1-(3-Methyl­phen­yl)-3-{5-[4-(trifluoro­meth­yl)phen­yl]-1,3,4-thia­diazol-2-yl}­urea

The mol­ecule of the title compound, C₁₇H₁₃F₃N₄OS, assumes a planar conformation except for the F atoms and methyl H atoms. Inter­molecular N—H...N hydrogen bonding between the urea and thia­diazole groups links neighbouring mol­ecules into centrosymmetric supra­molecular R₂²(8) dimers. The F atoms are disordered over two positions with a site occupancy ratio of 2:1.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.006 Å
• Disorder in main residue
• R factor = 0.069
• wR factor = 0.204
• Data-to-parameter ratio = 10.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        C17
PLAT431_ALERT_2_B Short Inter HL..A Contact  F3'    ..  F3'     ..       2.46 Ang.

Alert level C
PLAT213_ALERT_2_C Atom F3'     has ADP max/min Ratio .............       3.20 prola
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C14
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.09
PLAT301_ALERT_3_C Main Residue  Disorder .........................      10.00 Perc.
PLAT322_ALERT_2_C Check Hybridisation of  S1     in Main Residue .          ?
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          6
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1     ...          ?

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         12

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

1,3,4-Thiadiazole derivatives have been reported to possess broad spectrum bioactivities, such as insecticidal, fungicidal and plant-growth regulating activities (Zou et al., 2002; Song et al., 2005). Urea derivatives have attracted much attention owing to their diverse biological effects (Du et al., 2000; Wang et al., 2004). Furthermore, considerable interest has been shown in fluorine-containing compounds in the field of modern agrochemistry and medicinal chemistry. In our continuing search for biological active urea derivatives as plant-growth regulators, we would like to investigate substituted ureas incorporating both 1,3,4-thiadiazole and CF₃ groups, including the title compound.

The crystal structure (Fig. 1) revealed that the three rings in the molecule are essentially coplanar, the dihedral angles formed by the thiadiazole ring with methylbenzene and trifluoromethylbenzene moieties being only 1.4 (2)° and 4.8 (2)°. It is obvious that the molecule is nearly planar, as can be attributed to the presence of the extended π conjugated system throughout the whole molecule. Bond lengths and angles are as expected. In the crystal structure, neighbouring molecules are linked by complementary N—H···N hydrogen bonding into an R₂²(8) motif (Bernstein et al., 1995), as shown in Fig. 2 and Table 1.

Related literature

For general background, see: Du et al. (2000); Song et al. (2005); Wang et al. (2004); Zou et al. (2002); Bernstein et al. (1995). For synthesis, see: Song, Wang et al. (2007); Song, Tan & Wang (2007).

S2. Experimental

The required 2-amino-5-(4-trifluoromethyl-phenyl)-1,3,4-thiadiazole was obtained by dehydration-cyclization of 4-trifluoromethyl-benzoic acid and thiosemicarbozide in presence of phosphorus oxychloride according to a literature method (Song, Wang et al., 2007). The title compound was then prepared according to the procedure reported by Song, Tan & Wang (2007). Suitable crystals were obtained from a methanol–DMF (1:3) solution at room temperature. Elemental analysis: analysis calculated for C₁₇H₁₃F₃N₄OS: C 53.96, H 3.46, N 14.81%; found: C 54.03, H 3.59, N 14.67%.

S3. Refinement

Imino H atoms were located in a difference Fourier map and refined as riding in as-found relative positions, U_iso(H) = 1.2U_eq(N). The methyl H atoms were placed in calculated positions with C—H = 0.96 Å and torsion angle was refined to fit the electron density, U_iso(H) = 1.5U_eq(C). Other H atoms were positioned geometrically and constrained to ride on their parent atoms with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The F atoms of trifluoromethyl group are disordered over two sites, occupancies were initialy refined and fixed at 0.67 and 1/3, respectively; geometry constrains were applied for the disordered group.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of the molecule of (I) showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary size.
	Fig. 2. A partial packing diagram for (I) [symmetry code: (a) 2 - x, 2 - y, -z]. Hydrogen bonds are indicated by dashed lines.

