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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o2156.
Published online 2010 July 31. doi:  10.1107/S1600536810029612
PMCID: PMC3007377

N-[3,5-Dichloro-4-(1,1,2,2-tetra­fluoro­eth­oxy)phen­yl]-2,6-difluoro­benzamide

Abstract

In the title compound, C15H7Cl2F6NO2, the conformation of the N—H bond in the amide segment is anti to the C=O bond and the dihedral angle between the two benzene rings is 78.6 (3)°. The terminal –CHF2 group is disordered over two orientations in a 0.67:0.33 ratio. In the crystal, the mol­ecules are linked by N—H(...)O hydrogen bonds, generating C(4) chains propagating in [100].

Related literature

For background to the biological properties of related compounds, see: Liu, Li & Li (2004 [triangle]); Liu, Li & Zhong (2004 [triangle]); Shiga et al. (2003 [triangle]). For a related structure, see: Gowda et al. (2010 [triangle]). For reference structural data, see: Allen et al. (1987 [triangle]).

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Object name is e-66-o2156-scheme1.jpg

Experimental

Crystal data

  • C15H7Cl2F6NO2
  • M r = 418.12
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2156-efi1.jpg
  • a = 9.426 (2) Å
  • b = 15.568 (4) Å
  • c = 22.601 (6) Å
  • V = 3316.7 (15) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.47 mm−1
  • T = 298 K
  • 0.16 × 0.12 × 0.10 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.929, T max = 0.955
  • 16415 measured reflections
  • 2916 independent reflections
  • 2111 reflections with I > 2σ(I)
  • R int = 0.075

Refinement

  • R[F 2 > 2σ(F 2)] = 0.084
  • wR(F 2) = 0.253
  • S = 1.06
  • 2916 reflections
  • 254 parameters
  • 35 restraints
  • H-atom parameters constrained
  • Δρmax = 0.54 e Å−3
  • Δρmin = −0.41 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [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 global, I. DOI: 10.1107/S1600536810029612/hb5568sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810029612/hb5568Isup2.hkl

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

Acknowledgments

We gratefully acknowledge the financial support of this work by the Foundation of Hubei Agricultural Scientific and Technological Innovation.

supplementary crystallographic information

Comment

Amide derivatives showed diverse biological properties such as insecticidal (Liu, Li & Li, 2004), fungicidal (Liu, Li & Zhong, 2004) and acaricidal (Shiga et al., 2003) activities. Commercialized compounds include benzamide (flutolanil, fluopicolide), nicotinamide (boscalid) and thiazole carboxamide (thifluzamide, ethaboxam). As a part of our study on the synthesis of new fluorine-containing compounds with possible biological activities, we report here the crystal structure of the title compound, (I)(Fig. 1).

In the molecule, all bond lengths and angles are normal (Allen et al., 1987). The conformation of the N—H and the C=O bonds in the amide segment are anti to each other, which is similar to that observed in other amide compound (Gowda et al., 2010). The dihedral angles between the two phenyl rings is 78.6°. The crystal structure is stabilized by intermolecular N—H···O hydrogen-bonds (Table 1).

Experimental

Triethylamine (6 mmol) was added dropwise to a stirred solution of 3,5-dichloro-4-(1,1,2,2-tetrafluoroethoxy) aniline (5 mmol) and 2,6-dichlorobenzoyl chloride (5 mmol) in dry dichloromethane (20 ml) at 275–277 K. The mixture was stirred at 283–288 K for 2 h, then washed with 0.5% hydrochloric acid solution, and a saturated aqueous solution of sodium hydrogen carbonate, dried and evaporated. The residue was recrystallized from dichloromethane, giving colourless blocks of (I) after 3 weeks.

Refinement

All H-atoms bound to carbon were refined using a riding model with d(C—H) = 0.93 Å, Uiso=1.2Ueq (C) for aromatic 0.98 Å, Uiso = 1.2Ueq (C) for CH.

Figures

Fig. 1.
The structure of (I), showing 50% probability displacement ellipsoids.
Fig. 2.
Crystal packing diagram of (I). Hydrogen bonds are shown as dashed lines.

Crystal data

C15H7Cl2F6NO2Dx = 1.675 Mg m3
Mr = 418.12Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 3100 reflections
a = 9.426 (2) Åθ = 2.7–20.5°
b = 15.568 (4) ŵ = 0.47 mm1
c = 22.601 (6) ÅT = 298 K
V = 3316.7 (15) Å3Block, colorless
Z = 80.16 × 0.12 × 0.10 mm
F(000) = 1664

Data collection

Bruker SMART APEX CCD diffractometer2916 independent reflections
Radiation source: fine-focus sealed tube2111 reflections with I > 2σ(I)
graphiteRint = 0.075
[var phi] and ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −11→11
Tmin = 0.929, Tmax = 0.955k = −16→18
16415 measured reflectionsl = −26→24

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)] = 0.084Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.253H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.1378P)2 + 2.4511P] where P = (Fo2 + 2Fc2)/3
2916 reflections(Δ/σ)max = 0.001
254 parametersΔρmax = 0.54 e Å3
35 restraintsΔρmin = −0.40 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*/UeqOcc. (<1)
C10.2885 (5)0.6858 (3)0.5451 (2)0.0619 (12)
C20.2068 (8)0.6985 (5)0.5949 (3)0.096 (2)
C30.1779 (10)0.6367 (8)0.6345 (4)0.143 (4)
H30.12500.64810.66840.172*
C40.2302 (11)0.5553 (7)0.6230 (4)0.132 (4)
H40.21020.51100.64930.158*
C50.3106 (8)0.5382 (4)0.5739 (4)0.103 (2)
H50.34450.48310.56650.124*
C60.3391 (6)0.6032 (4)0.5365 (3)0.0741 (15)
C70.3282 (4)0.7581 (3)0.5045 (2)0.0564 (11)
C80.2294 (4)0.8573 (3)0.4316 (2)0.0559 (11)
C90.1389 (5)0.8554 (3)0.3827 (2)0.0613 (12)
H90.07750.80930.37730.074*
C100.1405 (5)0.9217 (3)0.3424 (2)0.0636 (12)
C110.2300 (6)0.9916 (3)0.3497 (2)0.0672 (13)
C120.3205 (5)0.9913 (3)0.3980 (3)0.0701 (14)
C130.3201 (5)0.9259 (3)0.4389 (3)0.0683 (14)
H130.38070.92800.47140.082*
C140.1507 (7)1.1246 (4)0.3126 (3)0.0855 (17)
C150.1869 (11)1.1839 (5)0.2601 (4)0.146 (3)
H150.28931.19450.25850.175*0.67
H15'0.21111.14130.22980.175*0.33
Cl10.43376 (19)1.07768 (10)0.40998 (10)0.1141 (8)
Cl20.0311 (2)0.91643 (11)0.28089 (7)0.1026 (7)
F10.1596 (6)0.7801 (4)0.6046 (2)0.1471 (19)
F20.4199 (4)0.5898 (2)0.48811 (18)0.1020 (12)
F30.0163 (5)1.1038 (3)0.3168 (3)0.1456 (19)
F40.1720 (6)1.1679 (3)0.3624 (2)0.1382 (18)
N10.2209 (4)0.7900 (2)0.47228 (18)0.0605 (10)
H10.13900.76670.47710.073*
O10.4498 (3)0.7837 (2)0.5020 (2)0.0816 (11)
O20.2375 (4)1.0559 (2)0.30668 (17)0.0788 (11)
F60.1153 (11)1.2577 (5)0.2708 (4)0.163 (3)0.67
F50.1452 (10)1.1438 (6)0.2108 (4)0.161 (3)0.67
F5'0.3088 (15)1.2237 (11)0.2688 (8)0.157 (6)0.33
F6'0.0536 (18)1.2059 (19)0.2406 (12)0.219 (10)0.33

