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Acta Crystallogr Sect E Struct Rep Online. 2008 September 1; 64(Pt 9): o1756.
Published online 2008 August 13. doi:  10.1107/S1600536808025506
PMCID: PMC2960696

N-{[2,5-Dichloro-4-(1,1,2,3,3,3-hexa­fluoro­prop­oxy)phen­yl]amino­carbon­yl}-2,6-difluoro­benzamide

Abstract

In the mol­ecule of the title compound, C17H8Cl2F8N2O3, the two aromatic rings are oriented at a dihedral angle of 50.12 (3)°. Intra­molecular N—H(...)O, C—H(...)O and N—H(...)Cl hydrogen bonds result in the formation of two six- and one five-membered rings. The six-membered rings have flattened-boat conformations, while the five-membered ring adopts an envelope conformation. In the crystal structure, inter­molecular N—H(...)O hydrogen bonds link the mol­ecules into centrosymmetric dimers.

Related literature

For related literature, see: Drabek & Boeger (1986 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]). For ring conformation puckering parameters, see: Cremer & Pople (1975 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1756-scheme1.jpg

Experimental

Crystal data

  • C17H8Cl2F8N2O3
  • M r = 511.15
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1756-efi1.jpg
  • a = 9.2300 (18) Å
  • b = 16.404 (3) Å
  • c = 14.074 (3) Å
  • β = 108.77 (3)°
  • V = 2017.6 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.42 mm−1
  • T = 294 (2) K
  • 0.40 × 0.30 × 0.20 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.851, T max = 0.921
  • 3609 measured reflections
  • 3609 independent reflections
  • 1922 reflections with I > 2σ(I)
  • 3 standard reflections every 200 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.086
  • wR(F 2) = 0.247
  • S = 1.09
  • 3609 reflections
  • 283 parameters
  • 96 restraints
  • H-atom parameters constrained
  • Δρmax = 0.42 e Å−3
  • Δρmin = −0.34 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808025506/hk2510sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808025506/hk2510Isup2.hkl

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

supplementary crystallographic information

Comment

The title compound is considered to belong to the fourth generation of insectides with properties such as high selectivity, low acute toxicity for mammals and high biological activity. It is generally recognized as a chitin-synthesis inhibitor that interrupts chitin-synthesis during the development and reproduction of the insectide. As part of our studies in this area, we report herein the crystal structure of the title compound.

In the molecule of the title compound, (Fig. 1) the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C1-C6) and B (C9-C14) are, of course, planar, and the dihedral angle between them is A/B = 50.12 (3)°. The intramolecular N-H···O, C-H···O and N-H···Cl hydrogen bonds (Table 1) result in the formation of two six- and one five-membered non-planar rings: C (O1/N1/N2/C7/C8/H2A), D (O2/N2/C8-C10/H10A) and E (Cl2/N2/C9/C14/H2A). Rings C and D adopt twisted [[var phi] = -169.19 (2)°, θ = 21.09 (3)° (for ring C) and [var phi] = 178.48 (3)°, θ = 127.74 (3)° (for ring D)] conformations, having total puckering amplitudes, QT, of 0.113 (3) and 0.201 (3) Å, respectively (Cremer & Pople, 1975). Ring E adopts envelope conformation, with H2A atom displaced by 0.190 (3) Å from the plane of the other ring atoms.

In the crystal structure, intermolecular N-H···O hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

The title compound was prepared according to the literature method (Drabek & Boeger, 1986). The crystals suitable for X-ray analysis were obtained by dissolving the title compound (0.3 g) in acetonitrile (25 ml) and evaporating the solvent slowly at room temperature for about 8 d.

Refinement

H atoms were positioned geometrically, with N-H = 0.86 Å (for NH) and C-H = 0.93 and 0.98 Å for aromatic and methine H, respectively, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C,N).

