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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2254.
Published online 2008 November 8. doi:  10.1107/S1600536808034818
PMCID: PMC2959890

(Z)-Ethyl 3-(4-chloro­phen­yl)-2-cyano-3-(2,6-difluoro­benzamido)acrylate

Abstract

The title compound, C19H13ClF2N2O3, was prepared by the reaction of (Z)-ethyl 3-amino-3-(4-chloro­phen­yl)-2-cyano­acrylate and 2,6-difluoro­benzoyl chloride. The dihedral angle between the chloro­benzene and fluoro­benzene rings is 37.0 (1)°. The ethyl group is disordered over two positions [occupancies = 0.52 (2):0.48 (2)]. In addition to intra­molecular N—H(...)O and N—H(...)F hydrogen bonds, the crystal packing shows the mol­ecules to be connected by inter­molecular C—H(...)O and C—H(...)N hydrogen bonds.

Related literature

The title compound is useful as an inhibitor of Pyricularia oryzae, Rhizoctonia solani, Botrytis cinerea and Gibberella zeae, see: Heller et al. (2004 [triangle]); Creagh & Hubbell (1992 [triangle]); Ibers & Hamilton (1964 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2254-scheme1.jpg

Experimental

Crystal data

  • C19H13ClF2N2O3
  • M r = 390.76
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2254-efi1.jpg
  • a = 8.919 (5) Å
  • b = 9.7560 (6) Å
  • c = 11.2717 (7) Å
  • α = 91.9710 (10)°
  • β = 110.0940 (10)°
  • γ = 91.4490 (10)°
  • V = 919.9 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.25 mm−1
  • T = 298 (2) K
  • 0.23 × 0.20 × 0.10 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: none
  • 7196 measured reflections
  • 3556 independent reflections
  • 2524 reflections with I > 2σ(I)
  • R int = 0.053

Refinement

  • R[F 2 > 2σ(F 2)] = 0.052
  • wR(F 2) = 0.154
  • S = 1.10
  • 3556 reflections
  • 265 parameters
  • 6 restraints
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.31 e Å−3

Data collection: SMART (Bruker, 1998 [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/S1600536808034818/fl2223sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808034818/fl2223Isup2.hkl

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

supplementary crystallographic information

Comment

Recently, 2-cyanoacrylates have been in widespread 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; Creagh & Hubbell, 1992; Ibers & Hamilton, 1964).

In the title compound(Fig.1),all bond lengths and angles are unexceptional.The planar chlorobenzene ring is approximately perpendicular to the fluorobenzene ring with a dihedral angle of 37.0 (1)°. The ethyl group is disordered over two positions occupancies (0.52 (2):0.48 (2)).The molecular conformation is stabilized by C—H···O and N—H···O hydrogen bonds (Table 1). The crystal packing is governed by additional N—H···O and N—H···F Interactions (Fig. 2).

Experimental

To a solution of (Z)-ethyl 3-amino-3-(4-chlorophenyl)-2-cyanoacrylate (1.25 g,0.0050 mol) in CH2Cl2(18 ml), 2,6-difluorobenzoyl chloride (2.65 g,0.015 mol) was added. Subsequently, Et3N(1.52 g,0.015 mol) waa dropped into the solution under stirring. Then, the reaction mixture was heated to reflux and stirred for 4 h and then 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. After column chromatography using ethylacetate/light petroleum (1:6) as the eluent. Small single crystals were grown from a solution of ethyl acetate/petroleum ether(3:1) after 45 days,at room temperature.

Refinement

Methyl H atoms were placed in calculated positions with C—H=0.96 Å and the torsion angle was refined to fit the electron density, with UUiso(H)=1.5UUeq(C). Other H atoms were placed in calculated positions with C—H =0.96 Å(methylene) and 0.93 Å(aromatic C—H), and refined in riding mode, with Uiso(H)=1.2Ueq(C). In the absence of significant anomalous scattering, Friedel pairs were merged.

Figures

Fig. 1.
The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
The packing of the title compound, viewed down the c axis.

