1-(2-Chloro­benzo­yl)-3-[4-(trifluoro­meth­oxy)phen­yl]urea

Liu, Y.; Li, F.; Yin, L.; Yu, D.

doi:10.1107/S1600536808016462

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1218

doi:10.1107/S1600536808016462

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1-(2-Chlorobenzoyl)-3-[4-(trifluoromethoxy)phenyl]urea

Yin-hong Liu,^a Fang-shi Li,^a ^* Li-he Yin ^a and Da-sheng Yu ^a

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Xinmofan Road No. 5, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: fangshi.li@njut.edu.cn

(Received 21 May 2008; accepted 29 May 2008; online 7 June 2008)

The title compound, C₁₅H₁₀ClF₃N₂O₃, is considered to belong to a fourth generation of insecticides with properties such as high selectivity, low acute toxicity for mammals and high biological activity. The dihedral angle between the two benzene rings is 59.3 (2)°. Intramolecular C—H⋯O and N—H⋯O hydrogen bonds are observed. Intermolecular N—H⋯O hydrogen bonding generates a centrosymmetric dimer. The F atoms are disordered over two positions; the site occupancy factors are 0.52 and 0.48.

Related literature

For related literature, see: Allen et al. (1987 ); Wang et al. (1998 ); Qiu et al. (12004 ).

Experimental

Crystal data

C₁₅H₁₀ClF₃N₂O₃
M_r = 358.70
Monoclinic, P 2₁ /c
a = 17.293 (4) Å
b = 8.2870 (17) Å
c = 11.073 (2) Å
β = 101.74 (3)°
V = 1553.6 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 298 (2) K
0.30 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.917, T_max = 0.943
2946 measured reflections
2784 independent reflections
1906 reflections with I > 2σ(I)
R_int = 0.012
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.079
wR(F²) = 0.186
S = 1.01
2784 reflections
209 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3	0.86	1.95	2.653 (4)	138
N2—H2A⋯O2ⁱ	0.86	2.00	2.851 (4)	172
C6—H6A⋯O2	0.93	2.24	2.838 (5)	121
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808016462/kp2174sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808016462/kp2174Isup2.hkl

checkCIF report

Comment top

The title compound, (I), 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). As part of our studies in this area, we report herein the crystal structure of the title compound (I).

In the molecule of (I) (Fig.1), the bond lengths and angles are within normal ranges (Allen et al., 1987). The intramolecular C—H···O and N—H···O hydrogen bonds are observed (Fig. 1, Table 1). Intermolecular N—H···O hydrogen bond generates a cyclic, centrosymmetric hydrogen bonded dimer (Table 1, Fig. 2).

Related literature top

For related literature, see: Allen et al. (1987); Wang et al. (1998); Qiu et al. (2004).

Experimental top

The title compound, (I), was prepared according to the literature method (Qiu et al., 1981). The crystals suitable for X-ray analysis were obtained by dissolving (I) (0.1 g) in acetonitrile (25 mL) and evaporating the solvent slowly at room temperature for about 6 d.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Intramolecular hydrogen bonds are shown by dased lines.
	Fig. 2. The crystal packing diagram with hydrogen bonds drawn as dashed lines.