1-(3-Methylphenyl)-3-{5-[4-(trifluoromethyl)phenyl]-1,3,4-thiadiazol-2-yl}urea

Crystal data

C17H13F3N4OS	Z = 2
Mr = 378.38	F(000) = 388
Triclinic, P1	Dx = 1.509 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.478 (1) Å	Cell parameters from 1187 reflections
b = 8.0133 (14) Å	θ = 2.6–22.1°
c = 19.351 (3) Å	µ = 0.24 mm^−1
α = 99.972 (3)°	T = 292 K
β = 92.435 (4)°	Block, colourless
γ = 94.290 (3)°	0.20 × 0.10 × 0.06 mm
V = 832.9 (2) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	2203 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 25.0°, θmin = 2.1°
φ and ω scans	h = −6→6
4221 measured reflections	k = −6→9
2889 independent reflections	l = −22→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.204	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.1058P)^2 + 0.1695P] where P = (Fo^2 + 2Fc^2)/3
2889 reflections	(Δ/σ)max = 0.001
264 parameters	Δρmax = 0.38 e Å^−3
12 restraints	Δρmin = −0.32 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.3164 (11)	0.3797 (7)	−0.3256 (2)	0.0919 (18)
H1A	0.4439	0.3032	−0.3295	0.138*
H1B	0.3728	0.4827	−0.3411	0.138*
H1C	0.1747	0.3273	−0.3544	0.138*
C2	0.4087 (7)	0.5277 (5)	−0.2014 (2)	0.0517 (10)
H2	0.5538	0.5741	−0.2163	0.062*
C3	0.2499 (9)	0.4203 (5)	−0.2499 (2)	0.0604 (12)
C4	0.0373 (9)	0.3538 (6)	−0.2259 (3)	0.0676 (12)
H4	−0.0733	0.2815	−0.2572	0.081*
C5	−0.0134 (8)	0.3925 (5)	−0.1569 (2)	0.0642 (11)
H5	−0.1593	0.3465	−0.1423	0.077*
C6	0.1433 (7)	0.4969 (5)	−0.1082 (2)	0.0503 (9)
H6	0.1076	0.5197	−0.0611	0.060*
C7	0.3573 (7)	0.5676 (4)	−0.13140 (18)	0.0423 (8)
C8	0.5228 (6)	0.7434 (5)	−0.01756 (18)	0.0424 (8)
C9	0.7631 (7)	0.9361 (5)	0.07428 (18)	0.0438 (9)
C10	0.7901 (6)	1.0522 (4)	0.19476 (18)	0.0428 (9)
C11	0.7676 (7)	1.1034 (5)	0.27066 (18)	0.0463 (9)
C12	0.5630 (9)	1.0524 (6)	0.3030 (2)	0.0731 (13)
H12	0.4356	0.9858	0.2758	0.088*
C13	0.5405 (10)	1.0969 (6)	0.3743 (2)	0.0795 (14)
H13	0.3998	1.0615	0.3948	0.095*
C14	0.7283 (9)	1.1941 (5)	0.4146 (2)	0.0638 (12)
C15	0.9277 (10)	1.2474 (7)	0.3834 (2)	0.0781 (14)
H15	1.0533	1.3154	0.4107	0.094*
C16	0.9507 (9)	1.2039 (6)	0.3120 (2)	0.0706 (12)
H16	1.0903	1.2428	0.2918	0.085*
C17	0.7119 (15)	1.2439 (9)	0.4920 (3)	0.096 (2)
F1	0.4700 (19)	1.2214 (17)	0.5122 (9)	0.121 (4)	0.67
F2	0.829 (2)	1.1386 (11)	0.5265 (4)	0.126 (3)	0.67
F3	0.788 (3)	1.3979 (13)	0.5189 (5)	0.147 (6)	0.67
F1'	0.552 (5)	1.180 (4)	0.5166 (18)	0.138 (9)	0.33
F2'	0.907 (4)	1.252 (4)	0.5279 (10)	0.181 (12)	0.33