Figures

Fig. 1.
The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.
Fig. 2.
A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C17H8Cl2F8N2O3F000 = 1016
Mr = 511.15Dx = 1.683 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 9.2300 (18) Åθ = 9–12º
b = 16.404 (3) ŵ = 0.42 mm1
c = 14.074 (3) ÅT = 294 (2) K
β = 108.77 (3)ºBlock, colorless
V = 2017.6 (8) Å30.40 × 0.30 × 0.20 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.0000
Radiation source: fine-focus sealed tubeθmax = 25.2º
Monochromator: graphiteθmin = 2.0º
T = 294(2) Kh = −11→10
ω/2θ scansk = 0→19
Absorption correction: ψ scan(North et al., 1968)l = 0→16
Tmin = 0.851, Tmax = 0.9213 standard reflections
3609 measured reflections every 200 reflections
3609 independent reflections intensity decay: none
1922 reflections with I > 2σ(I)

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.086H-atom parameters constrained
wR(F2) = 0.248  w = 1/[σ2(Fo2) + (0.1258P)2 + 1.1819P] where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max = 0.001
3609 reflectionsΔρmax = 0.42 e Å3
283 parametersΔρmin = −0.34 e Å3
96 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 > 2sigma(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
Cl11.21022 (15)1.15534 (9)0.61828 (12)0.0527 (5)
Cl21.06547 (19)0.83402 (11)0.80001 (17)0.0914 (8)
F10.4001 (5)0.7889 (3)0.7184 (3)0.0975 (16)
F20.4224 (4)0.8023 (3)0.3906 (3)0.0810 (13)
F31.5260 (5)1.0359 (3)0.6887 (5)0.1116 (18)
F41.5722 (4)0.9618 (3)0.8001 (4)0.1039 (17)
F51.8146 (6)1.0579 (3)0.7942 (5)0.145 (3)
F61.8127 (6)1.0156 (3)0.9703 (4)0.1121 (18)
F71.9281 (6)1.1152 (3)0.9350 (4)0.119 (2)
F81.6616 (6)1.1347 (3)0.9601 (4)0.1029 (15)
O10.6850 (4)0.7921 (2)0.6546 (4)0.0703 (15)
O20.6981 (4)1.0216 (3)0.5376 (3)0.0505 (11)
O31.4248 (4)1.0694 (3)0.7916 (4)0.0758 (16)
N10.5870 (4)0.9045 (2)0.5577 (3)0.0359 (11)
H1A0.50330.92420.51750.043*
N20.8483 (4)0.9219 (2)0.6377 (3)0.0327 (10)
H2A0.84680.87240.65760.039*
C10.1954 (8)0.7296 (5)0.5816 (6)0.074 (2)
H1B0.14140.71400.62420.089*
C20.1405 (7)0.7183 (4)0.4832 (5)0.0588 (17)
H2B0.04440.69450.45690.071*
C30.2142 (7)0.7389 (4)0.4199 (5)0.0607 (17)
H3A0.17040.72750.35190.073*
C40.3505 (6)0.7758 (4)0.4526 (4)0.0450 (14)
C50.4228 (6)0.7893 (3)0.5551 (4)0.0435 (14)
C60.3397 (7)0.7666 (4)0.6175 (5)0.0568 (16)
C70.5790 (6)0.8247 (3)0.5960 (4)0.0437 (14)
C80.7151 (6)0.9534 (3)0.5785 (4)0.0407 (14)
C90.9852 (5)0.9614 (3)0.6689 (4)0.0330 (12)
C101.0214 (5)1.0332 (3)0.6291 (4)0.0368 (12)
H10A0.94771.05950.57700.044*
C111.1661 (5)1.0655 (3)0.6667 (4)0.0355 (12)
C121.2807 (6)1.0310 (4)0.7494 (5)0.0518 (16)
C131.2445 (7)0.9591 (4)0.7901 (5)0.0572 (17)
H13A1.31590.93500.84530.069*
C141.1065 (5)0.9252 (3)0.7492 (4)0.0391 (13)
C151.5460 (7)1.0386 (4)0.8024 (7)0.079 (3)
C161.6854 (8)1.0845 (5)0.8271 (9)0.107 (4)
H16A1.65761.13940.79990.129*
C171.7772 (11)1.0946 (6)0.9319 (7)0.089

