N-(4-Meth­oxy-6-methyl-1,3,5-triazin-2-yl)-N-methyl-N′-(2,3,4-trifluoro­phen­yl)urea

In the title compound, C₁₃H₁₂F₃N₅O₂, intra­molecular N—H...F, N—H...N, C—H...O and C—H...N hydrogen bonds, and π–π stacking interactions generate a columnar structure along the a axis.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C)= 0.004 Å
• R factor = 0.061
• wR factor = 0.131
• Data-to-parameter ratio = 13.3

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S1. Comment

It is well known that substituted ureas containing a triazine group exhibit remarkable bioactivities such as herbicidal (Baumeister, et al., 1994), plant-growth regulatory (Douglass & Moon, 1987), antitubercular (Patel, et al., 2003) and antibacterial activity against Staphylococcus aureus and Escherichia coli (Patel, et al., 2003). We report here the crystal structure of the title compound, (I).

The molecular structure of (I) is shown in Fig. 1 and the selected bond lengths and angles are given in Table 1. The dihedral angle between the planes of the 1,3,5-triazine and trifluorophenyl fragments is 10.1 (2)°. Four intramolecular hydrogen bonds, N—H···F, N—H···N, C—H···O and C—H···N (Desiraju & Steiner, 1999), are observed in the molecule (Table 2, Fig 1). In the crystal structure, the molecules are stacked along the a axis, forming a columnar structure (Fig. 2). In the column, the interplanar distance of 3.35 (9) Å between benzene rings suggests π–π stacking interactions;this is shorter than the 'π-cloud thickness' (3.42 Å; Pauling, 1960).

S2. Experimental

4-Methoxy-N,6-dimethyl-1,3,5-triazin-2-amine (1.54 g, 10 mmol) was added to an anhydrous acetonitrile solution of 2,3,4-trifluorophenyl isocyanate (1.91 g, 10 mmol), and the mixture was stirred at 333 K for 3 h under nitrogen. A colourless precipatate was isolated, recrystallized from ethyl acetate–hexane mixture (3: 1 v/v) and dried in vacuo to give a pure compound in 86.2% yield. Colourless needle-like single crystals (m.p. 425–426 K) suitable for X-ray analysis were obtained by slow evaporation of a methanol solution. Analysis calculated for C₁₃H₁₂F₃N₅O₂: C47.71%, H3.70%, N21.40%; found: C47.74, H3.68, N21.45%.

S3. Refinement

All H atoms were placed in calculated positions and were refined isotropically, with U_iso(H) values constrained to 1.2U_eq(C, N), using a riding model, with C—H = 0.93–0.96 Å and N—H = 0.82 Å.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), drawn with 30% probability ellipsoids. Intramolecular hydrogen bonds are indicated by dashed lines.
	Fig. 2. A packing diagram for (I), with a pronounced column along the a axisa realised by π–π stacking.

N-(4-Methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methyl-N'-(2,3,4- trifluorophenyl)urea

Crystal data

C13H12F3N5O2	Z = 4
Mr = 327.28	F(000) = 672
Monoclinic, P21/c	Dx = 1.504 Mg m^−3
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 4.4215 (9) Å	µ = 0.13 mm^−1
b = 17.836 (4) Å	T = 291 K
c = 18.337 (4) Å	Needle, colourless
β = 91.55 (3)°	0.20 × 0.18 × 0.18 mm
V = 1445.6 (5) Å^3

Data collection

Bruker SMART EPEX CCD area-detector diffractometer	2853 independent reflections
Radiation source: sealed tube	2004 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ϕ and ω scans	θmax = 26.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −5→5
Tmin = 0.97, Tmax = 0.98	k = −21→22
7065 measured reflections	l = −22→22

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.05P)^2 + 0.66P] where P = (Fo^2 + 2Fc^2)/3
2853 reflections	(Δ/σ)max < 0.001
215 parameters	Δρmax = 0.18 e Å^−3
5 restraints	Δρmin = −0.17 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
C1	1.3580 (6)	0.84685 (14)	0.32140 (14)	0.0406 (6)
C2	1.5591 (6)	0.88786 (17)	0.27943 (15)	0.0487 (7)
C3	1.6664 (6)	0.95676 (15)	0.30487 (15)	0.0469 (7)
C4	1.5759 (7)	0.98402 (15)	0.37179 (16)	0.0514 (7)
H4A	1.6484	1.0299	0.3889	0.062*
C5	1.3753 (6)	0.94236 (14)	0.41338 (15)	0.0447 (7)
H5A	1.3166	0.9603	0.4585	0.054*
C6	1.2646 (6)	0.87501 (13)	0.38789 (14)	0.0375 (5)
C7	0.9725 (6)	0.83402 (14)	0.49500 (14)	0.0396 (6)
C8	0.6650 (5)	0.71991 (12)	0.48405 (13)	0.0338 (5)
C9	0.6187 (6)	0.64629 (14)	0.37602 (14)	0.0414 (6)
C10	0.3586 (6)	0.61059 (15)	0.48179 (16)	0.0463 (6)
C11	0.6924 (8)	0.78659 (17)	0.59864 (15)	0.0567 (8)
H11A	0.5552	0.7473	0.6114	0.085*
H11B	0.5972	0.8343	0.6055	0.085*
H11C	0.8718	0.7834	0.6292	0.085*
C12	0.7034 (7)	0.63214 (17)	0.30054 (15)	0.0584 (8)
H12A	0.6587	0.6756	0.2714	0.088*
H12B	0.5910	0.5901	0.2816	0.088*
H12C	0.9160	0.6215	0.2992	0.088*
C13	0.1304 (7)	0.57229 (18)	0.58781 (16)	0.0582 (8)
H13A	0.3146	0.5662	0.6161	0.087*
H13B	−0.0065	0.5323	0.5988	0.087*
H13C	0.0393	0.6195	0.5995	0.087*
F1	1.2525 (4)	0.78291 (9)	0.29433 (8)	0.0572 (5)
F2	1.6510 (5)	0.86056 (11)	0.21506 (9)	0.0727 (6)
F3	1.8663 (4)	0.99406 (11)	0.26409 (10)	0.0703 (6)
H1E	1.066 (9)	0.794 (2)	0.395 (2)	0.093 (13)*
N1	1.0659 (5)	0.82664 (12)	0.42591 (12)	0.0393 (5)
N2	0.7756 (5)	0.77826 (11)	0.52014 (11)	0.0396 (5)
N3	0.7406 (5)	0.70746 (12)	0.41227 (11)	0.0419 (5)
N4	0.4283 (5)	0.59705 (12)	0.41078 (13)	0.0497 (6)
N5	0.4759 (5)	0.67087 (12)	0.51916 (11)	0.0435 (5)
O1	1.0486 (5)	0.88538 (11)	0.53478 (10)	0.0605 (6)
O2	0.1962 (5)	0.57057 (12)	0.51147 (12)	0.0624 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0446 (15)	0.0360 (13)	0.0409 (13)	0.0014 (11)	−0.0032 (10)	−0.0044 (10)
C2	0.0457 (17)	0.0573 (17)	0.0431 (14)	0.0115 (12)	0.0015 (11)	0.0110 (12)
C3	0.0426 (16)	0.0490 (15)	0.0492 (16)	−0.0039 (12)	0.0036 (12)	0.0202 (13)
C4	0.0546 (18)	0.0369 (14)	0.0627 (18)	−0.0168 (12)	−0.0017 (14)	−0.0009 (13)
C5	0.0561 (18)	0.0360 (13)	0.0421 (15)	−0.0113 (12)	0.0018 (12)	0.0010 (11)
C6	0.0334 (14)	0.0323 (12)	0.0464 (13)	−0.0006 (10)	−0.0069 (10)	−0.0010 (10)
C7	0.0428 (14)	0.0370 (13)	0.0386 (13)	−0.0070 (11)	−0.0042 (10)	−0.0073 (10)
C8	0.0368 (13)	0.0260 (11)	0.0388 (13)	0.0026 (9)	0.0021 (10)	0.0036 (9)
C9	0.0387 (14)	0.0380 (13)	0.0474 (15)	−0.0066 (11)	−0.0035 (11)	−0.0080 (11)
C10	0.0474 (16)	0.0370 (14)	0.0545 (17)	−0.0041 (12)	0.0005 (13)	−0.0037 (12)
C11	0.077 (2)	0.0531 (17)	0.0407 (15)	−0.0197 (15)	0.0131 (14)	−0.0090 (13)
C12	0.068 (2)	0.0570 (18)	0.0508 (17)	−0.0022 (15)	0.0040 (14)	−0.0226 (14)
C13	0.061 (2)	0.0563 (18)	0.0579 (18)	−0.0167 (15)	0.0171 (15)	0.0016 (14)
F1	0.0779 (13)	0.0422 (9)	0.0517 (10)	−0.0155 (8)	0.0050 (8)	−0.0119 (7)
F2	0.0875 (14)	0.0882 (14)	0.0434 (10)	−0.0012 (11)	0.0216 (9)	−0.0016 (9)
F3	0.0673 (12)	0.0705 (12)	0.0735 (12)	−0.0222 (10)	0.0101 (9)	0.0225 (9)
N1	0.0459 (13)	0.0348 (11)	0.0374 (12)	−0.0092 (9)	0.0022 (9)	−0.0090 (9)
N2	0.0468 (13)	0.0375 (11)	0.0347 (11)	−0.0103 (9)	0.0059 (9)	−0.0031 (9)
N3	0.0451 (13)	0.0359 (11)	0.0449 (12)	−0.0030 (9)	0.0055 (10)	−0.0094 (9)
N4	0.0510 (15)	0.0378 (12)	0.0606 (15)	−0.0133 (10)	0.0051 (11)	−0.0065 (10)
N5	0.0460 (13)	0.0427 (12)	0.0419 (13)	−0.0039 (10)	0.0020 (10)	0.0030 (10)
O1	0.0864 (16)	0.0516 (12)	0.0440 (11)	−0.0313 (11)	0.0113 (10)	−0.0175 (9)
O2	0.0653 (15)	0.0620 (13)	0.0606 (13)	−0.0290 (11)	0.0131 (11)	−0.0061 (10)