Crystal data

C19H13ClF2N2O3Z = 2
Mr = 390.76F000 = 400
Triclinic, P1Dx = 1.411 Mg m3
a = 8.919 (5) ÅMo Kα radiation λ = 0.71073 Å
b = 9.7560 (6) ÅCell parameters from 2672 reflections
c = 11.2717 (7) Åθ = 2.4–26.8º
α = 91.9710 (10)ºµ = 0.25 mm1
β = 110.0940 (10)ºT = 298 (2) K
γ = 91.4490 (10)ºBlock, colorless
V = 919.9 (5) Å30.23 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer2524 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.053
Monochromator: graphiteθmax = 26.0º
T = 298(2) Kθmin = 1.9º
[var phi] and ω scansh = −10→9
Absorption correction: nonek = −12→12
7196 measured reflectionsl = −10→13
3556 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052H-atom parameters constrained
wR(F2) = 0.154  w = 1/[σ2(Fo2) + (0.0794P)2 + 0.0184P] where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
3556 reflectionsΔρmax = 0.22 e Å3
265 parametersΔρmin = −0.31 e Å3
6 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

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*/UeqOcc. (<1)
C10.7937 (2)0.8595 (2)0.98955 (19)0.0535 (5)
C20.9102 (3)0.7653 (3)1.0005 (2)0.0732 (7)
C31.0531 (3)0.7682 (3)1.0992 (3)0.0838 (8)
H31.12910.70361.10240.101*
C41.0803 (3)0.8678 (3)1.1917 (3)0.0803 (8)
H41.17560.86991.26010.096*
C50.9711 (3)0.9653 (3)1.1869 (2)0.0751 (7)
H50.99111.03361.25060.090*
C60.8309 (3)0.9595 (2)1.0850 (2)0.0595 (6)
C70.6359 (3)0.8440 (2)0.8831 (2)0.0559 (5)
C80.4458 (2)0.97457 (19)0.71787 (19)0.0488 (5)
C90.3884 (2)0.85359 (19)0.62766 (19)0.0502 (5)
C100.2296 (3)0.8088 (2)0.5863 (2)0.0622 (6)
H100.15860.85210.61800.075*
C110.1759 (3)0.7012 (2)0.4989 (2)0.0750 (8)
H110.06950.67030.47250.090*
C120.2800 (4)0.6397 (2)0.4511 (2)0.0769 (8)
C130.4383 (3)0.6827 (2)0.4905 (2)0.0755 (7)
H130.50820.64000.45730.091*
C140.4923 (3)0.7894 (2)0.5793 (2)0.0621 (6)
H140.59940.81840.60690.074*
C150.3749 (2)1.09761 (19)0.6912 (2)0.0513 (5)
C160.2483 (2)1.1126 (2)0.5730 (2)0.0560 (5)
C170.4278 (3)1.2223 (2)0.7746 (2)0.0620 (6)
C180.3811 (12)1.4663 (7)0.7837 (10)0.068 (2)0.523 (18)
H18A0.35631.52870.71500.081*0.523 (18)
H18B0.49461.47460.83160.081*0.523 (18)
C190.2853 (15)1.4949 (11)0.8666 (11)0.092 (3)0.523 (18)
H19A0.17361.48750.81690.138*0.523 (18)
H19B0.31201.58600.90440.138*0.523 (18)
H19C0.30871.42960.93170.138*0.523 (18)
H18C0.39681.40290.91880.105*0.477 (18)
H18D0.46381.49400.83430.105*0.477 (18)
H19D0.19271.54230.71920.136*0.477 (18)