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0401 (8)0.0436 (9)0.0782 (11)−0.0152 (6)0.0242 (7)−0.0007 (7)
Cl20.0513 (10)0.0599 (12)0.1330 (18)−0.0100 (8)−0.0123 (10)0.0497 (12)
F10.097 (3)0.135 (4)0.051 (3)−0.054 (3)0.010 (2)0.026 (2)
F20.086 (3)0.103 (3)0.059 (3)−0.045 (3)0.030 (2)−0.034 (2)
F30.099 (4)0.106 (4)0.133 (5)−0.034 (3)0.041 (3)−0.032 (3)
F40.054 (2)0.072 (3)0.172 (5)−0.010 (2)0.019 (3)−0.015 (3)
F50.092 (3)0.141 (5)0.225 (7)−0.023 (3)0.082 (4)−0.111 (5)
F60.127 (4)0.104 (4)0.095 (4)−0.017 (3)0.021 (3)0.052 (3)
F70.099 (3)0.083 (3)0.116 (4)−0.024 (3)−0.048 (3)0.006 (3)
F80.097 (3)0.111 (4)0.103 (4)−0.001 (3)0.034 (3)−0.012 (3)
O10.029 (2)0.047 (3)0.107 (4)0.0006 (18)−0.017 (2)0.037 (2)
O20.046 (2)0.047 (3)0.057 (3)−0.0033 (19)0.013 (2)−0.005 (2)
O30.035 (2)0.043 (3)0.129 (5)−0.009 (2)−0.001 (2)0.009 (3)
N10.028 (2)0.019 (2)0.058 (3)0.0007 (17)0.009 (2)0.0093 (19)
N20.028 (2)0.025 (2)0.043 (3)−0.0005 (17)0.0085 (19)−0.0044 (19)
C10.070 (4)0.082 (5)0.076 (4)−0.028 (4)0.032 (4)0.017 (4)
C20.046 (3)0.051 (4)0.071 (4)−0.016 (3)0.007 (3)0.003 (3)
C30.059 (4)0.061 (4)0.051 (4)−0.023 (3)0.002 (3)−0.014 (3)
C40.045 (3)0.046 (3)0.042 (3)−0.003 (3)0.011 (3)−0.004 (3)
C50.039 (3)0.042 (3)0.047 (3)−0.006 (2)0.011 (2)0.010 (3)
C60.044 (3)0.067 (4)0.053 (4)−0.009 (3)0.007 (3)0.014 (3)
C70.045 (3)0.039 (3)0.047 (4)−0.010 (3)0.016 (3)0.004 (3)
C80.037 (3)0.027 (3)0.051 (4)0.000 (2)0.005 (3)0.009 (3)
C90.026 (2)0.036 (3)0.036 (3)0.000 (2)0.009 (2)−0.005 (2)
C100.032 (2)0.040 (3)0.042 (3)−0.007 (2)0.016 (2)−0.003 (2)
C110.033 (3)0.035 (3)0.044 (3)−0.009 (2)0.020 (2)0.008 (2)
C120.030 (3)0.053 (4)0.065 (4)−0.003 (2)0.006 (3)0.004 (3)
C130.042 (3)0.051 (4)0.071 (4)0.013 (3)0.007 (3)0.017 (3)
C140.022 (2)0.042 (3)0.049 (3)0.012 (2)0.005 (2)0.009 (2)
C150.029 (3)0.050 (5)0.142 (8)0.006 (3)0.007 (4)−0.014 (4)
C160.041 (4)0.046 (4)0.219 (11)−0.009 (3)0.021 (5)0.007 (6)
C170.0800.0890.096−0.0060.0260.004

Geometric parameters (Å, °)

