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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o116.
Published online 2007 December 6. doi:  10.1107/S1600536807063167
PMCID: PMC2915187

(E)-3-(2-Chloro-3,3,3-trifluoro­prop-1-en­yl)-N-(3-methoxy­phen­yl)-2,2-dimethyl­cyclo­propane­carboxamide

Abstract

The title compound, C16H17ClF3NO2, was synthesized from 3-[(E)-2-chloro-3,3,3-trifluoro­prop-1-en­yl]-2,2-dimethyl­cyclo­propane­carboxylic acid and 3-methoxy­benzenamine. The propenyl and carboxamide substituents lie on the same side of the cyclo­propane ring plane, with the two methyl substituents on either side of the plane. The benzene ring makes a dihedral angle of 76.4 (3)° with the plane of the cyclo­propane ring. The crystal structure involves intermolecular N—H(...)O hydrogen bonds.

Related literature

For related literature, see: Liu & Yan (2007 [triangle]); Punja (1981 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o116-scheme1.jpg

Experimental

Crystal data

  • C16H17ClF3NO2
  • M r = 347.76
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o116-efi1.jpg
  • a = 16.785 (2) Å
  • b = 22.246 (3) Å
  • c = 9.4791 (12) Å
  • V = 3539.5 (8) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.25 mm−1
  • T = 294 (2) K
  • 0.22 × 0.10 × 0.01 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1997 [triangle]) T min = 0.947, T max = 0.998
  • 16415 measured reflections
  • 3119 independent reflections
  • 1325 reflections with I > 2σ(I)
  • R int = 0.081

Refinement

  • R[F 2 > 2σ(F 2)] = 0.077
  • wR(F 2) = 0.236
  • S = 1.02
  • 3119 reflections
  • 216 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.69 e Å−3
  • Δρmin = −0.55 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Bruker, 1997 [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/S1600536807063167/sf2011sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063167/sf2011Isup2.hkl

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

Acknowledgments

This work was supported by the National Natural Science Foundation (No. 20376059) and Tianjin Polytechnic University.

supplementary crystallographic information

Comment

We reasoned that a structure containing both of 3-((E)-2-Chloro- 3,3,3-trifluoroprop-1-enyl)-2,2- dimethylcyclopropanecarboxylic acid and 3-methoxybenzenamine bioactive units may show enhanced insecticidal activity and prepared the title compound (I), Fig. 1. For preparation of the title compound, see: Liu & Yan (2007); and for the insecticidal properties of related compounds, see: Punja (1981). The propenyl and carboxamide substituents lie on the same side of the C4, C5, C6 cyclopropane ring plane, with the two methyl substituents, C7 and C8 on either side of this plane. The benzene ring system is essentially planar and makes a dihedral angle of 76.4 (3)° with the plane of the cyclopropane ring. The crystal packing of (I) is shown in Fig. 2 at the end of the Comment. The packing can be described as a dimeric arrangement of molecules linked through N—H···O···H—C hydrogen bond as shown in Fig. 2 and Table 1, the packing diagram also shows F and Cl interactions..

Experimental

The title compound was prepared according to the method of Liu & Yan (2007). The product was recrystallized from acetone and ethyl acetate (9:1, v/v) over 2days at ambient temperature, giving colourless single crystals of (I), (E)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-N– (3-methoxyphenyl)-2,2-dimethylcyclopropanecarboxamide.

Refinement

H atoms were positioned geometrically with C—H = 0.93–0.98 Å and refined using riding model with Uiso(H) = 1.2Ueq(carrier).The N—H hydrogen atom was located in a difference Fourier map and refined freely with an isotropic displacement parameter.

