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Acta Crystallogr Sect E Struct Rep Online. 2009 January 1; 65(Pt 1): o90.
Published online 2008 December 10. doi:  10.1107/S1600536808041469
PMCID: PMC2967997

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

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 [triangle]); Ibers & Hamilton (1964 [triangle]).

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Object name is e-65-00o90-scheme1.jpg

Experimental

Crystal data

  • C19H14ClFN2O3
  • M r = 372.77
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-00o90-efi1.jpg
  • 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
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1999 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808041469/rz2277sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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.

Refinement

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.

Figures

Fig. 1.
The molecular structure of The title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
Packing diagram of the title compound, viewed approximately along the a axis. Hydrogen bonds are shown as dashed lines.

Crystal data

C19H14ClFN2O3F(000) = 768
Mr = 372.77Dx = 1.337 Mg m3
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 mm1
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

Bruker SMART 1000 CCD area-detector diffractometer2138 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

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 = 1.07w = 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 Å3
0 restraintsΔρmin = −0.23 e Å3

Special details

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)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2277).

References

  • 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. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography