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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2946.
Published online 2009 October 31. doi:  10.1107/S1600536809044584
PMCID: PMC2971195

N-{N-[5-(2,4-Dichloro­phen­yl)-1,3,4-thia­diazol-2-yl]carbamo­yl}-2,6-difluoro­benzamide

Abstract

In the title compound, C16H8Cl2F2N4O2S, the thia­diazole ring makes dihedral angles of 24.94 (14) and 48.11 (14)°, respectively, with the dichloro- and difluoro-substituted benzene rings. An intra­molecular N—H(...)O hydrogen bond results in the formation of a planar (mean deviation 0.0091 Å) six-membered ring. In the crystal structure, mol­ecules form centrosymmetric dimers through pairs of inter­molecular N—H(...)O hydrogen bonds.

Related literature

For 1,3,4-thia­diazole aryl­urea derivatives, see: Hajjar & Casida (1978 [triangle]); Leighton et al. (1981 [triangle]); Metcalf et al. (1975 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-65-o2946-scheme1.jpg

Experimental

Crystal data

  • C16H8Cl2F2N4O2S
  • M r = 429.22
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2946-efi1.jpg
  • a = 8.1600 (16) Å
  • b = 7.6100 (15) Å
  • c = 27.102 (5) Å
  • β = 92.42 (3)°
  • V = 1681.5 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.55 mm−1
  • T = 293 K
  • 0.30 × 0.20 × 0.20 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.852, T max = 0.898
  • 5228 measured reflections
  • 3053 independent reflections
  • 2195 reflections with I > 2σ(I)
  • R int = 0.034
  • 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.122
  • S = 1.01
  • 3053 reflections
  • 244 parameters
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.30 e Å−3

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994 [triangle]); cell refinement: CAD-4 EXPRESS; 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: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809044584/is2477sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809044584/is2477Isup2.hkl

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

Acknowledgments

The authors gratefully acknowledge Professor Hua-Qin Wang of the Analysis Center, Nanjing University, for providing the Enraf–Nonius CAD-4 diffractometer for this research project.

supplementary crystallographic information

Comment

1,3,4-Thiadiazole aroylurea derivatives are promising and effective insecticides used for the control of insects attacking a wide range of crops. These compounds are generally recognized as insect growth regulators that interfere with chitin synthesis in target pests, causing death or abortive development (Hajjar & Casida, 1978; Leighton et al., 1981). They are considered to be a fourth generation of insecticides with many attractive properties such as high selectivity, low acute toxicity for mammals, and high biological activity, resulting in low application rates (Metcalf et al., 1975).

We report herein the crystal structure of the title compound,(I). 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), B(S/C9/N3/N4/C10) and C(C11–C16) are, of course, planar. The dihedral angle between them is A/B = 47.8 (3)°, A/C=23.1 (3)° and B/C= 24.9 (4)°. The intramolecular N—H···O hydrogen bond (Table 1) results in the formation of one planar six-membered ring D(N2/H2A/O1/C7/N1/C8). They are oriented with respect to the adjacent rings at dihedral angles of A/D= 40.3 (4)°, B/D= 8.6 (4)° and C/D= 17.3 (1)°. So rings B and D are nearly coplanar. In the crystal structure, intermolecular N—H···O hydrogen bonds (Table 1) link the molecules to form a dimeric unit (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

2,6-Difluorobenzoyl isocyanate (14 mmol) was added dropwise to the solution of 5-(2,4-dichlorophenyl)-1,3,4-thiadiazol-2-amine (10 mmol) in toluene under the reflux temperature. The reaction mixture was stirred and refluxed for 5 h. After cooling and filtering, crude compound (I) was obtained. Pure compound (I) was obtained by recrystallization from DMF (15 ml). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of a DMF-H2O solution.

Refinement

H atoms were placed geometrically (C—H = 0.93 and N—H = 0.86 Å) and included in the refinement in riding motion approximation, with Uiso(H) = 1.2Ueq of the carrier atom.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The hydrogen bond is shown as a dashed line.
Fig. 2.
A partial packing diagram of (I). Hydrogen bonds are shown as dashed lines.