F3'	0.672 (5)	1.410 (3)	0.5021 (11)	0.163 (12)	0.33
N1	0.5294 (5)	0.6798 (4)	−0.08729 (15)	0.0476 (8)
H1	0.6555	0.7089	−0.1080	0.057*
N2	0.7195 (5)	0.8563 (4)	0.00599 (14)	0.0492 (8)
H2A	0.8396	0.8756	−0.0201	0.059*
N3	0.9620 (5)	1.0398 (4)	0.09270 (15)	0.0494 (8)
N4	0.9775 (6)	1.1066 (4)	0.16332 (15)	0.0495 (8)
O1	0.3635 (5)	0.7090 (3)	0.02018 (13)	0.0579 (7)
S1	0.57658 (17)	0.91409 (12)	0.14109 (5)	0.0467 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.139 (5)	0.089 (4)	0.044 (2)	0.022 (3)	−0.004 (3)	−0.004 (2)
C2	0.058 (2)	0.046 (2)	0.053 (2)	0.0083 (18)	0.0051 (18)	0.0107 (18)
C3	0.083 (3)	0.053 (2)	0.044 (2)	0.022 (2)	−0.011 (2)	0.0009 (19)
C4	0.065 (3)	0.059 (3)	0.071 (3)	−0.002 (2)	−0.021 (2)	−0.001 (2)
C5	0.052 (3)	0.061 (3)	0.078 (3)	0.003 (2)	−0.002 (2)	0.011 (2)
C6	0.048 (2)	0.048 (2)	0.054 (2)	−0.0001 (17)	0.0043 (17)	0.0054 (18)
C7	0.049 (2)	0.0362 (18)	0.0413 (19)	0.0059 (16)	0.0018 (16)	0.0049 (15)
C8	0.0359 (19)	0.049 (2)	0.0427 (19)	−0.0027 (16)	0.0104 (15)	0.0098 (16)
C9	0.045 (2)	0.046 (2)	0.0398 (19)	0.0003 (16)	0.0062 (15)	0.0078 (16)
C10	0.045 (2)	0.0402 (19)	0.0433 (19)	0.0026 (16)	0.0040 (16)	0.0078 (16)
C11	0.060 (2)	0.039 (2)	0.0401 (19)	0.0041 (17)	0.0046 (17)	0.0079 (16)
C12	0.090 (3)	0.080 (3)	0.043 (2)	−0.016 (3)	0.009 (2)	−0.001 (2)
C13	0.103 (4)	0.086 (4)	0.046 (2)	−0.013 (3)	0.017 (2)	0.007 (2)
C14	0.092 (3)	0.052 (2)	0.046 (2)	0.003 (2)	0.010 (2)	0.0050 (19)
C15	0.089 (4)	0.086 (3)	0.049 (2)	−0.013 (3)	−0.003 (2)	−0.008 (2)
C16	0.074 (3)	0.076 (3)	0.054 (3)	−0.007 (2)	0.002 (2)	−0.003 (2)
C17	0.142 (6)	0.090 (5)	0.049 (3)	−0.017 (4)	0.012 (4)	0.000 (3)
F1	0.121 (6)	0.167 (9)	0.061 (5)	0.004 (5)	0.036 (5)	−0.019 (5)
F2	0.184 (9)	0.154 (7)	0.044 (4)	0.017 (6)	−0.002 (4)	0.031 (5)
F3	0.243 (13)	0.112 (8)	0.059 (5)	−0.074 (9)	0.024 (7)	−0.026 (4)
F1'	0.18 (2)	0.165 (15)	0.057 (8)	−0.019 (15)	0.022 (15)	0.008 (10)
F2'	0.167 (18)	0.29 (4)	0.066 (9)	0.09 (2)	−0.046 (11)	−0.047 (18)
F3'	0.29 (3)	0.109 (14)	0.073 (11)	0.067 (18)	−0.005 (13)	−0.047 (8)
N1	0.0454 (18)	0.0529 (19)	0.0420 (17)	−0.0085 (14)	0.0128 (14)	0.0044 (14)
N2	0.0479 (18)	0.060 (2)	0.0366 (16)	−0.0112 (15)	0.0137 (13)	0.0021 (14)
N3	0.0477 (19)	0.0543 (19)	0.0424 (17)	−0.0063 (15)	0.0092 (13)	0.0008 (14)
N4	0.0540 (19)	0.0483 (18)	0.0426 (17)	−0.0028 (15)	0.0055 (14)	0.0006 (14)
O1	0.0574 (17)	0.0684 (18)	0.0435 (14)	−0.0139 (13)	0.0116 (13)	0.0038 (13)
S1	0.0495 (6)	0.0502 (6)	0.0390 (5)	−0.0053 (4)	0.0075 (4)	0.0068 (4)

