N,N-Dimethyl-N′-[3-(trifluoro­methyl)­phenyl]­urea

Yu, D.; Li, F.; Yao, W.; Liu, Y.; Lu, C.

doi:10.1107/S1600536808016656

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1220

doi:10.1107/S1600536808016656

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N,N-Dimethyl-N′-[3-(trifluoromethyl)phenyl]urea

Da-sheng Yu,^a Fang-shi Li,^a ^* Wei Yao,^a Yin-hong Liu ^a and Chui Lu ^a

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

(Received 26 May 2008; accepted 31 May 2008; online 7 June 2008)

The title compound, C₁₀H₁₁F₃N₂O, is an important urea-based herbicide. In the crystal structure, the molecular packing is stabilized by two intramolecular C—H⋯O hydrogen bonds and one intermolecular N—H⋯O hydrogen bond, generating a C(4) graph-set motif running parallel to the [001] direction. The F atoms are disordered over two sites, with occupancies of 0.176 (9) and 0.824 (9).

Related literature

For related literature, see: Bernstein et al. (1995 ); Xu et al. (2005 ); Zhao & Wilkins (2003 ); Li et al. (2007 ).

Experimental

Crystal data

C₁₀H₁₁F₃N₂O
M_r = 232.20
Monoclinic, P 2₁ /c
a = 11.005 (2) Å
b = 9.991 (2) Å
c = 10.012 (2) Å
β = 96.89 (3)°
V = 1092.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 298 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD4 diffractometer
Absorption correction: multi-scan (North et al., 1968 ) T_min = 0.963, T_max = 0.987
2076 measured reflections
1953 independent reflections
1335 reflections with I > 2σi(I)
R_int = 0.020
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.137
S = 1.00
1953 reflections
169 parameters
36 restraints
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Oⁱ	0.86	2.08	2.880 (3)	155
C3—H3A⋯O	0.93	2.48	2.884 (3)	106
C9—H9A⋯O	0.96	2.28	2.721 (4)	107
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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 datablock I. DOI: 10.1107/S1600536808016656/bx2148sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808016656/bx2148Isup2.hkl

checkCIF report

Comment top

The title compound, (I), is a pre- and postemergence herbicide used widely as water dispersible and suspension concentrate formulations for the control of grass and broadleaf weeds in cotton and sugarcane (Zhao & Wilkins, 2003). As part of our studies in this area (Li et al., 2007), we report herein the crystal structure of the title compound, (I), Fig 1. In the crystal structure the molecular packing is stabilized by two intramolecular C—H···O as well as one intermolecular N—H···O hydrogen bond generating a graph-set motif C(4) running parallel to [001] direction (Bernstein et al., 1995), Table 1.

Related literature top

For related literature, see: Bernstein et al. (1995); Xu et al. (2005); Zhao & Wilkins (2003); Li et al. (2007).

Experimental top

The title compound, (I), was prepared according to the literature method (Xu et al., 2005). 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 7 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.
	Fig. 2. The molecule packing diagram.

N,N-Dimethyl-N'-[3-(trifluoromethyl)phenyl]urea top

Crystal data top

C₁₀H₁₁F₃N₂O	F(000) = 480
M_r = 232.20	D_x = 1.411 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 11.005 (2) Å	θ = 10–13°
b = 9.991 (2) Å	µ = 0.13 mm⁻¹
c = 10.012 (2) Å	T = 298 K
β = 96.89 (3)°	Needle, colourless
V = 1092.9 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD4 diffractometer	1335 reflections with I > 2σi(I)
Radiation source: fine-focus sealed tube	R_int = 0.020
Graphite monochromator	θ_max = 25.2°, θ_min = 1.9°
ω/2θ scans	h = −13→13
Absorption correction: multi-scan (North et al., 1968)	k = −11→0
T_min = 0.963, T_max = 0.987	l = 0→11
2076 measured reflections	3 standard reflections every 200 reflections
1953 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H-atom parameters constrained
wR(F²) = 0.137	w = 1/[σ²(F_o²) + (0.050P)² + 0.630P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1953 reflections	Δρ_max = 0.19 e Å⁻³
169 parameters	Δρ_min = −0.15 e Å⁻³
36 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.162 (9)

Crystal data top

C₁₀H₁₁F₃N₂O	V = 1092.9 (4) Å³
M_r = 232.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.005 (2) Å	µ = 0.13 mm⁻¹
b = 9.991 (2) Å	T = 298 K
c = 10.012 (2) Å	0.30 × 0.20 × 0.10 mm
β = 96.89 (3)°