Crystal data

C16H8Cl2F2N4O2SF(000) = 864
Mr = 429.22Dx = 1.696 Mg m3
Monoclinic, P21/cMelting point: 498 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 8.1600 (16) ÅCell parameters from 25 reflections
b = 7.6100 (15) Åθ = 10–13°
c = 27.102 (5) ŵ = 0.55 mm1
β = 92.42 (3)°T = 293 K
V = 1681.5 (6) Å3Block, yellow
Z = 40.30 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer2195 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.034
graphiteθmax = 25.3°, θmin = 1.5°
ω/2θ scansh = 0→9
Absorption correction: ψ scan (North et al., 1968)k = −4→9
Tmin = 0.852, Tmax = 0.898l = −32→32
5228 measured reflections3 standard reflections every 200 reflections
3053 independent reflections intensity decay: 1%

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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.07P)2] where P = (Fo2 + 2Fc2)/3
3053 reflections(Δ/σ)max < 0.001
244 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = −0.30 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
S0.24677 (10)0.99323 (10)0.44933 (3)0.0422 (2)
Cl10.07127 (15)1.02058 (11)0.34523 (3)0.0704 (3)
Cl2−0.13977 (11)1.65344 (11)0.29072 (3)0.0557 (3)
F10.6408 (2)0.7102 (3)0.70051 (7)0.0601 (5)
F20.4085 (3)0.2644 (2)0.60078 (7)0.0616 (5)
O10.3906 (3)0.7670 (3)0.63370 (8)0.0534 (6)
O20.3952 (3)0.6786 (3)0.48524 (7)0.0584 (7)
N10.4499 (3)0.6085 (3)0.56566 (8)0.0433 (6)
H1A0.49570.51310.55620.052*
N20.3126 (3)0.8663 (3)0.54369 (9)0.0419 (6)
H2A0.31020.88430.57500.050*
N30.1602 (3)1.1185 (3)0.53201 (9)0.0429 (6)
N40.0980 (3)1.2319 (3)0.49659 (9)0.0433 (6)
C10.6387 (4)0.2440 (5)0.71587 (13)0.0592 (10)
H1B0.67650.16020.73860.071*
C20.5527 (4)0.1908 (4)0.67364 (13)0.0526 (9)
H2B0.53240.07240.66750.063*
C30.4981 (4)0.3162 (4)0.64105 (11)0.0432 (7)
C40.5219 (3)0.4949 (4)0.64808 (10)0.0372 (7)
C50.6099 (4)0.5392 (4)0.69135 (11)0.0447 (8)
C60.6695 (4)0.4191 (5)0.72498 (12)0.0557 (9)
H6A0.72920.45460.75320.067*
C70.4482 (4)0.6364 (4)0.61606 (10)0.0390 (7)
C80.3853 (4)0.7180 (4)0.52848 (11)0.0417 (7)
C90.2414 (3)0.9916 (4)0.51268 (10)0.0363 (7)
C100.1319 (3)1.1852 (4)0.45196 (10)0.0359 (7)
C110.0728 (3)1.2949 (4)0.40993 (10)0.0366 (7)
C120.0397 (4)1.2367 (4)0.36183 (11)0.0381 (7)