1-(2-Chlorobenzoyl)-3-[4-(trifluoromethoxy)phenyl]urea top

Crystal data top

C₁₅H₁₀ClF₃N₂O₃	F(000) = 728
M_r = 358.70	D_x = 1.534 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 17.293 (4) Å	θ = 10–14°
b = 8.2870 (17) Å	µ = 0.30 mm⁻¹
c = 11.073 (2) Å	T = 298 K
β = 101.74 (3)°	Block, colourless
V = 1553.6 (6) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1906 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.012
Graphite monochromator	θ_max = 25.2°, θ_min = 1.2°
ω/2θ scans	h = −20→20
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
T_min = 0.917, T_max = 0.943	l = 0→13
2946 measured reflections	3 standard reflections every 200 reflections
2784 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.079	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.186	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.06P)² + 3P] where P = (F_o² + 2F_c²)/3
2784 reflections	(Δ/σ)_max < 0.001
209 parameters	Δρ_max = 0.58 e Å⁻³
1 restraint	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₅H₁₀ClF₃N₂O₃	V = 1553.6 (6) Å³
M_r = 358.70	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.293 (4) Å	µ = 0.30 mm⁻¹
b = 8.2870 (17) Å	T = 298 K
c = 11.073 (2) Å	0.30 × 0.20 × 0.20 mm
β = 101.74 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1906 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.012
T_min = 0.917, T_max = 0.943	3 standard reflections every 200 reflections
2946 measured reflections	intensity decay: none
2784 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.079	1 restraint
wR(F²) = 0.186	H-atom parameters constrained
S = 1.01	Δρ_max = 0.58 e Å⁻³
2784 reflections	Δρ_min = −0.38 e Å⁻³
209 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl	0.39377 (8)	0.46678 (16)	0.93229 (10)	0.0767 (4)
F1	0.9765 (5)	0.8806 (12)	0.8631 (10)	0.147	0.52
F2	0.9962 (5)	0.7066 (11)	0.7283 (8)	0.131	0.52
F3	1.0673 (5)	0.7391 (10)	0.9039 (8)	0.127	0.52
F1'	0.9962 (6)	0.8363 (13)	0.9452 (9)	0.145	0.48
F2'	0.9788 (6)	0.7985 (12)	0.7564 (10)	0.140	0.48
F3'	1.0763 (4)	0.6519 (9)	0.8854 (7)	0.111	0.48
O1	0.9560 (2)	0.6074 (6)	0.8858 (4)	0.1185 (16)
O2	0.59902 (15)	0.5358 (4)	0.5609 (2)	0.0661 (8)
O3	0.50002 (17)	0.7159 (4)	0.8415 (3)	0.0733 (9)
N1	0.62777 (18)	0.6359 (4)	0.7569 (3)	0.0578 (9)
H1A	0.6061	0.6732	0.8145	0.069*
N2	0.49834 (18)	0.6012 (4)	0.6534 (3)	0.0552 (8)
H2A	0.4665	0.5691	0.5876	0.066*
C1	0.9996 (3)	0.7289 (13)	0.8574 (9)	0.146 (3)
C2	0.8720 (3)	0.6213 (7)	0.8485 (5)	0.0820 (15)
C3	0.8311 (3)	0.6917 (7)	0.9265 (5)	0.0849 (16)
H3A	0.8573	0.7353	1.0010	0.102*
C4	0.7488 (3)	0.6978 (6)	0.8930 (4)	0.0742 (13)
H4A	0.7194	0.7466	0.9445	0.089*
C5	0.7113 (2)	0.6298 (5)	0.7812 (3)	0.0570 (10)
C6	0.7545 (2)	0.5566 (6)	0.7047 (4)	0.0694 (12)
H6A	0.7294	0.5092	0.6310	0.083*
C7	0.8363 (3)	0.5553 (7)	0.7400 (5)	0.0802 (14)
H7A	0.8666	0.5088	0.6888	0.096*
C8	0.5786 (2)	0.5883 (5)	0.6510 (4)	0.0532 (10)
C9	0.4632 (2)	0.6571 (5)	0.7445 (4)	0.0527 (9)
C10	0.3755 (2)	0.6418 (5)	0.7208 (4)	0.0539 (10)
C11	0.3384 (2)	0.5638 (5)	0.8036 (4)	0.0561 (10)
C12	0.2570 (3)	0.5556 (6)	0.7844 (5)	0.0755 (13)
H12A	0.2327	0.5031	0.8410	0.091*
C13	0.2120 (3)	0.6263 (7)	0.6803 (5)	0.0842 (15)
H13A	0.1572	0.6227	0.6672	0.101*
C14	0.2478 (3)	0.7012 (7)	0.5968 (5)	0.0842 (15)
H14A	0.2172	0.7477	0.5267	0.101*
C15	0.3293 (3)	0.7087 (6)	0.6157 (4)	0.0687 (12)
H15A	0.3532	0.7588	0.5576	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0925 (9)	0.0813 (8)	0.0561 (6)	0.0109 (7)	0.0145 (6)	0.0084 (6)
F1	0.147	0.147	0.147	0.000	0.030	0.000
F2	0.131	0.131	0.131	0.000	0.027	0.000
F3	0.127	0.127	0.127	0.000	0.026	0.000
F1'	0.145	0.145	0.145	0.000	0.030	0.000
F2'	0.140	0.140	0.140	0.000	0.029	0.000
F3'	0.111	0.111	0.111	0.000	0.023	0.000
O1	0.0479 (19)	0.170 (4)	0.123 (3)	−0.013 (2)	−0.017 (2)	0.038 (3)
O2	0.0487 (15)	0.092 (2)	0.0543 (16)	−0.0083 (15)	0.0024 (13)	−0.0147 (16)
O3	0.0656 (18)	0.083 (2)	0.0648 (18)	−0.0052 (16)	−0.0016 (15)	−0.0225 (17)
N1	0.0467 (18)	0.072 (2)	0.0491 (18)	−0.0096 (16)	−0.0039 (14)	−0.0009 (17)
N2	0.0502 (18)	0.064 (2)	0.0468 (17)	−0.0067 (16)	−0.0008 (14)	−0.0074 (16)
C1	0.025 (2)	0.234 (10)	0.168 (7)	−0.022 (4)	−0.005 (3)	0.020 (8)
C2	0.050 (3)	0.106 (4)	0.080 (3)	−0.017 (3)	−0.010 (2)	0.024 (3)
C3	0.056 (3)	0.126 (5)	0.063 (3)	−0.028 (3)	−0.012 (2)	0.007 (3)
C4	0.062 (3)	0.097 (4)	0.059 (3)	−0.023 (3)	−0.002 (2)	−0.001 (2)
C5	0.052 (2)	0.066 (3)	0.048 (2)	−0.014 (2)	−0.0026 (18)	0.0114 (19)
C6	0.049 (2)	0.089 (3)	0.063 (3)	−0.003 (2)	−0.004 (2)	0.002 (2)
C7	0.055 (3)	0.098 (4)	0.084 (3)	−0.001 (3)	0.006 (2)	0.004 (3)
C8	0.049 (2)	0.059 (2)	0.047 (2)	−0.0097 (19)	0.0009 (17)	−0.0001 (19)
C9	0.056 (2)	0.046 (2)	0.052 (2)	−0.0018 (18)	0.0009 (18)	0.0000 (18)
C10	0.053 (2)	0.047 (2)	0.058 (2)	0.0019 (18)	0.0017 (18)	−0.0064 (19)
C11	0.063 (2)	0.055 (3)	0.051 (2)	0.0033 (19)	0.0140 (19)	−0.0095 (19)
C12	0.066 (3)	0.082 (3)	0.083 (3)	0.002 (3)	0.027 (3)	−0.007 (3)
C13	0.057 (3)	0.098 (4)	0.097 (4)	0.007 (3)	0.013 (3)	−0.011 (3)
C14	0.071 (3)	0.088 (4)	0.082 (3)	0.022 (3)	−0.011 (3)	0.002 (3)
C15	0.061 (3)	0.077 (3)	0.064 (3)	0.005 (2)	0.003 (2)	0.012 (2)

