1,1-Dimethyl-3-[4-(tri­fluoro­meth­yl)phen­yl]urea

El-Hiti, G.A.; Smith, K.; Hegazy, A.S.; Alshammari, M.B.; Kariuki, B.M.

doi:10.1107/S2414314618000408

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 1| January 2018| x180040

https://doi.org/10.1107/S2414314618000408

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1,1-Dimethyl-3-[4-(trifluoromethyl)phenyl]urea

Gamal A. El-Hiti,^a ^* Keith Smith,^b Amany S. Hegazy,^b Mohammed B. Alshammari ^c and Benson M. Kariuki ^b ‡

^aCornea Research Chair, Department of Optometry, College of Applied Medical Sciences, King Saud University, PO Box 10219, Riyadh 11433, Saudi Arabia, ^bSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, Wales, and ^cChemistry Department, College of Sciences and Humanities, Prince Sattam bin Abdulaziz University, PO Box 83, Al-Kharij 11942, Saudi Arabia
^*Correspondence e-mail: gelhiti@ksu.edu.sa

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 5 January 2018; accepted 7 January 2018; online 12 January 2018)

In the title compound, C₁₀H₁₁F₃N₂O, the dihedral angle between the dimethylurea and phenyl group planes is 37.49 (7)°. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, generating chains propagating in the [010] direction. The trifluoromethyl group is disordered over two orientations in a 0.577 (12):0.423 (12) ratio.

Keywords: crystal structure; disorder; hydrogen bond; urea.

CCDC reference: 1815173

Structure description

Various synthetic methods are known for the production of ureas (e.g.: Artuso et al., 2007 ; Carnaroglio et al., 2013 ). As part of our studies in this area, we now describe the synthesis and structure of the title compound (Fig. 1).

Figure 1
The molecular structure of the title compound, showing 50% displacement ellipsoids.

The angle between the planes through the non-hydrogen atoms of the dimethylurea and phenyl groups is 37.49 (7)°. In the crystal (Fig. 2), the molecules are linked by N—H⋯O hydrogen bonds (Table 1) to generate C(4) amide chains propagating in the [010] direction with adjacent molecules in the chain related by b-glide symmetry.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.08	2.8939 (13)	157
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Figure 2
A view of the crystal packing down [100]. H atoms have been omitted for clarity.

Synthesis and crystallization

4-Trifluoromethylaniline (10 mmol) and dimethylcarbamoyl chloride (11 mmol) in anhydrous dichloromethane containing triethylamine (15 mmol) were heated under reflux for 1 h. The mixture was allowed to cool down and poured into water. The layers were separated and the organic layer was dried (anhydrous magnesium sulfate) and evaporated under reduced pressure. The solid obtained was recrystallized from ethyl acetate solution to give colourless blocks of (I), m.p. 195–196°C (lit. 193–194°C; Hutchby, 2013 ).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The trifluoromethyl group is disordered over two orientations in a 0.577 (12):0.423 (12) ratio.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₁₁F₃N₂O
M_r	232.21
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	9.8152 (3), 10.0783 (2), 22.5120 (7)
V (Å³)	2226.90 (11)
Z	8
Radiation type	Cu Kα
μ (mm⁻¹)	1.10
Crystal size (mm)	0.30 × 0.23 × 0.10

Data collection
Diffractometer	Agilent SuperNova, Dual, Cu at zero, Atlas
Absorption correction	Gaussian (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.940, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	7168, 2217, 1708
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.139, 1.06
No. of reflections	2217
No. of parameters	176
No. of restraints	60
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.17
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS2013 (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2015>), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and CHEMDRAW Ultra (Cambridge Soft, 2001 ).

Structural data

CCDC reference: 1815173

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618000408/hb4201sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618000408/hb4201Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618000408/hb4201Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001).

1,1-Dimethyl-3-[4-(trifluoromethyl)phenyl]urea top

Crystal data top

C₁₀H₁₁F₃N₂O	D_x = 1.385 Mg m⁻³
M_r = 232.21	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pbca	Cell parameters from 2946 reflections
a = 9.8152 (3) Å	θ = 3.9–73.8°
b = 10.0783 (2) Å	µ = 1.10 mm⁻¹
c = 22.5120 (7) Å	T = 293 K
V = 2226.90 (11) Å³	Block, colourless
Z = 8	0.30 × 0.23 × 0.10 mm
F(000) = 960

Data collection top

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer	1708 reflections with I > 2σ(I)
ω scans	R_int = 0.030
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014)	θ_max = 74.0°, θ_min = 3.9°
T_min = 0.940, T_max = 0.974	h = −11→7
7168 measured reflections	k = −12→10
2217 independent reflections	l = −28→25