C13−0.0232 (4)1.3465 (4)0.32543 (11)0.0425 (7)
H13A−0.04311.30520.29340.051*
C14−0.0561 (4)1.5183 (4)0.33714 (10)0.0395 (7)
C15−0.0260 (4)1.5824 (4)0.38409 (11)0.0481 (8)
H15A−0.04881.69880.39160.058*
C160.0386 (4)1.4703 (4)0.41965 (11)0.0455 (8)
H16A0.06011.51340.45140.055*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S0.0482 (5)0.0403 (5)0.0384 (4)0.0116 (4)0.0050 (3)−0.0003 (3)
Cl10.1326 (9)0.0327 (5)0.0451 (5)0.0130 (5)−0.0047 (5)−0.0082 (4)
Cl20.0709 (6)0.0489 (5)0.0469 (5)0.0135 (4)−0.0026 (4)0.0082 (4)
F10.0674 (13)0.0525 (12)0.0589 (12)−0.0073 (10)−0.0146 (10)−0.0105 (9)
F20.0766 (14)0.0489 (12)0.0578 (12)−0.0075 (10)−0.0145 (10)−0.0106 (9)
O10.0714 (16)0.0449 (14)0.0436 (12)0.0189 (12)0.0004 (11)−0.0060 (10)
O20.0841 (17)0.0548 (15)0.0363 (12)0.0297 (13)0.0035 (11)−0.0017 (10)
N10.0530 (16)0.0385 (15)0.0382 (13)0.0141 (12)−0.0017 (11)−0.0005 (11)
N20.0498 (15)0.0402 (15)0.0354 (13)0.0098 (12)−0.0024 (11)−0.0021 (11)
N30.0494 (15)0.0373 (15)0.0415 (14)0.0091 (12)−0.0035 (12)−0.0026 (12)
N40.0510 (16)0.0396 (15)0.0390 (14)0.0107 (12)−0.0015 (12)−0.0031 (11)
C10.062 (2)0.064 (3)0.052 (2)0.0136 (19)−0.0012 (18)0.0170 (18)
C20.055 (2)0.0393 (19)0.064 (2)0.0022 (16)0.0085 (17)0.0071 (16)
C30.0423 (17)0.0447 (19)0.0427 (17)−0.0009 (15)0.0026 (13)−0.0031 (14)
C40.0361 (15)0.0392 (17)0.0363 (15)−0.0001 (13)0.0028 (12)−0.0007 (13)
C50.0415 (18)0.048 (2)0.0449 (17)−0.0003 (15)0.0009 (14)−0.0045 (15)
C60.055 (2)0.065 (2)0.0464 (19)0.0020 (18)−0.0079 (16)0.0048 (17)
C70.0402 (16)0.0381 (17)0.0386 (16)0.0004 (14)−0.0009 (13)−0.0042 (13)
C80.0433 (17)0.0418 (18)0.0399 (17)0.0086 (14)0.0011 (14)0.0004 (14)
C90.0378 (16)0.0343 (16)0.0365 (15)0.0011 (13)−0.0032 (12)−0.0050 (13)
C100.0385 (16)0.0279 (15)0.0410 (16)0.0011 (13)−0.0003 (13)−0.0042 (12)
C110.0399 (16)0.0315 (16)0.0387 (15)0.0019 (13)0.0052 (13)−0.0024 (13)
C120.0456 (17)0.0281 (16)0.0408 (16)0.0000 (13)0.0056 (13)−0.0062 (12)
C130.0507 (18)0.0406 (18)0.0360 (15)0.0008 (15)0.0001 (13)−0.0035 (14)
C140.0420 (17)0.0375 (18)0.0393 (16)0.0009 (14)0.0055 (13)0.0025 (13)
C150.069 (2)0.0321 (17)0.0429 (17)0.0119 (16)0.0016 (15)−0.0034 (14)
C160.063 (2)0.0365 (18)0.0368 (16)0.0031 (16)0.0006 (14)−0.0060 (13)