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.051 (3)0.069 (3)0.066 (3)−0.002 (2)−0.004 (2)0.006 (2)
C20.095 (4)0.118 (6)0.073 (4)0.010 (4)0.008 (3)0.010 (4)
C30.139 (7)0.207 (11)0.084 (5)−0.018 (8)0.013 (5)0.049 (7)
C40.142 (8)0.139 (7)0.115 (7)−0.049 (6)−0.032 (6)0.069 (6)
C50.122 (6)0.076 (4)0.112 (6)−0.022 (4)−0.030 (5)0.038 (4)
C60.075 (3)0.065 (3)0.082 (4)−0.007 (3)−0.013 (3)0.011 (3)
C70.048 (2)0.048 (2)0.074 (3)0.006 (2)0.002 (2)−0.003 (2)
C80.043 (2)0.048 (2)0.076 (3)0.0048 (18)0.007 (2)0.000 (2)
C90.063 (3)0.051 (3)0.069 (3)−0.005 (2)0.010 (2)−0.008 (2)
C100.072 (3)0.061 (3)0.058 (3)0.003 (2)0.009 (2)−0.012 (2)
C110.071 (3)0.053 (3)0.077 (3)0.007 (2)0.015 (3)−0.001 (2)
C120.058 (3)0.046 (3)0.105 (4)0.002 (2)0.001 (3)0.008 (2)
C130.059 (3)0.046 (3)0.100 (4)0.006 (2)−0.015 (3)0.000 (2)
C140.105 (5)0.058 (3)0.093 (4)0.006 (3)−0.008 (3)0.002 (3)
C150.155 (5)0.127 (5)0.154 (5)0.027 (4)−0.017 (4)0.016 (4)
Cl10.0934 (12)0.0600 (9)0.189 (2)−0.0223 (7)−0.0398 (12)0.0268 (10)
Cl20.1460 (16)0.0985 (12)0.0632 (9)−0.0185 (10)−0.0191 (9)−0.0054 (7)
F10.174 (5)0.159 (4)0.109 (3)0.050 (4)0.041 (3)−0.021 (3)
F20.123 (3)0.067 (2)0.116 (3)0.0233 (19)0.022 (2)0.0026 (18)
F30.097 (3)0.097 (3)0.243 (6)0.021 (2)0.027 (3)0.002 (3)
F40.186 (5)0.104 (3)0.125 (3)0.062 (3)−0.023 (3)−0.016 (3)
N10.042 (2)0.055 (2)0.084 (3)−0.0037 (16)0.0022 (18)0.0098 (19)
O10.0474 (19)0.064 (2)0.134 (3)−0.0028 (16)−0.014 (2)0.020 (2)
O20.091 (3)0.059 (2)0.086 (3)0.0114 (18)0.022 (2)0.0166 (18)
F60.179 (5)0.136 (4)0.174 (5)0.032 (4)−0.008 (4)0.038 (4)
F50.189 (5)0.165 (5)0.129 (4)0.017 (4)−0.020 (4)0.012 (4)
F5'0.157 (7)0.154 (7)0.160 (7)−0.004 (5)0.007 (5)0.006 (5)
F6'0.217 (11)0.221 (11)0.218 (11)0.004 (5)−0.006 (5)0.005 (5)

Geometric parameters (Å, °)