Figures

Fig. 1.
The molecular structure of (I), drawn with 30% probability ellipsoids.
Fig. 2.
The crystal structure of (I), viewed along c axis

Crystal data

C16H17ClF3NO2Dx = 1.305 Mg m3
Mr = 347.76Mo Kα radiation λ = 0.71073 Å
Orthorhombic, PccnCell parameters from 2222 reflections
a = 16.785 (2) Åθ = 2.4–25.9º
b = 22.246 (3) ŵ = 0.25 mm1
c = 9.4791 (12) ÅT = 294 (2) K
V = 3539.5 (8) Å3Block, colourless
Z = 80.22 × 0.10 × 0.01 mm
F000 = 1440

Data collection

Bruker SMART CCD area-detector diffractometer3119 independent reflections
Radiation source: fine-focus sealed tube1325 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.081
T = 294(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 1.5º
Absorption correction: MULTI-SCAN(SADABS; Bruker, 1997)h = −16→19
Tmin = 0.947, Tmax = 0.998k = −26→26
16415 measured reflectionsl = −11→8

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.077H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.236  w = 1/[σ2(Fo2) + (0.P)2 + 13.2989P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
3119 reflectionsΔρmax = 0.69 e Å3
216 parametersΔρmin = −0.55 e Å3
1 restraintExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0014 (5)

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
Cl10.1468 (2)0.28489 (9)0.5467 (3)0.1433 (13)
C10.1084 (5)0.3528 (4)0.3245 (8)0.085 (2)
F10.0466 (4)0.3193 (3)0.2950 (5)0.160 (3)
F20.1668 (4)0.3302 (3)0.2454 (5)0.155 (2)
F30.0957 (4)0.4067 (2)0.2724 (4)0.129 (2)
O10.2154 (3)0.51918 (18)0.5554 (4)0.0682 (12)
O20.3834 (4)0.6927 (2)0.4146 (6)0.113 (2)
N10.2915 (3)0.5393 (2)0.7504 (5)0.0606 (14)
C20.1288 (4)0.3544 (3)0.4765 (7)0.0666 (18)
C30.1300 (4)0.4042 (3)0.5513 (6)0.0613 (16)
H30.11900.44000.50430.074*
C40.1473 (4)0.4082 (3)0.7024 (6)0.0652 (17)
H40.15380.36920.74920.078*
C50.1987 (4)0.4585 (3)0.7641 (6)0.0635 (17)
H50.23190.44570.84360.076*
C60.1101 (4)0.4567 (3)0.7950 (6)0.0722 (19)
C70.0558 (4)0.5034 (3)0.7319 (8)0.091 (2)
H7A0.05470.53820.79180.136*
H7B0.00300.48720.72340.136*
H7C0.07510.51460.64030.136*
C80.0874 (5)0.4372 (4)0.9438 (7)0.114 (3)