Geometric parameters (Å, º)

C1—C3	1.511 (6)	C10—C11	1.468 (5)
C1—H1A	0.9600	C10—S1	1.726 (4)
C1—H1B	0.9600	C11—C16	1.372 (6)
C1—H1C	0.9600	C11—C12	1.376 (6)
C2—C7	1.383 (5)	C12—C13	1.378 (6)
C2—C3	1.385 (6)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.369 (7)
C3—C4	1.377 (7)	C13—H13	0.9300
C4—C5	1.364 (6)	C14—C15	1.348 (7)
C4—H4	0.9300	C14—C17	1.490 (7)
C5—C6	1.369 (6)	C15—C16	1.379 (6)
C5—H5	0.9300	C15—H15	0.9300
C6—C7	1.389 (5)	C16—H16	0.9300
C6—H6	0.9300	C17—F1'	1.15 (3)
C7—N1	1.402 (4)	C17—F2'	1.24 (2)
C8—O1	1.208 (4)	C17—F3	1.284 (12)
C8—N1	1.360 (4)	C17—F2	1.344 (12)
C8—N2	1.363 (4)	C17—F3'	1.35 (2)
C9—N3	1.316 (5)	C17—F1	1.405 (14)
C9—N2	1.367 (5)	N1—H1	0.8513
C9—S1	1.706 (3)	N2—H2A	0.8663
C10—N4	1.300 (5)	N3—N4	1.375 (4)
C3—C1—H1A	109.5	C11—C12—C13	122.2 (5)
C3—C1—H1B	109.5	C11—C12—H12	118.9
H1A—C1—H1B	109.5	C13—C12—H12	118.9
C3—C1—H1C	109.5	C14—C13—C12	119.1 (5)
H1A—C1—H1C	109.5	C14—C13—H13	120.5
H1B—C1—H1C	109.5	C12—C13—H13	120.5
C7—C2—C3	121.7 (4)	C15—C14—C13	119.3 (4)
C7—C2—H2	119.2	C15—C14—C17	120.0 (5)
C3—C2—H2	119.2	C13—C14—C17	120.7 (5)
C4—C3—C2	117.5 (4)	C14—C15—C16	121.9 (5)
C4—C3—C1	123.0 (4)	C14—C15—H15	119.0
C2—C3—C1	119.5 (5)	C16—C15—H15	119.0
C5—C4—C3	120.9 (4)	C11—C16—C15	119.9 (4)
C5—C4—H4	119.5	C11—C16—H16	120.0
C3—C4—H4	119.5	C15—C16—H16	120.0
C4—C5—C6	122.2 (4)	F1'—C17—F2'	111.9 (18)
C4—C5—H5	118.9	F3—C17—F2	108.7 (8)
C6—C5—H5	118.9	F1'—C17—F3'	105.1 (14)
C5—C6—C7	117.9 (4)	F2'—C17—F3'	99.8 (14)
C5—C6—H6	121.0	F3—C17—F1	105.8 (8)
C7—C6—H6	121.0	F2—C17—F1	102.3 (7)
C2—C7—C6	119.8 (4)	F1'—C17—C14	116.7 (18)
C2—C7—N1	116.8 (3)	F2'—C17—C14	116.0 (12)
C6—C7—N1	123.5 (3)	F3—C17—C14	116.4 (7)
O1—C8—N1	125.8 (3)	F2—C17—C14	110.9 (6)
O1—C8—N2	122.5 (3)	F3'—C17—C14	104.9 (11)
