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Acta Cryst. (2008). E64, o1729    [ doi:10.1107/S1600536808024987 ]

Ethyl 4-{2,6-dichloro-4-[3-(2,6-difluorobenzoyl)ureido]phenoxy}butanoate

Y.-H. Liu, F.-S. Li, Y. Li, D.-S. Yu and C. Lu

Abstract top

The title compound, C20H18Cl2F2N2O5, is considered to belong to the fourth generation of insecticides with properties such as high selectivity, low acute toxicity for mammals and high biological activity. An intramolecular N-H...O hydrogen bond results in the formation of a six-membered ring. In the crystal structure, intermolecular N-H...O and C-H...F hydrogen bonds link the molecules.

Comment top

The title compound is generally recognized as an insect growth regulator that interferes with chitin synthesis in target pests, causing death or abortive development (Wang et al. 1998). Bonding dimensions conform to expected values (Allen et al., 1987).

Related literature top

For related literature, see: Wang et al. (1998, 1999). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared according to a literature method (Wang et al. 1999). The crystals suitable for X-ray analysis were obtained by dissolving it (0.1 g) in acetonitrile (25 ml) and evaporating the solvent slowly at room temperature for about 6 d.

Refinement top

H atoms were positioned geometrically, with C—H distances of 0.93 and of 0.97 Å for aromatic and methyl H atoms and with N—H = 0.86 Å for amido H atoms. All H atoms were constrained to ride on their parent atoms with Uiso(H) = xUeq(C,N), where x = 1.2 for all H atoms.

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. N—H···O intramolecular hydrogen bond is shown by dashed line.
[Figure 2] Fig. 2. A packing diagram detail from the crystal structure. N—H···O and C—H···F intermolecular hydrogen bonds are shown by dashed lines.
Ethyl 4-{2,6-dichloro-4-[3-(2,6-difluorobenzoyl)ureido]phenoxy}butanoate top
Crystal data top
C20H18Cl2F2N2O5F000 = 976
Mr = 475.26Dx = 1.456 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 11.262 (2) Åθ = 9–12º
b = 10.463 (2) ŵ = 0.35 mm−1
c = 18.613 (4) ÅT = 293 (2) K
β = 98.78 (3)ºBlock, colourless
V = 2167.5 (8) Å30.40 × 0.30 × 0.20 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.041
Radiation source: fine-focus sealed tubeθmax = 25.3º
Monochromator: graphiteθmin = 2.0º
T = 293(2) Kh = −13→13
ω/2θ scansk = 0→12
Absorption correction: ψ scan
(North et al., 1968)		l = 0→22
Tmin = 0.872, Tmax = 0.9333 standard reflections
4157 measured reflections every 200 reflections
3944 independent reflections intensity decay: none
2385 reflections with I > 2σ(I)
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.082H-atom parameters constrained
wR(F2) = 0.290  w = 1/[σ2(Fo2) + (0.1372P)2 + 4.2262P]
where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max < 0.001
3944 reflectionsΔρmax = 0.77 e Å−3
268 parametersΔρmin = −0.99 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C20H18Cl2F2N2O5V = 2167.5 (8) Å3
Mr = 475.26Z = 4
Monoclinic, P21/nMo Kα
a = 11.262 (2) ŵ = 0.35 mm−1
b = 10.463 (2) ÅT = 293 (2) K
c = 18.613 (4) Å0.40 × 0.30 × 0.20 mm
β = 98.78 (3)º
Data collection top
Enraf–Nonius CAD-4
diffractometer		2385 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.041
Tmin = 0.872, Tmax = 0.9333 standard reflections
4157 measured reflections every 200 reflections
3944 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.082268 parameters
wR(F2) = 0.290H-atom parameters constrained
S = 1.13Δρmax = 0.77 e Å−3
3944 reflectionsΔρmin = −0.99 e Å−3
Special details top