Data collection top

Enraf–Nonius CAD4 diffractometer	1335 reflections with I > 2σi(I)
Absorption correction: multi-scan (North et al., 1968)	R_int = 0.020
T_min = 0.963, T_max = 0.987	3 standard reflections every 200 reflections
2076 measured reflections	intensity decay: none
1953 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	36 restraints
wR(F²) = 0.137	H-atom parameters constrained
S = 1.00	Δρ_max = 0.19 e Å⁻³
1953 reflections	Δρ_min = −0.15 e Å⁻³
169 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)
C1	−0.4416 (3)	0.3310 (5)	0.7481 (4)	0.083
F1	−0.4245 (19)	0.355 (3)	0.6336 (15)	0.097 (6)	0.176 (9)
F2	−0.444 (2)	0.1924 (18)	0.754 (3)	0.127 (8)	0.176 (9)
F3	−0.5413 (13)	0.368 (3)	0.773 (2)	0.102 (6)	0.176 (9)
F1'	−0.4988 (5)	0.4328 (5)	0.6794 (6)	0.149 (2)	0.824 (9)
F2'	−0.4081 (3)	0.2491 (7)	0.6573 (5)	0.126 (2)	0.824 (9)
F3'	−0.5304 (4)	0.2692 (7)	0.8022 (4)	0.1244 (19)	0.824 (9)
O	−0.00769 (19)	0.2044 (2)	0.79738 (17)	0.0702 (7)
N1	−0.0375 (2)	0.2618 (2)	1.0096 (2)	0.0532 (7)
H1A	−0.0106	0.2548	1.0935	0.064*
N2	0.1237 (2)	0.1254 (3)	0.9701 (2)	0.0569 (7)
C2	−0.3406 (3)	0.3766 (3)	0.8510 (3)	0.0553 (8)
C3	−0.2362 (2)	0.2993 (3)	0.8761 (3)	0.0508 (7)
H3A	−0.2280	0.2211	0.8277	0.061*
C4	−0.1437 (2)	0.3397 (3)	0.9745 (2)	0.0460 (7)
C5	−0.1575 (3)	0.4563 (3)	1.0448 (3)	0.0572 (8)
H5A	−0.0954	0.4840	1.1102	0.069*
C6	−0.2618 (3)	0.5322 (3)	1.0194 (3)	0.0649 (9)
H6A	−0.2703	0.6103	1.0680	0.078*
C7	−0.3543 (3)	0.4927 (3)	0.9216 (3)	0.0627 (9)
H7A	−0.4249	0.5439	0.9037	0.075*
C8	0.0253 (2)	0.1970 (3)	0.9195 (2)	0.0492 (7)
C9	0.1950 (3)	0.0560 (4)	0.8790 (3)	0.0814 (11)
H9A	0.1592	0.0706	0.7879	0.122*
H9B	0.1957	−0.0381	0.8983	0.122*
H9C	0.2773	0.0896	0.8903	0.122*
C10	0.1652 (3)	0.1137 (4)	1.1124 (3)	0.0765 (11)
H10A	0.0972	0.0913	1.1599	0.115*
H10B	0.1997	0.1974	1.1454	0.115*
H10C	0.2262	0.0448	1.1264	0.115*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.059	0.100	0.086	−0.002	−0.002	−0.005
F1	0.102 (10)	0.117 (11)	0.066 (7)	−0.013 (8)	−0.012 (6)	−0.014 (7)
F2	0.118 (11)	0.114 (10)	0.134 (12)	−0.017 (8)	−0.041 (8)	−0.013 (8)
F3	0.052 (7)	0.134 (11)	0.115 (10)	−0.004 (8)	−0.004 (6)	−0.016 (9)
F1'	0.135 (4)	0.122 (3)	0.162 (4)	0.004 (3)	−0.093 (3)	0.022 (3)
F2'	0.073 (2)	0.192 (5)	0.105 (3)	0.005 (3)	−0.0191 (18)	−0.077 (4)
F3'	0.081 (2)	0.153 (4)	0.140 (3)	−0.058 (3)	0.014 (2)	−0.016 (3)
O	0.0692 (13)	0.1123 (19)	0.0284 (10)	0.0120 (12)	0.0031 (9)	−0.0004 (10)
N1	0.0590 (14)	0.0718 (16)	0.0269 (10)	0.0113 (13)	−0.0028 (10)	−0.0003 (11)
N2	0.0562 (14)	0.0701 (17)	0.0433 (13)	0.0112 (13)	0.0017 (11)	−0.0004 (12)
C2	0.0476 (16)	0.067 (2)	0.0508 (16)	−0.0061 (15)	0.0040 (13)	0.0053 (15)
C3	0.0542 (17)	0.0543 (17)	0.0430 (15)	−0.0044 (14)	0.0027 (12)	−0.0013 (13)
C4	0.0501 (15)	0.0563 (17)	0.0312 (12)	0.0004 (13)	0.0040 (11)	0.0034 (12)
C5	0.0628 (18)	0.066 (2)	0.0417 (15)	−0.0010 (16)	0.0002 (13)	−0.0058 (14)
C6	0.074 (2)	0.063 (2)	0.0579 (18)	0.0033 (17)	0.0088 (16)	−0.0090 (15)
C7	0.0570 (18)	0.068 (2)	0.0637 (19)	0.0106 (16)	0.0093 (15)	0.0088 (17)
C8	0.0505 (16)	0.0645 (18)	0.0323 (14)	−0.0022 (14)	0.0039 (11)	0.0020 (12)
C9	0.078 (2)	0.098 (3)	0.071 (2)	0.022 (2)	0.0198 (18)	−0.004 (2)
C10	0.079 (2)	0.095 (3)	0.0517 (18)	0.023 (2)	−0.0079 (16)	0.0085 (18)

