organic compounds
1,1-Dimethyl-3-[4-(trifluoromethyl)phenyl]urea
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
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).
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.
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 . The trifluoromethyl group is disordered over two orientations in a 0.577 (12):0.423 (12) ratio.
details are summarized in Table 2Structural data
CCDC reference: 1815173
https://doi.org/10.1107/S2414314618000408/hb4201sup1.cif
contains datablock I. DOI: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
Data collection: CrysAlis PRO (Agilent, 2014); cell
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).C10H11F3N2O | Dx = 1.385 Mg m−3 |
Mr = 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 |
Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer | 1708 reflections with I > 2σ(I) |
ω scans | Rint = 0.030 |
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014) | θmax = 74.0°, θmin = 3.9° |
Tmin = 0.940, Tmax = 0.974 | h = −11→7 |
7168 measured reflections | k = −12→10 |
2217 independent reflections | l = −28→25 |
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(Fo2) + (0.0878P)2 + 0.0492P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.139 | (Δ/σ)max < 0.001 |
S = 1.06 | Δρmax = 0.16 e Å−3 |
2217 reflections | Δρmin = −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) |
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 Ueq(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 Ueq for the atoms to which they are bonded. |
x | y | z | Uiso*/Ueq | 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) |
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) |
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 |
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.
References
Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Artuso, E., Degani, I., Fochi, R. & Magistris, C. (2007). Synthesis, pp. 3497–3506. Google Scholar
Cambridge Soft (2001). CHEMDRAW Ultra, Cambridge Soft Corporation, Cambridge, Massachusetts, USA. Google Scholar
Carnaroglio, D., Martina, K., Palmisano, G., Penoni, A., Domini, C. & Cravotto, G. (2013). Beilstein J. Org. Chem. 9, 2378–2386. Web of Science CrossRef CAS PubMed Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hutchby, M. (2013). Novel Synthetic Chemistry of Ureas and Amides. Springer Thesis. Berlin Heidelberg: Springer-Verlag. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
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