Experimental. (North et al., 1968)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.23061 (14)0.09615 (16)0.16895 (10)0.0611 (5)
Cl20.02268 (15)−0.30602 (15)0.02019 (10)0.0672 (6)
F1−0.5092 (6)0.3204 (6)0.2109 (3)0.127 (2)
F2−0.5604 (4)0.3418 (6)−0.0403 (2)0.0995 (17)
N1−0.2177 (4)0.0877 (5)0.0826 (3)0.0473 (12)
H1A−0.21320.16060.10420.057*
O10.5929 (5)0.0111 (5)0.2331 (3)0.0813 (16)
C10.7375 (8)0.1501 (10)0.2970 (5)0.095
H1B0.76220.19380.34210.142*
H1C0.71730.21160.25880.142*
H1D0.80190.09690.28610.142*
N2−0.4207 (4)0.1420 (5)0.0532 (3)0.0481 (12)
H2A−0.49080.12020.03160.058*
O20.4801 (5)−0.1199 (6)0.2895 (3)0.092
C20.6371 (8)0.0743 (9)0.3027 (4)0.092 (3)
H2B0.57380.12710.31700.110*
H2C0.65830.01000.34000.110*
O30.2254 (3)−0.1568 (4)0.09703 (19)0.0458 (10)
C30.5158 (6)−0.0854 (7)0.2341 (3)0.0544 (16)
O4−0.3529 (4)−0.0477 (4)0.0170 (2)0.0578 (12)
C40.4795 (5)−0.1407 (6)0.1610 (4)0.0545 (16)
H4A0.5512−0.16380.14110.065*
H4B0.4376−0.07570.12970.065*
O5−0.3196 (4)0.3054 (5)0.1175 (3)0.0775 (16)
C50.3991 (5)−0.2578 (6)0.1597 (4)0.0513 (15)
H5A0.4037−0.30580.11560.062*
H5B0.4293−0.31210.20060.062*
C60.2705 (5)−0.2267 (6)0.1628 (3)0.0436 (13)
H6A0.2246−0.30460.16550.052*
H6B0.2640−0.17510.20530.052*
C70.1154 (5)−0.1029 (6)0.0964 (3)0.0419 (13)
C80.1028 (5)0.0189 (6)0.1269 (3)0.0431 (13)
C9−0.0055 (5)0.0791 (6)0.1230 (3)0.0455 (14)
H9A−0.01080.15910.14400.055*
C10−0.1091 (5)0.0182 (5)0.0867 (3)0.0440 (14)
C11−0.1009 (5)−0.1023 (5)0.0560 (3)0.0453 (14)
H11A−0.1688−0.14370.03230.054*
C120.0113 (5)−0.1586 (5)0.0618 (3)0.0464 (14)
C13−0.3273 (5)0.0529 (6)0.0489 (3)0.0428 (13)
C14−0.4138 (6)0.2591 (6)0.0874 (3)0.0509 (15)
C15−0.5308 (5)0.3250 (5)0.0855 (3)0.0431 (13)
C16−0.5738 (7)0.3548 (7)0.1491 (4)0.0622 (18)
C17−0.6834 (8)0.4151 (7)0.1493 (5)0.076 (2)
H17A−0.71080.43250.19300.091*
C18−0.7493 (7)0.4481 (7)0.0858 (5)0.074 (2)
H18A−0.82360.48710.08540.089*
C19−0.7083 (6)0.4251 (7)0.0223 (4)0.071 (2)
H19A−0.75350.4498−0.02150.085*
C20−0.6010 (6)0.3657 (7)0.0230 (3)0.0574 (17)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0473 (9)0.0581 (10)0.0746 (11)−0.0088 (7)−0.0015 (7)−0.0205 (8)