H8A0.12340.40650.97540.171*
H8B0.03400.42170.94370.171*
H8C0.09050.47111.00620.171*
C90.2344 (4)0.5077 (2)0.6786 (6)0.0558 (15)
C100.3371 (4)0.5896 (3)0.7084 (6)0.0598 (16)
C110.3868 (4)0.6149 (3)0.8111 (7)0.077 (2)
H110.38900.59830.90110.092*
C120.4326 (5)0.6643 (4)0.7784 (10)0.096 (3)
H120.46480.68150.84740.115*
C130.4313 (5)0.6888 (3)0.6451 (10)0.092 (2)
H130.46360.72150.62330.111*
C140.3815 (4)0.6643 (3)0.5434 (8)0.078 (2)
C150.3347 (4)0.6142 (3)0.5744 (7)0.0675 (18)
H150.30220.59740.50540.081*
C160.3299 (6)0.6743 (4)0.3071 (9)0.133 (4)
H16A0.33760.63230.28780.199*
H16B0.33980.69710.22300.199*
H16C0.27610.68090.33780.199*
H10.297 (4)0.529 (3)0.842 (2)0.09 (2)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.222 (3)0.0645 (13)0.143 (2)0.0358 (16)−0.034 (2)−0.0058 (13)
C10.108 (7)0.078 (5)0.071 (5)−0.016 (5)0.004 (5)−0.016 (4)
F10.181 (6)0.187 (6)0.112 (4)−0.107 (5)−0.039 (4)−0.009 (4)
F20.177 (5)0.184 (6)0.105 (4)−0.016 (5)0.042 (4)−0.075 (4)
F30.212 (6)0.118 (4)0.055 (3)−0.006 (4)−0.025 (3)0.001 (3)
O10.090 (3)0.079 (3)0.036 (2)−0.016 (2)−0.003 (2)0.007 (2)
O20.116 (5)0.107 (4)0.116 (5)−0.055 (4)−0.012 (4)0.031 (4)
N10.077 (4)0.062 (3)0.043 (3)−0.008 (3)−0.003 (3)0.000 (3)
C20.076 (5)0.061 (4)0.063 (4)0.003 (3)0.000 (3)−0.003 (3)
C30.077 (5)0.059 (4)0.048 (3)−0.005 (3)0.003 (3)0.004 (3)
C40.086 (5)0.059 (4)0.051 (3)−0.007 (4)0.003 (3)0.002 (3)
C50.084 (5)0.070 (4)0.037 (3)−0.013 (4)−0.003 (3)0.006 (3)
C60.093 (5)0.078 (5)0.046 (3)−0.016 (4)0.020 (4)−0.003 (3)
C70.078 (5)0.087 (5)0.107 (6)−0.005 (4)0.016 (5)−0.022 (5)
C80.148 (8)0.139 (7)0.054 (4)−0.057 (6)0.037 (5)−0.013 (5)
C90.070 (4)0.056 (4)0.042 (3)−0.003 (3)0.006 (3)0.000 (3)
C100.061 (4)0.057 (4)0.061 (4)0.000 (3)−0.004 (3)−0.006 (3)
C110.079 (5)0.078 (5)0.074 (5)−0.002 (4)−0.012 (4)−0.014 (4)
C120.081 (6)0.081 (6)0.126 (8)−0.012 (5)−0.018 (5)−0.025 (5)
C130.082 (6)0.075 (5)0.120 (7)−0.019 (4)−0.008 (5)−0.005 (5)
C140.076 (5)0.067 (4)0.091 (5)−0.012 (4)−0.006 (4)0.005 (4)
C150.078 (5)0.062 (4)0.063 (4)−0.015 (4)0.001 (3)−0.002 (3)
C160.160 (9)0.130 (8)0.109 (7)−0.060 (7)−0.034 (7)0.041 (6)