Geometric parameters (Å, º) top

Cl—C11	1.743 (4)	C3—C4	1.397 (6)
F1—C1	1.324 (12)	C3—H3A	0.9300
F2—C1	1.431 (11)	C4—C5	1.394 (6)
F3—C1	1.181 (10)	C4—H4A	0.9300
F1'—C1	1.327 (12)	C5—C6	1.379 (6)
F2'—C1	1.244 (11)	C6—C7	1.389 (6)
F3'—C1	1.447 (10)	C6—H6A	0.9300
O1—C1	1.334 (9)	C7—H7A	0.9300
O1—C2	1.432 (5)	C9—C10	1.490 (5)
O2—C8	1.205 (4)	C10—C11	1.382 (6)
O3—C9	1.233 (4)	C10—C15	1.386 (5)
N1—C8	1.360 (5)	C11—C12	1.381 (6)
N1—C5	1.416 (5)	C12—C13	1.383 (7)
N1—H1A	0.8600	C12—H12A	0.9300
N2—C9	1.361 (5)	C13—C14	1.362 (7)
N2—C8	1.398 (5)	C13—H13A	0.9300
N2—H2A	0.8600	C14—C15	1.384 (6)
C2—C7	1.350 (7)	C14—H14A	0.9300
C2—C3	1.354 (7)	C15—H15A	0.9300