Cl20.0649 (11)0.0426 (9)0.0892 (13)0.0079 (8)−0.0042 (9)−0.0222 (8)
F10.181 (6)0.146 (5)0.057 (3)0.081 (5)0.027 (3)0.020 (3)
F20.104 (3)0.145 (5)0.048 (2)0.052 (3)0.006 (2)−0.015 (3)
N10.047 (3)0.041 (3)0.050 (3)0.010 (2)−0.007 (2)−0.010 (2)
O10.092 (4)0.072 (3)0.068 (3)−0.033 (3)−0.024 (3)0.011 (3)
C10.0950.0950.0950.0000.0140.000
N20.048 (3)0.038 (3)0.056 (3)0.009 (2)0.001 (2)−0.010 (2)
O20.0920.0920.0920.0000.0140.000
C20.109 (7)0.085 (6)0.068 (5)−0.039 (5)−0.029 (5)−0.001 (4)
O30.042 (2)0.058 (3)0.038 (2)0.0023 (19)0.0072 (16)−0.0027 (18)
C30.055 (4)0.060 (4)0.047 (4)−0.001 (3)0.006 (3)0.015 (3)
O40.048 (2)0.041 (2)0.077 (3)0.0065 (19)−0.015 (2)−0.021 (2)
C40.045 (3)0.056 (4)0.063 (4)−0.008 (3)0.009 (3)−0.001 (3)
O50.053 (3)0.058 (3)0.111 (4)0.000 (2)−0.020 (3)−0.034 (3)
C50.038 (3)0.052 (4)0.063 (4)0.002 (3)0.008 (3)−0.001 (3)
C60.043 (3)0.042 (3)0.045 (3)0.003 (3)0.004 (2)0.001 (3)
C70.041 (3)0.048 (3)0.036 (3)0.002 (3)0.004 (2)0.004 (3)
C80.046 (3)0.043 (3)0.040 (3)−0.009 (3)0.004 (2)−0.003 (3)
C90.052 (3)0.043 (3)0.039 (3)0.002 (3)0.001 (3)−0.008 (3)
C100.047 (3)0.040 (3)0.041 (3)0.002 (3)−0.004 (2)−0.001 (3)
C110.045 (3)0.038 (3)0.051 (3)0.002 (3)−0.001 (3)−0.006 (3)
C120.054 (3)0.035 (3)0.049 (3)0.001 (3)0.005 (3)0.000 (3)
C130.040 (3)0.043 (3)0.043 (3)0.011 (3)−0.004 (2)−0.003 (3)
C140.053 (4)0.046 (4)0.051 (4)0.001 (3)0.003 (3)−0.002 (3)
C150.044 (3)0.037 (3)0.049 (3)−0.005 (2)0.008 (3)−0.001 (3)
C160.091 (5)0.051 (4)0.049 (4)0.010 (4)0.024 (4)0.011 (3)
C170.101 (6)0.055 (4)0.085 (6)0.026 (4)0.056 (5)0.005 (4)
C180.060 (4)0.050 (4)0.114 (7)0.015 (3)0.020 (4)−0.022 (4)
C190.062 (4)0.073 (5)0.074 (5)0.016 (4)0.001 (4)−0.019 (4)
C200.059 (4)0.061 (4)0.050 (4)0.007 (3)−0.002 (3)−0.018 (3)
Geometric parameters (Å, °) top
Cl1—C81.730 (6)C4—H4B0.9700
Cl2—C121.739 (6)O5—C141.222 (7)
F1—C161.314 (9)C5—C61.494 (8)
F2—C201.350 (7)C5—H5A0.9700
N1—C131.347 (7)C5—H5B0.9700
N1—C101.414 (7)C6—H6A0.9700
N1—H1A0.8600C6—H6B0.9700
O1—C31.333 (8)C7—C121.379 (8)
O1—C21.472 (9)C7—C81.410 (8)
C1—C21.399 (11)C8—C91.365 (8)
C1—H1B0.9600C9—C101.408 (8)
C1—H1C0.9600C9—H9A0.9300
C1—H1D0.9600C10—C111.394 (8)