Geometric parameters (Å, °)

Cl1—C21.710 (6)C6—C81.524 (8)
C1—F11.308 (8)C7—H7A0.9600
C1—F31.314 (8)C7—H7B0.9600
C1—F21.333 (9)C7—H7C0.9600
C1—C21.481 (9)C8—H8A0.9600
O1—C91.238 (6)C8—H8B0.9600
O2—C141.375 (8)C8—H8C0.9600
O2—C161.419 (9)C10—C151.383 (8)
N1—C91.370 (7)C10—C111.401 (8)
N1—C101.412 (7)C11—C121.377 (10)
N1—H10.901 (10)C11—H110.9300
C2—C31.316 (8)C12—C131.377 (10)
C3—C41.464 (8)C12—H120.9300
C3—H30.9300C13—C141.388 (9)
C4—C61.524 (9)C13—H130.9300
C4—C51.530 (8)C14—C151.396 (8)
C4—H40.9800C15—H150.9300
C5—C91.487 (7)C16—H16A0.9600
C5—C61.516 (9)C16—H16B0.9600
C5—H50.9800C16—H16C0.9600
C6—C71.506 (9)
F1—C1—F3108.1 (8)C6—C7—H7C109.5
F1—C1—F2104.3 (6)H7A—C7—H7C109.5
F3—C1—F2104.6 (7)H7B—C7—H7C109.5
F1—C1—C2113.9 (7)C6—C8—H8A109.5
F3—C1—C2112.5 (6)C6—C8—H8B109.5
F2—C1—C2112.8 (7)H8A—C8—H8B109.5
C14—O2—C16119.3 (6)C6—C8—H8C109.5
C9—N1—C10130.2 (5)H8A—C8—H8C109.5
C9—N1—H1114 (4)H8B—C8—H8C109.5
C10—N1—H1115 (4)O1—C9—N1122.8 (5)
C3—C2—C1123.2 (6)O1—C9—C5124.2 (6)
C3—C2—Cl1123.3 (5)N1—C9—C5113.0 (5)
C1—C2—Cl1113.4 (5)C15—C10—C11119.8 (6)
C2—C3—C4125.5 (6)C15—C10—N1123.8 (6)
C2—C3—H3117.2C11—C10—N1116.4 (6)
C4—C3—H3117.2C12—C11—C10119.7 (7)
C3—C4—C6121.6 (6)C12—C11—H11120.1
C3—C4—C5122.0 (5)C10—C11—H11120.1
C6—C4—C559.5 (4)C13—C12—C11121.0 (7)
C3—C4—H4114.3C13—C12—H12119.5
C6—C4—H4114.3C11—C12—H12119.5
C5—C4—H4114.3C12—C13—C14119.4 (7)
C9—C5—C6121.4 (6)C12—C13—H13120.3
C9—C5—C4123.9 (5)C14—C13—H13120.3
C6—C5—C460.1 (4)O2—C14—C13115.0 (7)
C9—C5—H5113.7O2—C14—C15124.6 (7)
C6—C5—H5113.7C13—C14—C15120.5 (7)
C4—C5—H5113.7C10—C15—C14119.5 (6)
C7—C6—C5119.9 (6)C10—C15—H15120.2
C7—C6—C4120.5 (6)C14—C15—H15120.2
C5—C6—C460.4 (4)O2—C16—H16A109.5
C7—C6—C8114.4 (7)O2—C16—H16B109.5
C5—C6—C8115.5 (6)H16A—C16—H16B109.5
C4—C6—C8115.7 (6)O2—C16—H16C109.5
C6—C7—H7A109.5H16A—C16—H16C109.5
C6—C7—H7B109.5H16B—C16—H16C109.5
H7A—C7—H7B109.5
F1—C1—C2—C3−120.4 (8)C5—C4—C6—C8−106.1 (7)
F3—C1—C2—C33.0 (11)C10—N1—C9—O12.2 (10)
F2—C1—C2—C3121.0 (8)C10—N1—C9—C5−178.0 (6)
F1—C1—C2—Cl157.3 (9)C6—C5—C9—O1−59.5 (8)
F3—C1—C2—Cl1−179.3 (6)C4—C5—C9—O113.4 (10)
F2—C1—C2—Cl1−61.3 (8)C6—C5—C9—N1120.7 (6)
C1—C2—C3—C4178.0 (7)C4—C5—C9—N1−166.4 (6)
Cl1—C2—C3—C40.6 (10)C9—N1—C10—C15−4.8 (10)
C2—C3—C4—C6−149.2 (7)C9—N1—C10—C11175.1 (6)
C2—C3—C4—C5139.4 (7)C15—C10—C11—C120.5 (10)
C3—C4—C5—C90.8 (10)N1—C10—C11—C12−179.4 (6)
C6—C4—C5—C9−109.7 (7)C10—C11—C12—C13−1.2 (12)
C3—C4—C5—C6110.5 (7)C11—C12—C13—C141.8 (13)
C9—C5—C6—C73.4 (9)C16—O2—C14—C13−174.8 (8)
C4—C5—C6—C7−110.3 (7)C16—O2—C14—C155.7 (12)
C9—C5—C6—C4113.7 (6)C12—C13—C14—O2178.7 (7)
C9—C5—C6—C8−139.9 (6)C12—C13—C14—C15−1.8 (12)
C4—C5—C6—C8106.4 (7)C11—C10—C15—C14−0.5 (10)
C3—C4—C6—C7−1.8 (9)N1—C10—C15—C14179.4 (6)
C5—C4—C6—C7109.3 (7)O2—C14—C15—C10−179.4 (7)
C3—C4—C6—C5−111.0 (6)C13—C14—C15—C101.2 (11)
C3—C4—C6—C8142.9 (7)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.901 (10)2.046 (19)2.928 (6)166 (6)

Symmetry codes: (i) −x+1/2, y, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SF2011).

References

  • Bruker (1997). SADABS, SMART, SAINT and SHELXTL Bruker AXS Inc., Madison, Wisconsin, USA.
  • Liu, D.-Q. & Yan, F.-Y. (2007). Acta Cryst. E63, o4202.
  • Punja, N. (1981). European Patent EP 0031199.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.

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