N1—C8—N2	111.7 (3)	F1—C17—C14	111.7 (8)
N3—C9—N2	120.0 (3)	C8—N1—C7	129.2 (3)
N3—C9—S1	114.8 (3)	C8—N1—H1	117.4
N2—C9—S1	125.2 (3)	C7—N1—H1	113.4
N4—C10—C11	121.7 (3)	C8—N2—C9	124.2 (3)
N4—C10—S1	115.1 (3)	C8—N2—H2A	122.7
C11—C10—S1	123.2 (3)	C9—N2—H2A	112.7
C16—C11—C12	117.6 (4)	C9—N3—N4	112.1 (3)
C16—C11—C10	121.0 (4)	C10—N4—N3	111.6 (3)
C12—C11—C10	121.4 (4)	C9—S1—C10	86.44 (17)
C7—C2—C3—C4	−0.1 (6)	C13—C14—C17—F2'	144.9 (19)
C7—C2—C3—C1	−179.4 (4)	C15—C14—C17—F3	40.9 (12)
C2—C3—C4—C5	−0.1 (6)	C13—C14—C17—F3	−137.9 (10)
C1—C3—C4—C5	179.2 (4)	C15—C14—C17—F2	−84.0 (8)
C3—C4—C5—C6	−0.6 (7)	C13—C14—C17—F2	97.2 (9)
C4—C5—C6—C7	1.6 (6)	C15—C14—C17—F3'	72.7 (14)
C3—C2—C7—C6	1.1 (5)	C13—C14—C17—F3'	−106.1 (13)
C3—C2—C7—N1	−179.0 (3)	C15—C14—C17—F1	162.5 (7)
C5—C6—C7—C2	−1.8 (5)	C13—C14—C17—F1	−16.3 (10)
C5—C6—C7—N1	178.3 (3)	O1—C8—N1—C7	2.1 (6)
N4—C10—C11—C16	−3.4 (6)	N2—C8—N1—C7	−176.8 (3)
S1—C10—C11—C16	175.3 (3)	C2—C7—N1—C8	178.2 (3)
N4—C10—C11—C12	176.6 (4)	C6—C7—N1—C8	−1.9 (6)
S1—C10—C11—C12	−4.7 (5)	O1—C8—N2—C9	2.9 (6)
C16—C11—C12—C13	−1.1 (7)	N1—C8—N2—C9	−178.1 (3)
C10—C11—C12—C13	178.9 (4)	N3—C9—N2—C8	178.1 (3)
C11—C12—C13—C14	−0.4 (8)	S1—C9—N2—C8	−2.1 (5)
C12—C13—C14—C15	1.6 (8)	N2—C9—N3—N4	−179.2 (3)
C12—C13—C14—C17	−179.6 (5)	S1—C9—N3—N4	1.0 (4)
C13—C14—C15—C16	−1.4 (8)	C11—C10—N4—N3	178.8 (3)
C17—C14—C15—C16	179.8 (5)	S1—C10—N4—N3	0.0 (4)
C12—C11—C16—C15	1.3 (7)	C9—N3—N4—C10	−0.6 (4)
C10—C11—C16—C15	−178.7 (4)	N3—C9—S1—C10	−0.8 (3)
C14—C15—C16—C11	−0.1 (8)	N2—C9—S1—C10	179.4 (3)
C15—C14—C17—F1'	−171.5 (17)	N4—C10—S1—C9	0.4 (3)
C13—C14—C17—F1'	9.7 (18)	C11—C10—S1—C9	−178.4 (3)
C15—C14—C17—F2'	−36 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N3^i	0.87	1.99	2.829 (4)	162

Symmetry code: (i) −x+2, −y+2, −z.