H19E0.26131.61030.85610.136*0.477 (18)
H19F0.14981.47760.82940.136*0.477 (18)
Cl10.21456 (12)0.50444 (8)0.33944 (8)0.1331 (5)
F10.72205 (17)1.05606 (16)1.07956 (13)0.0850 (5)
F20.8855 (2)0.66854 (19)0.90845 (19)0.1238 (7)
N10.57876 (19)0.96329 (16)0.82386 (16)0.0544 (5)
H10.63191.03820.85670.065*
N20.1517 (2)1.1285 (2)0.4780 (2)0.0741 (6)
O10.5673 (2)0.73410 (15)0.85157 (17)0.0825 (6)
O20.5482 (2)1.23045 (16)0.86745 (17)0.0837 (6)
O30.3324 (2)1.32363 (15)0.73535 (19)0.0887 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0522 (12)0.0567 (11)0.0446 (11)−0.0027 (9)0.0076 (9)0.0076 (9)
C20.0721 (16)0.0698 (14)0.0661 (16)0.0128 (12)0.0083 (13)0.0047 (12)
C30.0652 (16)0.0906 (18)0.082 (2)0.0167 (13)0.0062 (15)0.0179 (16)
C40.0527 (14)0.111 (2)0.0633 (16)−0.0062 (14)0.0010 (12)0.0252 (15)
C50.0707 (16)0.0961 (18)0.0465 (14)−0.0138 (14)0.0067 (12)−0.0015 (12)
C60.0531 (13)0.0744 (14)0.0479 (12)−0.0006 (10)0.0138 (10)0.0029 (10)
C70.0562 (12)0.0551 (11)0.0467 (12)−0.0040 (9)0.0056 (10)0.0024 (9)
C80.0412 (10)0.0534 (10)0.0477 (12)−0.0037 (8)0.0106 (9)−0.0004 (9)
C90.0500 (11)0.0491 (10)0.0445 (11)0.0017 (8)0.0076 (9)0.0003 (8)
C100.0521 (12)0.0533 (11)0.0711 (15)0.0009 (9)0.0098 (11)−0.0098 (10)
C110.0645 (15)0.0569 (13)0.0773 (17)0.0016 (11)−0.0080 (13)−0.0112 (12)
C120.0947 (19)0.0522 (12)0.0568 (15)0.0208 (12)−0.0091 (13)−0.0072 (11)
C130.095 (2)0.0717 (15)0.0563 (15)0.0297 (14)0.0200 (14)−0.0033 (12)
C140.0616 (14)0.0673 (13)0.0572 (14)0.0130 (11)0.0197 (11)0.0023 (11)
C150.0438 (11)0.0514 (11)0.0498 (12)−0.0033 (8)0.0056 (9)−0.0014 (9)
C160.0464 (12)0.0516 (11)0.0612 (14)0.0009 (9)0.0076 (11)−0.0018 (10)
C170.0554 (13)0.0512 (11)0.0671 (15)−0.0036 (10)0.0063 (12)−0.0033 (10)
C180.084 (4)0.037 (3)0.067 (5)−0.004 (3)0.007 (4)0.001 (3)
C190.102 (8)0.082 (6)0.082 (6)−0.018 (5)0.022 (5)−0.025 (5)
Cl10.1606 (9)0.0804 (5)0.0965 (6)0.0416 (5)−0.0328 (6)−0.0442 (4)
F10.0830 (10)0.0996 (10)0.0646 (9)0.0167 (8)0.0164 (8)−0.0169 (8)
F20.1283 (15)0.1036 (12)0.1083 (14)0.0450 (11)0.0014 (11)−0.0327 (11)
N10.0465 (10)0.0488 (9)0.0534 (11)−0.0040 (7)−0.0005 (8)−0.0004 (8)
N20.0581 (12)0.0760 (13)0.0698 (14)0.0017 (10)−0.0014 (11)0.0026 (10)
O10.0875 (12)0.0556 (9)0.0744 (12)−0.0176 (8)−0.0097 (9)0.0096 (8)
O20.0777 (11)0.0612 (9)0.0783 (12)−0.0010 (8)−0.0145 (10)−0.0155 (8)
O30.0693 (11)0.0497 (9)0.1138 (15)0.0055 (7)−0.0093 (10)−0.0193 (9)

Geometric parameters (Å, °)