N2—C141.378 (8)C11—C121.383 (8)
N2—C131.417 (7)C11—H11A0.9300
N2—H2A0.8600C14—C151.482 (8)
O2—C31.217 (8)C15—C201.372 (9)
C2—H2B0.9700C15—C161.381 (8)
C2—H2C0.9700C16—C171.386 (10)
O3—C71.360 (6)C17—C181.342 (11)
O3—C61.449 (7)C17—H17A0.9300
C3—C41.477 (9)C18—C191.354 (10)
O4—C131.223 (7)C18—H18A0.9300
C4—C51.522 (9)C19—C201.358 (9)
C4—H4A0.9700C19—H19A0.9300
C13—N1—C10127.6 (5)O3—C7—C8121.3 (5)
C13—N1—H1A116.2C12—C7—C8116.1 (5)
C10—N1—H1A116.2C9—C8—C7122.6 (5)
C3—O1—C2117.4 (6)C9—C8—Cl1118.9 (4)
C2—C1—H1B109.5C7—C8—Cl1118.4 (4)
C2—C1—H1C109.5C8—C9—C10119.1 (5)
H1B—C1—H1C109.5C8—C9—H9A120.5
C2—C1—H1D109.5C10—C9—H9A120.5
H1B—C1—H1D109.5C11—C10—C9120.2 (5)
H1C—C1—H1D109.5C11—C10—N1123.7 (5)
C14—N2—C13128.4 (5)C9—C10—N1116.1 (5)
C14—N2—H2A115.8C12—C11—C10118.1 (5)
C13—N2—H2A115.8C12—C11—H11A121.0
C1—C2—O1110.9 (8)C10—C11—H11A121.0
C1—C2—H2B109.5C7—C12—C11123.9 (5)
O1—C2—H2B109.5C7—C12—Cl2117.9 (5)
C1—C2—H2C109.5C11—C12—Cl2118.1 (5)
O1—C2—H2C109.5O4—C13—N1126.2 (5)
H2B—C2—H2C108.1O4—C13—N2118.2 (5)
C7—O3—C6114.7 (4)N1—C13—N2115.6 (5)
O2—C3—O1122.5 (7)O5—C14—N2123.3 (6)
O2—C3—C4125.6 (6)O5—C14—C15122.2 (6)
O1—C3—C4111.9 (5)N2—C14—C15114.5 (5)
C3—C4—C5114.3 (6)C20—C15—C16115.1 (6)
C3—C4—H4A108.7C20—C15—C14124.0 (5)
C5—C4—H4A108.7C16—C15—C14120.8 (6)
C3—C4—H4B108.7F1—C16—C15117.9 (6)
C5—C4—H4B108.7F1—C16—C17119.7 (6)
H4A—C4—H4B107.6C15—C16—C17122.3 (7)
C6—C5—C4113.7 (5)C18—C17—C16119.2 (7)
C6—C5—H5A108.8C18—C17—H17A120.4
C4—C5—H5A108.8C16—C17—H17A120.4
C6—C5—H5B108.8C17—C18—C19120.4 (7)
C4—C5—H5B108.8C17—C18—H18A119.8
H5A—C5—H5B107.7C19—C18—H18A119.8
O3—C6—C5107.1 (5)C18—C19—C20119.7 (7)
O3—C6—H6A110.3C18—C19—H19A120.1
C5—C6—H6A110.3C20—C19—H19A120.1
O3—C6—H6B110.3F2—C20—C19119.8 (6)
C5—C6—H6B110.3F2—C20—C15117.1 (6)
H6A—C6—H6B108.5C19—C20—C15123.2 (6)
O3—C7—C12122.4 (5)
C3—O1—C2—C1165.2 (8)C10—C11—C12—C70.4 (9)
C2—O1—C3—O21.5 (10)C10—C11—C12—Cl2−177.4 (4)
C2—O1—C3—C4−179.5 (7)C10—N1—C13—O42.0 (10)
O2—C3—C4—C5−5.6 (10)C10—N1—C13—N2−179.6 (5)
O1—C3—C4—C5175.5 (5)C14—N2—C13—O4178.4 (6)
C3—C4—C5—C679.5 (7)C14—N2—C13—N1−0.2 (9)
C7—O3—C6—C5−169.7 (5)C13—N2—C14—O53.4 (10)
C4—C5—C6—O364.3 (7)C13—N2—C14—C15−176.1 (5)