Cl1—C111.727 (5)C2—C31.326 (9)
Cl2—C141.751 (6)C2—H2B0.9300
F1—C61.398 (7)O3—C151.191 (7)
F2—C41.327 (7)O3—C121.418 (6)
F3—C151.552 (10)C3—C41.338 (8)
F4—C151.284 (8)C3—H3A0.9300
F5—C161.477 (9)C4—C51.399 (8)
F6—C171.403 (10)C5—C61.389 (8)
F7—C171.420 (10)C5—C71.488 (7)
F8—C171.415 (10)C9—C101.390 (7)
O1—C71.186 (6)C9—C141.439 (7)
N1—C81.380 (6)C10—C111.374 (7)
N1—C71.427 (7)C10—H10A0.9300
N1—H1A0.8600C11—C121.414 (7)
C1—C21.327 (10)C12—C131.398 (8)
C1—C61.401 (9)C13—C141.338 (8)
C1—H1B0.9300C13—H13A0.9300
N2—C81.347 (6)C15—C161.434 (9)
N2—C91.361 (6)C16—C171.455 (13)
N2—H2A0.8600C16—H16A0.9800
O2—C81.245 (6)
C8—N1—C7126.7 (4)C11—C10—C9120.1 (5)
C8—N1—H1A116.6C11—C10—H10A120.0
C7—N1—H1A116.6C9—C10—H10A120.0
C2—C1—C6115.8 (6)C10—C11—C12122.7 (5)
C2—C1—H1B122.1C10—C11—Cl1120.0 (4)
C6—C1—H1B122.1C12—C11—Cl1117.2 (4)
C8—N2—C9125.8 (4)C13—C12—C11117.4 (5)
C8—N2—H2A117.1C13—C12—O3121.2 (5)
C9—N2—H2A117.1C11—C12—O3121.4 (5)
C1—C2—C3124.0 (6)C14—C13—C12119.7 (5)
C1—C2—H2B118.0C14—C13—H13A120.2
C3—C2—H2B118.0C12—C13—H13A120.2
C15—O3—C12125.5 (6)C13—C14—C9123.9 (5)
C2—C3—C4120.9 (6)C13—C14—Cl2118.8 (4)
C2—C3—H3A119.6C9—C14—Cl2117.2 (4)
C4—C3—H3A119.6O3—C15—F4126.1 (6)
F2—C4—C3122.4 (6)O3—C15—C16122.7 (7)
F2—C4—C5117.0 (5)F4—C15—C16111.1 (6)
C3—C4—C5120.7 (6)O3—C15—F394.9 (6)
C6—C5—C4115.6 (5)F4—C15—F384.7 (6)
C6—C5—C7121.6 (5)C16—C15—F393.7 (7)
C4—C5—C7122.8 (5)C15—C16—C17119.4 (9)
C5—C6—F1116.8 (5)C15—C16—F5121.4 (7)
C5—C6—C1122.9 (6)C17—C16—F594.9 (6)
F1—C6—C1120.1 (6)C15—C16—H16A106.6
O1—C7—N1123.1 (5)C17—C16—H16A106.6
O1—C7—C5125.0 (5)F5—C16—H16A106.6
N1—C7—C5111.9 (5)F6—C17—F8115.2 (7)
O2—C8—N2125.8 (5)F6—C17—F795.9 (6)
O2—C8—N1116.9 (4)F8—C17—F7134.6 (8)
N2—C8—N1117.2 (5)F6—C17—C16105.8 (7)
N2—C9—C10126.3 (5)F8—C17—C1695.3 (7)
N2—C9—C14117.6 (5)F7—C17—C16107.7 (7)
C10—C9—C14116.0 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···Cl20.862.432.892 (4)115
N2—H2A···O10.861.982.664 (6)135
N1—H1A···O2i0.861.982.814 (6)163
C10—H10A···O20.932.282.851 (6)119

Symmetry codes: (i) −x+1, −y+2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2510).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc.97, 1354–1358.
  • Drabek, J. & Boeger, M. (1986). European Patent No. 179022.
  • Enraf–Nonius (1989). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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