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.044	w = 1/[σ²(F_o²) + (0.0878P)² + 0.0492P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.139	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.16 e Å⁻³
2217 reflections	Δρ_min = −0.17 e Å⁻³
176 parameters	Extinction correction: SHELXL2013 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
60 restraints	Extinction coefficient: 0.0102 (9)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. All hydrogen atoms were placed in calculated positions and refined using a riding model. Methyl C—H bonds were fixed at 0.96 Å, with displacement parameters 1.5 times U_eq(C), and were allowed to spin about the C—N bond. The N—H bond was fixed at 0.86 Å and aromatic C—H distances were set to 0.93 Å and their U(iso) set to 1.2 times the U_eq for the atoms to which they are bonded.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.5872 (3)	0.0387 (3)	0.72719 (10)	0.1049 (8)
C2	0.49935 (19)	0.02575 (19)	0.67302 (8)	0.0730 (5)
C3	0.5321 (2)	−0.06604 (19)	0.62979 (9)	0.0800 (5)
H3	0.6070	−0.1214	0.6349	0.096*
C4	0.45445 (17)	−0.07598 (15)	0.57921 (8)	0.0678 (4)
H4	0.4774	−0.1378	0.5502	0.081*
C5	0.34195 (14)	0.00549 (12)	0.57108 (6)	0.0517 (3)
C6	0.30912 (16)	0.09806 (14)	0.61453 (7)	0.0613 (4)
H6	0.2341	0.1533	0.6096	0.074*
C7	0.38819 (18)	0.10778 (17)	0.66514 (7)	0.0707 (5)
H7	0.3664	0.1701	0.6941	0.085*
C8	0.20108 (14)	0.08594 (11)	0.48853 (6)	0.0517 (3)
C9	0.0580 (2)	0.15002 (18)	0.40623 (10)	0.0831 (5)
H9A	0.0521	0.2304	0.4290	0.125*
H9B	−0.0320	0.1199	0.3964	0.125*
H9C	0.1082	0.1665	0.3704	0.125*
C10	0.1105 (2)	−0.08604 (16)	0.42132 (9)	0.0778 (5)
H10A	0.1922	−0.1151	0.4019	0.117*
H10B	0.0354	−0.0912	0.3941	0.117*
H10C	0.0928	−0.1418	0.4550	0.117*
N1	0.26294 (13)	−0.01353 (10)	0.51968 (5)	0.0546 (3)
H1	0.2529	−0.0934	0.5070	0.065*
N2	0.12717 (14)	0.04922 (11)	0.44086 (6)	0.0622 (4)
O1	0.21290 (14)	0.20262 (9)	0.50340 (5)	0.0728 (4)
F1	0.7132 (6)	0.024 (2)	0.7171 (3)	0.169 (5)	0.423 (12)
F2	0.5686 (15)	0.1449 (10)	0.7571 (5)	0.170 (5)	0.423 (12)
F3	0.5525 (14)	−0.0492 (11)	0.7660 (4)	0.164 (4)	0.423 (12)
F1A	0.6752 (9)	0.1385 (8)	0.7205 (3)	0.148 (3)	0.577 (12)
F3A	0.6621 (13)	−0.0643 (6)	0.7389 (4)	0.179 (4)	0.577 (12)
F2A	0.5211 (7)	0.0711 (18)	0.7739 (2)	0.206 (6)	0.577 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.108 (2)	0.137 (2)	0.0695 (13)	−0.0207 (16)	−0.0197 (12)	0.0095 (13)
C2	0.0724 (11)	0.0874 (10)	0.0592 (9)	−0.0186 (8)	−0.0063 (7)	0.0109 (7)
C3	0.0773 (11)	0.0784 (10)	0.0841 (12)	0.0059 (8)	−0.0200 (9)	0.0042 (8)
C4	0.0750 (10)	0.0551 (7)	0.0734 (10)	0.0061 (6)	−0.0107 (8)	−0.0048 (6)
C5	0.0568 (8)	0.0428 (5)	0.0554 (7)	−0.0081 (5)	0.0007 (6)	0.0026 (5)
C6	0.0601 (9)	0.0642 (8)	0.0597 (8)	−0.0048 (6)	0.0068 (6)	−0.0068 (6)
C7	0.0772 (11)	0.0825 (10)	0.0523 (8)	−0.0172 (8)	0.0104 (7)	−0.0088 (7)
C8	0.0574 (8)	0.0389 (5)	0.0587 (7)	−0.0017 (5)	0.0043 (6)	0.0007 (5)
C9	0.0924 (13)	0.0718 (10)	0.0850 (12)	0.0069 (8)	−0.0206 (10)	0.0156 (8)
C10	0.0931 (13)	0.0589 (8)	0.0814 (11)	−0.0074 (7)	−0.0245 (9)	−0.0080 (7)
N1	0.0669 (7)	0.0348 (5)	0.0620 (7)	−0.0007 (4)	−0.0077 (5)	−0.0041 (4)
N2	0.0704 (8)	0.0499 (6)	0.0664 (7)	0.0012 (5)	−0.0119 (6)	0.0021 (5)
O1	0.1053 (10)	0.0351 (5)	0.0781 (7)	0.0012 (4)	−0.0095 (6)	−0.0024 (4)
F1	0.086 (3)	0.322 (15)	0.099 (4)	−0.005 (5)	−0.029 (2)	−0.024 (6)
F2	0.213 (12)	0.172 (6)	0.124 (7)	0.007 (5)	−0.083 (8)	−0.061 (5)
F3	0.203 (9)	0.210 (7)	0.078 (4)	−0.017 (6)	−0.043 (4)	0.056 (4)
F1A	0.148 (5)	0.178 (5)	0.116 (4)	−0.073 (4)	−0.067 (3)	0.023 (3)
F3A	0.217 (8)	0.168 (4)	0.152 (6)	0.037 (5)	−0.117 (6)	0.009 (3)
F2A	0.140 (4)	0.421 (18)	0.0560 (18)	−0.029 (8)	−0.0078 (18)	−0.026 (5)