C1—C21.377 (8)C10—Cl21.733 (5)
C1—C61.385 (7)C11—C121.385 (7)
C1—C71.500 (7)C11—O21.398 (6)
C2—C31.344 (11)C12—C131.375 (7)
C2—F11.363 (8)C12—Cl11.738 (5)
C3—C41.384 (13)C13—H130.9300
C3—H30.9300C14—F31.311 (8)
C4—C51.370 (13)C14—F41.328 (7)
C4—H40.9300C14—O21.352 (7)
C5—C61.346 (8)C14—C151.540 (8)
C5—H50.9300C15—F5'1.321 (10)
C6—F21.350 (7)C15—F51.335 (8)
C7—O11.215 (5)C15—F61.355 (8)
C7—N11.341 (6)C15—F6'1.375 (10)
C8—C131.379 (6)C15—H150.9800
C8—N11.395 (6)C15—H15'0.9791
C8—C91.398 (7)N1—H10.8600
C9—C101.375 (7)F5—H15'0.7554
C9—H90.9300F5'—H150.5415
C10—C111.388 (7)
C2—C1—C6116.1 (5)C12—C13—C8119.7 (5)
C2—C1—C7122.1 (5)C12—C13—H13120.2
C6—C1—C7121.6 (5)C8—C13—H13120.2
C3—C2—F1119.6 (8)F3—C14—F4102.1 (6)
C3—C2—C1123.7 (8)F3—C14—O2113.3 (5)
F1—C2—C1116.7 (6)F4—C14—O2113.2 (5)
C2—C3—C4117.3 (9)F3—C14—C15114.7 (6)
C2—C3—H3121.4F4—C14—C15108.4 (6)
C4—C3—H3121.4O2—C14—C15105.3 (6)
C5—C4—C3121.8 (7)F5'—C15—F5126.8 (12)
C5—C4—H4119.1F5'—C15—F690.5 (10)
C3—C4—H4119.1F5—C15—F6113.5 (9)
C6—C5—C4118.2 (8)F5'—C15—F6'136.5 (16)
C6—C5—H5120.9F5—C15—F6'65.2 (13)
C4—C5—H5120.9F6—C15—F6'52.4 (12)
C5—C6—F2120.3 (6)F5'—C15—C14111.1 (10)
C5—C6—C1122.8 (7)F5—C15—C14107.3 (8)
F2—C6—C1116.8 (4)F6—C15—C14105.1 (7)
O1—C7—N1124.4 (4)F6'—C15—C14101.2 (13)
O1—C7—C1120.6 (4)F5'—C15—H1521.3
N1—C7—C1115.0 (4)F5—C15—H15109.8
C13—C8—N1122.6 (5)F6—C15—H15110.7
C13—C8—C9119.3 (4)F6'—C15—H15147.7
N1—C8—C9118.1 (4)C14—C15—H15110.3
C10—C9—C8120.1 (4)F5'—C15—H15'102.6
C10—C9—H9120.0F5—C15—H15'33.9
C8—C9—H9120.0F6—C15—H15'144.6
C9—C10—C11121.1 (5)F6'—C15—H15'99.0
C9—C10—Cl2119.3 (4)C14—C15—H15'100.6
C11—C10—Cl2119.6 (4)H15—C15—H15'82.0
C12—C11—C10117.7 (5)C7—N1—C8126.3 (4)
C12—C11—O2121.3 (5)C7—N1—H1116.9
C10—C11—O2120.6 (5)C8—N1—H1116.9
C13—C12—C11122.1 (5)C14—O2—C11117.9 (4)
C13—C12—Cl1118.0 (4)C15—F5—H15'46.3
C11—C12—Cl1119.9 (4)C15—F5'—H1541.2
C6—C1—C2—C31.5 (10)C10—C11—C12—Cl1−179.3 (4)
C7—C1—C2—C3−174.9 (7)O2—C11—C12—Cl16.7 (7)
C6—C1—C2—F1178.3 (5)C11—C12—C13—C81.4 (8)
C7—C1—C2—F11.9 (9)Cl1—C12—C13—C8178.6 (4)
F1—C2—C3—C4−179.0 (8)N1—C8—C13—C12−178.3 (5)
C1—C2—C3—C4−2.3 (13)C9—C8—C13—C12−0.1 (7)
C2—C3—C4—C51.3 (14)F3—C14—C15—F5'159.9 (10)
C3—C4—C5—C60.4 (13)F4—C14—C15—F5'46.6 (12)
C4—C5—C6—F2178.8 (6)O2—C14—C15—F5'−74.8 (11)
C4—C5—C6—C1−1.2 (10)F3—C14—C15—F5−57.7 (10)
C2—C1—C6—C50.4 (8)F4—C14—C15—F5−171.1 (7)
C7—C1—C6—C5176.8 (5)O2—C14—C15—F567.5 (9)
C2—C1—C6—F2−179.7 (5)F3—C14—C15—F663.3 (10)
C7—C1—C6—F2−3.3 (7)F4—C14—C15—F6−50.0 (10)
C2—C1—C7—O1109.9 (6)O2—C14—C15—F6−171.4 (8)
C6—C1—C7—O1−66.3 (7)F3—C14—C15—F6'9.5 (16)
C2—C1—C7—N1−70.5 (7)F4—C14—C15—F6'−103.8 (15)
C6—C1—C7—N1113.3 (5)O2—C14—C15—F6'134.8 (15)
C13—C8—C9—C10−0.2 (7)O1—C7—N1—C8−0.8 (8)
N1—C8—C9—C10178.0 (4)C1—C7—N1—C8179.6 (4)
C8—C9—C10—C11−0.6 (7)C13—C8—N1—C7−33.8 (7)
C8—C9—C10—Cl2178.1 (4)C9—C8—N1—C7148.1 (5)
C9—C10—C11—C121.8 (7)F3—C14—O2—C11−55.4 (7)
Cl2—C10—C11—C12−177.0 (4)F4—C14—O2—C1160.3 (7)
C9—C10—C11—O2175.9 (4)C15—C14—O2—C11178.5 (6)
Cl2—C10—C11—O2−2.9 (6)C12—C11—O2—C14−94.2 (6)
C10—C11—C12—C13−2.2 (8)C10—C11—O2—C1492.0 (6)
O2—C11—C12—C13−176.2 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.002.861 (5)174

Symmetry codes: (i) x−1/2, −y+3/2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5568).

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.
  • Bruker (2000). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Gowda, B. T., Tokarčík, M., Shakuntala, K., Kožíšek, J. & Fuess, H. (2010). Acta Cryst. E66, o1529–o1530. [PMC free article] [PubMed]
  • Liu, C. L., Li, L. & Li, Z. M. (2004). Bioorg. Med. Chem.12, 2825–2830. [PubMed]
  • Liu, C. L., Li, Z. M. & Zhong, B. (2004). J. Fluorine Chem.125, 1287–1290.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Shiga, Y., Okada, I. & Fukuchi, T. (2003). J. Pestic. Sci.28, 310–312.

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