Geometric parameters (Å, °)

S—C91.719 (3)C1—H1B0.9300
S—C101.738 (3)C2—C31.362 (4)
Cl1—C121.727 (3)C2—H2B0.9300
Cl2—C141.742 (3)C3—C41.386 (4)
F1—C51.347 (4)C4—C51.390 (4)
F2—C31.347 (4)C4—C71.494 (4)
O1—C71.206 (3)C5—C61.365 (4)
O2—C81.216 (3)C6—H6A0.9300
N1—C71.383 (4)C10—C111.477 (4)
N1—C81.394 (4)C11—C161.391 (4)
N1—H1A0.8600C11—C121.393 (4)
N2—C81.348 (4)C12—C131.375 (4)
N2—C91.383 (4)C13—C141.375 (4)
N2—H2A0.8600C13—H13A0.9300
N3—C91.294 (3)C14—C151.375 (4)
N3—N41.372 (3)C15—C161.375 (4)
N4—C101.302 (4)C15—H15A0.9300
C1—C61.376 (5)C16—H16A0.9300
C1—C21.378 (5)
C9—S—C1085.91 (14)N1—C7—C4116.3 (3)
C7—N1—C8127.1 (3)O2—C8—N2123.3 (3)
C7—N1—H1A116.5O2—C8—N1120.7 (3)
C8—N1—H1A116.5N2—C8—N1115.9 (3)
C8—N2—C9124.8 (2)N3—C9—N2118.5 (2)
C8—N2—H2A117.6N3—C9—S115.7 (2)
C9—N2—H2A117.6N2—C9—S125.7 (2)
C9—N3—N4111.5 (2)N4—C10—C11119.1 (3)
C10—N4—N3113.0 (2)N4—C10—S113.8 (2)
C6—C1—C2121.1 (3)C11—C10—S127.1 (2)
C6—C1—H1B119.5C16—C11—C12116.7 (3)
C2—C1—H1B119.5C16—C11—C10117.3 (3)
C3—C2—C1118.3 (3)C12—C11—C10125.9 (3)
C3—C2—H2B120.9C13—C12—C11122.0 (3)
C1—C2—H2B120.9C13—C12—Cl1116.5 (2)
F2—C3—C2118.1 (3)C11—C12—Cl1121.4 (2)
F2—C3—C4117.8 (3)C12—C13—C14118.9 (3)
C2—C3—C4123.9 (3)C12—C13—H13A120.6
C3—C4—C5114.7 (3)C14—C13—H13A120.6
C3—C4—C7125.2 (3)C15—C14—C13121.5 (3)
C5—C4—C7119.8 (3)C15—C14—Cl2120.5 (2)
F1—C5—C6117.7 (3)C13—C14—Cl2118.0 (2)
F1—C5—C4118.4 (3)C14—C15—C16118.5 (3)
C6—C5—C4123.9 (3)C14—C15—H15A120.8
C5—C6—C1118.1 (3)C16—C15—H15A120.8
C5—C6—H6A121.0C15—C16—C11122.4 (3)
C1—C6—H6A121.0C15—C16—H16A118.8
O1—C7—N1122.6 (3)C11—C16—H16A118.8
O1—C7—C4121.2 (3)
C9—N3—N4—C101.1 (4)N4—N3—C9—S−1.6 (3)
C6—C1—C2—C3−0.2 (5)C8—N2—C9—N3172.6 (3)
C1—C2—C3—F2−177.4 (3)C8—N2—C9—S−5.9 (4)
C1—C2—C3—C4−0.9 (5)C10—S—C9—N31.2 (2)
F2—C3—C4—C5177.6 (3)C10—S—C9—N2179.8 (3)
C2—C3—C4—C51.0 (5)N3—N4—C10—C11180.0 (3)
F2—C3—C4—C73.7 (5)N3—N4—C10—S−0.2 (3)
C2—C3—C4—C7−172.8 (3)C9—S—C10—N4−0.5 (2)
C3—C4—C5—F1178.9 (3)C9—S—C10—C11179.3 (3)
C7—C4—C5—F1−6.9 (4)N4—C10—C11—C1623.2 (4)
C3—C4—C5—C6−0.1 (5)S—C10—C11—C16−156.5 (2)
C7—C4—C5—C6174.2 (3)N4—C10—C11—C12−153.1 (3)
F1—C5—C6—C1−179.9 (3)S—C10—C11—C1227.1 (4)
C4—C5—C6—C1−0.9 (5)C16—C11—C12—C130.2 (4)
C2—C1—C6—C51.1 (5)C10—C11—C12—C13176.6 (3)
C8—N1—C7—O1−1.6 (5)C16—C11—C12—Cl1−178.2 (2)
C8—N1—C7—C4178.2 (3)C10—C11—C12—Cl1−1.9 (4)
C3—C4—C7—O1136.8 (3)C11—C12—C13—C14−0.8 (5)
C5—C4—C7—O1−36.8 (4)Cl1—C12—C13—C14177.7 (2)
C3—C4—C7—N1−43.1 (4)C12—C13—C14—C150.6 (5)
C5—C4—C7—N1143.3 (3)C12—C13—C14—Cl2−178.7 (2)
C9—N2—C8—O2−0.3 (5)C13—C14—C15—C160.0 (5)
C9—N2—C8—N1179.9 (3)Cl2—C14—C15—C16179.3 (2)
C7—N1—C8—O2179.7 (3)C14—C15—C16—C11−0.6 (5)
C7—N1—C8—N2−0.5 (5)C12—C11—C16—C150.5 (5)
N4—N3—C9—N2179.8 (3)C10—C11—C16—C15−176.2 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.862.072.902 (3)164
N2—H2A···O10.861.922.607 (3)136

Symmetry codes: (i) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2477).

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.
  • Enraf–Nonius (1994). CAD-4 EXPRESS Enraf–Nonius, Delft, The Netherlands.
  • Hajjar, N. P. & Casida, J. E. (1978). Science, 200, 1499–1501. [PubMed]
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • Leighton, T., Marks, E. & Leighton, F. (1981). Science, 213, 905–907. [PubMed]
  • Metcalf, R. L., Lu, P. Y. & Bowlus, S. (1975). J. Agric. Food Chem.23, 359–363. [PubMed]
  • 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]

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