Geometric parameters (Å, º) top

C1—F1	1.208 (16)	C2—C3	1.382 (4)
C1—F3	1.214 (15)	C3—C4	1.389 (4)
C1—F2'	1.308 (5)	C3—H3A	0.9300
C1—F3'	1.325 (6)	C4—C5	1.380 (4)
C1—F1'	1.341 (6)	C5—C6	1.374 (4)
C1—F2	1.386 (18)	C5—H5A	0.9300
C1—C2	1.494 (5)	C6—C7	1.383 (4)
O—C8	1.235 (3)	C6—H6A	0.9300
N1—C8	1.364 (3)	C7—H7A	0.9300
N1—C4	1.412 (3)	C9—H9A	0.9600
N1—H1A	0.8600	C9—H9B	0.9600
N2—C8	1.345 (3)	C9—H9C	0.9600
N2—C10	1.448 (4)	C10—H10A	0.9600
N2—C9	1.449 (4)	C10—H10B	0.9600
C2—C7	1.376 (4)	C10—H10C	0.9600

F1—C1—F3	112.7 (14)	C2—C3—C4	119.3 (3)
F1—C1—F2'	51.4 (11)	C2—C3—H3A	120.3
F3—C1—F2'	132.5 (9)	C4—C3—H3A	120.3
F1—C1—F3'	133.4 (8)	C5—C4—C3	119.4 (3)
F3—C1—F3'	47.9 (13)	C5—C4—N1	118.5 (2)
F2'—C1—F3'	106.1 (5)	C3—C4—N1	122.1 (2)
F1—C1—F1'	58.6 (12)	C6—C5—C4	120.8 (3)
F3—C1—F1'	59.6 (12)	C6—C5—H5A	119.6
F2'—C1—F1'	105.8 (5)	C4—C5—H5A	119.6
F3'—C1—F1'	103.9 (4)	C5—C6—C7	120.1 (3)
F1—C1—F2	104.2 (15)	C5—C6—H6A	120.0
F3—C1—F2	106.2 (16)	C7—C6—H6A	120.0
F2'—C1—F2	54.1 (12)	C2—C7—C6	119.2 (3)
F3'—C1—F2	60.0 (12)	C2—C7—H7A	120.4
F1'—C1—F2	140.5 (8)	C6—C7—H7A	120.4
F1—C1—C2	113.9 (8)	O—C8—N2	122.2 (3)
F3—C1—C2	112.2 (9)	O—C8—N1	120.9 (3)
F2'—C1—C2	114.9 (3)	N2—C8—N1	116.9 (2)
F3'—C1—C2	112.6 (4)	N2—C9—H9A	109.5
F1'—C1—C2	112.7 (4)	N2—C9—H9B	109.5
F2—C1—C2	106.8 (8)	H9A—C9—H9B	109.5
C8—N1—C4	124.5 (2)	N2—C9—H9C	109.5
C8—N1—H1A	117.7	H9A—C9—H9C	109.5
C4—N1—H1A	117.7	H9B—C9—H9C	109.5
C8—N2—C10	123.9 (2)	N2—C10—H10A	109.5
C8—N2—C9	119.3 (2)	N2—C10—H10B	109.5
C10—N2—C9	116.8 (3)	H10A—C10—H10B	109.5
C7—C2—C3	121.2 (3)	N2—C10—H10C	109.5
C7—C2—C1	119.6 (3)	H10A—C10—H10C	109.5
C3—C2—C1	119.3 (3)	H10B—C10—H10C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Oⁱ	0.86	2.08	2.880 (3)	155
C3—H3A···O	0.93	2.48	2.884 (3)	106
C9—H9A···O	0.96	2.28	2.721 (4)	107

Symmetry code: (i) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁F₃N₂O
M_r	232.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	11.005 (2), 9.991 (2), 10.012 (2)
β (°)	96.89 (3)
V (Å³)	1092.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD4 diffractometer
Absorption correction	Multi-scan (North et al., 1968)
T_min, T_max	0.963, 0.987
No. of measured, independent and observed [I > 2σi(I)] reflections	2076, 1953, 1335
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.137, 1.00
No. of reflections	1953
No. of parameters	169
No. of restraints	36
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.15

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···Oⁱ	0.8600	2.0800	2.880 (3)	155.00
C3—H3A···O	0.9300	2.4800	2.884 (3)	106.00
C9—H9A···O	0.9600	2.2800	2.721 (4)	107.00

Symmetry code: (i) x, −y+1/2, z+1/2.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Li, F. S., Sun, F., Liu, X. J. & Cui, H. H. (2007). Agric. Sci. China, 6, 964–969. CrossRef CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, X. S., Du, X. H., Hu, Z. Y. & Xu, Z. Y. (2005). Nongyao, 44, 210–211. CAS Google Scholar
Zhao, J. & Wilkins, R. M. (2003). J. Agric. Food Chem. 51, 4023–4028. Web of Science CrossRef PubMed CAS Google Scholar

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1220

doi:10.1107/S1600536808016656

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