C1—C61.372 (3)C11—C121.365 (4)
C1—C21.382 (3)C11—H110.9300
C1—C71.504 (3)C12—C131.376 (4)
C2—F21.335 (3)C12—Cl11.734 (2)
C2—C31.373 (3)C13—C141.374 (3)
C3—C41.355 (4)C13—H130.9300
C3—H30.9300C14—H140.9300
C4—C51.368 (4)C15—C161.435 (3)
C4—H40.9300C15—C171.474 (3)
C5—C61.375 (3)C16—N21.139 (3)
C5—H50.9300C17—O21.214 (3)
C6—F11.358 (3)C17—O31.308 (3)
C7—O11.200 (2)C18—O31.475 (6)
C7—N11.382 (3)C18—C191.491 (8)
C8—C151.365 (3)C18—H18A0.9700
C8—N11.374 (2)C18—H18B0.9700
C8—C91.489 (3)C19—H19A0.9600
C9—C141.379 (3)C19—H19B0.9600
C9—C101.384 (3)C19—H19C0.9600
C10—C111.372 (3)N1—H10.8600
C10—H100.9300
C6—C1—C2115.1 (2)C12—C11—H11120.3
C6—C1—C7124.45 (19)C10—C11—H11120.3
C2—C1—C7120.34 (19)C11—C12—C13121.0 (2)
F2—C2—C3117.8 (2)C11—C12—Cl1120.3 (2)
F2—C2—C1118.6 (2)C13—C12—Cl1118.7 (2)
C3—C2—C1123.6 (2)C14—C13—C12119.5 (2)
C4—C3—C2118.2 (3)C14—C13—H13120.3
C4—C3—H3120.9C12—C13—H13120.3
C2—C3—H3120.9C13—C14—C9120.3 (2)
C3—C4—C5121.6 (2)C13—C14—H14119.9
C3—C4—H4119.2C9—C14—H14119.9
C5—C4—H4119.2C8—C15—C16119.88 (17)
C4—C5—C6118.1 (2)C8—C15—C17123.52 (18)
C4—C5—H5121.0C16—C15—C17116.48 (17)
C6—C5—H5121.0N2—C16—C15177.2 (2)
F1—C6—C1118.17 (18)O2—C17—O3124.01 (19)
F1—C6—C5118.3 (2)O2—C17—C15123.6 (2)
C1—C6—C5123.5 (2)O3—C17—C15112.34 (18)
O1—C7—N1123.20 (19)O3—C18—C19103.8 (6)
O1—C7—C1121.33 (19)O3—C18—H18A111.0
N1—C7—C1115.46 (16)C19—C18—H18A111.0
C15—C8—N1120.33 (16)O3—C18—H18B111.0
C15—C8—C9120.59 (17)C19—C18—H18B111.0
N1—C8—C9118.91 (17)H18A—C18—H18B109.0
C14—C9—C10119.25 (19)C8—N1—C7126.72 (16)
C14—C9—C8119.85 (19)C8—N1—H1116.6
C10—C9—C8120.82 (18)C7—N1—H1116.6
C11—C10—C9120.6 (2)C17—O3—C18121.6 (5)
C11—C10—H10119.7C17—O3—C18'110.6 (4)
C9—C10—H10119.7C18—O3—C18'26.1 (5)
C12—C11—C10119.4 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O20.862.052.674 (2)129
N1—H1···F10.862.362.827 (2)115
C18—H18B···O1i0.972.582.990 (7)106
C10—H10···N2ii0.932.623.302 (3)131
C5—H5···N2iii0.932.593.432 (3)150

Symmetry codes: (i) x, y+1, z; (ii) −x, −y+2, −z+1; (iii) x+1, y, z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FL2223).

References

  • Bruker (1998). SMART Bruker AXS Inc., Madison,Wisconsin, USA.
  • Bruker (1999). SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Creagh, D. C. & Hubbell, J. H. (1992). International Tables for Crystallography, Vol. C, pp. 200–206. Dordrecht: Kluwer.
  • 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]

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