C6—O3—C7—C12−99.1 (6)O5—C14—C15—C20116.7 (8)
C6—O3—C7—C885.8 (6)N2—C14—C15—C20−63.8 (8)
O3—C7—C8—C9175.6 (5)O5—C14—C15—C16−60.2 (9)
C12—C7—C8—C90.3 (8)N2—C14—C15—C16119.3 (6)
O3—C7—C8—Cl1−2.8 (7)C20—C15—C16—F1−178.7 (7)
C12—C7—C8—Cl1−178.2 (4)C14—C15—C16—F1−1.5 (10)
C7—C8—C9—C10−0.5 (9)C20—C15—C16—C173.5 (10)
Cl1—C8—C9—C10177.9 (4)C14—C15—C16—C17−179.3 (6)
C8—C9—C10—C110.7 (9)F1—C16—C17—C18−179.1 (8)
C8—C9—C10—N1−178.0 (5)C15—C16—C17—C18−1.3 (12)
C13—N1—C10—C11−1.2 (9)C16—C17—C18—C19−1.3 (12)
C13—N1—C10—C9177.4 (6)C17—C18—C19—C201.4 (12)
C9—C10—C11—C12−0.6 (9)C18—C19—C20—F2179.5 (7)
N1—C10—C11—C12178.0 (5)C18—C19—C20—C151.1 (11)
O3—C7—C12—C11−175.5 (5)C16—C15—C20—F2178.1 (6)
C8—C7—C12—C11−0.2 (9)C14—C15—C20—F21.0 (10)
O3—C7—C12—Cl22.2 (8)C16—C15—C20—C19−3.4 (10)
C8—C7—C12—Cl2177.5 (4)C14—C15—C20—C19179.5 (6)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O4i0.862.002.856 (6)173
C5—H5A···F2ii0.972.443.201 (8)135
N1—H1A···O50.861.972.675 (7)138
Symmetry codes: (i) −x−1, −y, −z; (ii) −x, −y, −z.
Table 1
Selected geometric parameters (Å, °) top
Cl1—C81.730 (6)N2—C141.378 (8)
Cl2—C121.739 (6)N2—C131.417 (7)
F1—C161.314 (9)O2—C31.217 (8)
F2—C201.350 (7)O3—C71.360 (6)
N1—C131.347 (7)O3—C61.449 (7)
N1—C101.414 (7)O4—C131.223 (7)
O1—C31.333 (8)O5—C141.222 (7)
O1—C21.472 (9)
C13—N1—C10127.6 (5)C9—C10—N1116.1 (5)
C10—N1—H1A116.2C7—C12—Cl2117.9 (5)
C3—O1—C2117.4 (6)C11—C12—Cl2118.1 (5)
C1—C2—O1110.9 (8)O4—C13—N1126.2 (5)
C7—O3—C6114.7 (4)O4—C13—N2118.2 (5)
O2—C3—O1122.5 (7)N1—C13—N2115.6 (5)
O2—C3—C4125.6 (6)O5—C14—N2123.3 (6)
O1—C3—C4111.9 (5)O5—C14—C15122.2 (6)
O3—C6—C5107.1 (5)N2—C14—C15114.5 (5)
O3—C7—C12122.4 (5)F1—C16—C15117.9 (6)
O3—C7—C8121.3 (5)F1—C16—C17119.7 (6)
C9—C8—Cl1118.9 (4)F2—C20—C19119.8 (6)
C7—C8—Cl1118.4 (4)F2—C20—C15117.1 (6)
C11—C10—N1123.7 (5)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O4i0.862.002.856 (6)173
C5—H5A···F2ii0.972.443.201 (8)135
N1—H1A···O50.861.972.675 (7)138
Symmetry codes: (i) −x−1, −y, −z; (ii) −x, −y, −z.
Acknowledgements top

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references
References top

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