Geometric parameters (Å, º) top

C1—F1	1.267 (6)	C6—C7	1.382 (2)
C1—F2	1.277 (7)	C6—H6	0.9300
C1—F2A	1.277 (7)	C7—H7	0.9300
C1—F3	1.290 (7)	C8—O1	1.2281 (16)
C1—F3A	1.300 (6)	C8—N2	1.3471 (19)
C1—F1A	1.334 (5)	C8—N1	1.3658 (17)
C1—C2	1.499 (3)	C9—N2	1.449 (2)
C2—C7	1.380 (3)	C9—H9A	0.9600
C2—C3	1.381 (3)	C9—H9B	0.9600
C3—C4	1.374 (3)	C9—H9C	0.9600
C3—H3	0.9300	C10—N2	1.4417 (19)
C4—C5	1.388 (2)	C10—H10A	0.9600
C4—H4	0.9300	C10—H10B	0.9600
C5—C6	1.390 (2)	C10—H10C	0.9600
C5—N1	1.4060 (18)	N1—H1	0.8600

F1—C1—F2	109.5 (6)	C5—C6—H6	120.1
F1—C1—F3	107.3 (7)	C2—C7—C6	120.49 (16)
F2—C1—F3	100.4 (6)	C2—C7—H7	119.8
F2A—C1—F3A	108.9 (6)	C6—C7—H7	119.8
F2A—C1—F1A	103.3 (6)	O1—C8—N2	122.07 (12)
F3A—C1—F1A	105.0 (5)	O1—C8—N1	121.39 (13)
F1—C1—C2	113.9 (3)	N2—C8—N1	116.54 (11)
F2—C1—C2	114.9 (4)	N2—C9—H9A	109.5
F2A—C1—C2	113.6 (4)	N2—C9—H9B	109.5
F3—C1—C2	109.8 (4)	H9A—C9—H9B	109.5
F3A—C1—C2	114.9 (3)	N2—C9—H9C	109.5
F1A—C1—C2	110.3 (2)	H9A—C9—H9C	109.5
C7—C2—C3	119.65 (16)	H9B—C9—H9C	109.5
C7—C2—C1	120.4 (2)	N2—C10—H10A	109.5
C3—C2—C1	119.9 (2)	N2—C10—H10B	109.5
C4—C3—C2	120.26 (17)	H10A—C10—H10B	109.5
C4—C3—H3	119.9	N2—C10—H10C	109.5
C2—C3—H3	119.9	H10A—C10—H10C	109.5
C3—C4—C5	120.50 (16)	H10B—C10—H10C	109.5
C3—C4—H4	119.8	C8—N1—C5	124.59 (10)
C5—C4—H4	119.8	C8—N1—H1	117.7
C4—C5—C6	119.25 (14)	C5—N1—H1	117.7
C4—C5—N1	117.81 (13)	C8—N2—C10	124.32 (12)
C6—C5—N1	122.89 (13)	C8—N2—C9	119.22 (13)
C7—C6—C5	119.85 (15)	C10—N2—C9	116.46 (14)
C7—C6—H6	120.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.08	2.8939 (13)	157

Symmetry code: (i) −x+1/2, y−1/2, z.

Footnotes

‡Additional corresponding author, e-mail: kariukib@cardiff.ac.uk.

Funding information

The project was supported by King Saud University, Deanship of Scientific Research, Research Chairs and Cardiff University.

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