 (3)
C4—C5—C6—C10.7 (5)C9—C8—C15—C16−0.5 (5)
C2—C1—C6—C5−1.3 (5)N1—C8—C15—C17−2.5 (5)
C7—C1—C6—C5177.8 (3)C9—C8—C15—C17−179.7 (3)
C2—C1—C7—O1−172.5 (3)C8—C15—C17—O27.0 (5)
C6—C1—C7—O18.5 (5)C16—C15—C17—O2−172.2 (3)
C2—C1—C7—N18.1 (5)C8—C15—C17—O3−173.4 (3)
C6—C1—C7—N1−170.9 (3)C16—C15—C17—O37.4 (4)
C15—C8—C9—C10−64.0 (4)C15—C8—N1—C7164.6 (3)
N1—C8—C9—C10118.9 (4)C9—C8—N1—C7−18.2 (5)
C15—C8—C9—C14112.5 (4)O1—C7—N1—C80.0 (5)
N1—C8—C9—C14−64.7 (4)C1—C7—N1—C8179.4 (3)
C14—C9—C10—C11−1.2 (6)O2—C17—O3—C18−0.1 (4)
C8—C9—C10—C11175.4 (3)C15—C17—O3—C18−179.7 (3)
C9—C10—C11—C12−1.4 (6)C19—C18—O3—C17−179.3 (3)
C10—C11—C12—F1−178.6 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O20.862.002.668 (3)134
C3—H3···N2i0.932.533.314 (5)143
C6—H6···O1ii0.932.413.170 (4)140
C14—H14···N2iii0.932.553.463 (5)169
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z; (iii) x+1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O20.862.002.668 (3)134
C3—H3···N2i0.932.533.314 (5)143
C6—H6···O1ii0.932.413.170 (4)140
C14—H14···N2iii0.932.553.463 (5)169
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z; (iii) x+1, y, z.
Acknowledgements top

No acknowledgements required

references
References top

Bruker (1997). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Heller, D., Drexler, H. J., You, J. & Zhang, S. L. (2004). WO Patent 011 414.

Ibers, J. A. & Hamilton, W. C. (1964). Acta Cryst. 17, 781–782.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.