C1—O1—C2	117.4 (5)	C5—C4—H4A	120.5
C8—N1—C5	126.0 (4)	C3—C4—H4A	120.5
C8—N1—H1A	117.0	C6—C5—C4	120.8 (4)
C5—N1—H1A	117.0	C6—C5—N1	123.9 (4)
C9—N2—C8	129.5 (3)	C4—C5—N1	115.2 (4)
C9—N2—H2A	115.3	C5—C6—C7	118.6 (4)
C8—N2—H2A	115.3	C5—C6—H6A	120.7
F3—C1—F2'	115.9 (9)	C7—C6—H6A	120.7
F3—C1—F1	101.2 (9)	C2—C7—C6	120.2 (5)
F2'—C1—F1	64.4 (8)	C2—C7—H7A	119.9
F3—C1—F1'	79.7 (8)	C6—C7—H7A	119.9
F2'—C1—F1'	107.4 (11)	O2—C8—N1	125.6 (4)
F1—C1—F1'	43.2 (6)	O2—C8—N2	120.2 (3)
F3—C1—O1	120.6 (9)	N1—C8—N2	114.2 (4)
F2'—C1—O1	119.2 (7)	O3—C9—N2	123.4 (4)
F1—C1—O1	121.0 (7)	O3—C9—C10	120.9 (4)
F1'—C1—O1	102.8 (8)	N2—C9—C10	115.7 (3)
F3—C1—F2	106.3 (8)	C11—C10—C15	118.6 (4)
F2'—C1—F2	38.4 (6)	C11—C10—C9	121.1 (3)
F1—C1—F2	102.6 (9)	C15—C10—C9	120.4 (4)
F1'—C1—F2	145.0 (11)	C12—C11—C10	121.1 (4)
O1—C1—F2	103.1 (8)	C12—C11—Cl	118.5 (4)
F3—C1—F3'	32.4 (5)	C10—C11—Cl	120.4 (3)
F2'—C1—F3'	118.7 (9)	C11—C12—C13	119.4 (5)
F1—C1—F3'	132.9 (8)	C11—C12—H12A	120.3
F1'—C1—F3'	108.3 (8)	C13—C12—H12A	120.3
O1—C1—F3'	98.9 (8)	C14—C13—C12	120.2 (5)
F2—C1—F3'	90.4 (7)	C14—C13—H13A	119.9
C7—C2—C3	122.6 (4)	C12—C13—H13A	119.9
C7—C2—O1	118.5 (5)	C13—C14—C15	120.5 (5)
C3—C2—O1	118.8 (5)	C13—C14—H14A	119.7
C2—C3—C4	118.8 (4)	C15—C14—H14A	119.7
C2—C3—H3A	120.6	C14—C15—C10	120.3 (5)
C4—C3—H3A	120.6	C14—C15—H15A	119.9
C5—C4—C3	119.0 (5)	C10—C15—H15A	119.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.86	1.95	2.653 (4)	138
N2—H2A···O2ⁱ	0.86	2.00	2.851 (4)	172
C6—H6A···O2	0.93	2.24	2.838 (5)	121

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₀ClF₃N₂O₃
M_r	358.70
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	17.293 (4), 8.2870 (17), 11.073 (2)
β (°)	101.74 (3)
V (Å³)	1553.6 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.917, 0.943
No. of measured, independent and observed [I > 2σ(I)] reflections	2946, 2784, 1906
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.079, 0.186, 1.01
No. of reflections	2784
No. of parameters	209
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.38

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.8600	1.9500	2.653 (4)	138.00
N2—H2A···O2ⁱ	0.8600	2.0000	2.851 (4)	172.00
C6—H6A···O2	0.9300	2.2400	2.838 (5)	121.00

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The authors thank Professor Yuan-wen Wu of Nanjing University of Technology for his kind help with the crystal structure analysis.

References

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