Geometric parameters (Å, º)

C1—F1	1.324 (3)	C9—N3	1.380 (3)
C1—C6	1.392 (4)	C9—N4	1.384 (3)
C1—C2	1.398 (4)	C9—C12	1.466 (4)
C2—F2	1.350 (3)	C10—O2	1.158 (3)
C2—C3	1.393 (4)	C10—N4	1.368 (4)
C3—F3	1.349 (3)	C10—N5	1.369 (3)
C3—C4	1.389 (4)	C11—N2	1.503 (3)
C4—C5	1.399 (4)	C11—H11A	0.9600
C4—H4A	0.9300	C11—H11B	0.9600
C5—C6	1.374 (3)	C11—H11C	0.9600
C5—H5A	0.9300	C12—H12A	0.9600
C6—N1	1.427 (3)	C12—H12B	0.9600
C7—O1	1.213 (3)	C12—H12C	0.9600
C7—N1	1.350 (3)	C13—O2	1.438 (4)
C7—N2	1.408 (3)	C13—H13A	0.9600
C8—N2	1.320 (3)	C13—H13B	0.9600
C8—N5	1.381 (3)	C13—H13C	0.9600
C8—N3	1.385 (3)	N1—H1E	0.82 (4)
F1—C1—C6	122.0 (2)	N4—C10—N5	121.5 (2)
F1—C1—C2	117.9 (2)	N2—C11—H11A	109.5
C6—C1—C2	120.1 (2)	N2—C11—H11B	109.5
F2—C2—C3	120.2 (3)	H11A—C11—H11B	109.5
F2—C2—C1	120.2 (3)	N2—C11—H11C	109.5
C3—C2—C1	119.5 (3)	H11A—C11—H11C	109.5
F3—C3—C4	121.7 (3)	H11B—C11—H11C	109.5
F3—C3—C2	118.2 (3)	C9—C12—H12A	109.5
C4—C3—C2	120.0 (2)	C9—C12—H12B	109.5
C3—C4—C5	119.9 (2)	H12A—C12—H12B	109.5
C3—C4—H4A	120.1	C9—C12—H12C	109.5
C5—C4—H4A	120.1	H12A—C12—H12C	109.5
C6—C5—C4	120.3 (3)	H12B—C12—H12C	109.5
C6—C5—H5A	119.9	O2—C13—H13A	109.5
C4—C5—H5A	119.9	O2—C13—H13B	109.5
C5—C6—C1	120.1 (2)	H13A—C13—H13B	109.5
C5—C6—N1	125.5 (2)	O2—C13—H13C	109.5
C1—C6—N1	114.3 (2)	H13A—C13—H13C	109.5
O1—C7—N1	123.5 (2)	H13B—C13—H13C	109.5
O1—C7—N2	120.0 (2)	C7—N1—C6	127.4 (2)
N1—C7—N2	116.5 (2)	C7—N1—H1E	137 (3)
N2—C8—N5	119.1 (2)	C6—N1—H1E	94 (3)
N2—C8—N3	120.5 (2)	C8—N2—C7	128.1 (2)
N5—C8—N3	120.4 (2)	C8—N2—C11	117.5 (2)
N3—C9—N4	121.0 (2)	C7—N2—C11	114.4 (2)
N3—C9—C12	119.0 (2)	C9—N3—C8	118.9 (2)
N4—C9—C12	120.0 (2)	C10—N4—C9	118.8 (2)
O2—C10—N4	119.8 (3)	C10—N5—C8	119.3 (2)
O2—C10—N5	118.7 (3)	C10—O2—C13	126.1 (2)
F1—C1—C2—F2	−3.0 (4)	N3—C8—N2—C7	0.2 (4)
C6—C1—C2—F2	179.7 (2)	N5—C8—N2—C11	1.3 (3)
F1—C1—C2—C3	177.7 (2)	N3—C8—N2—C11	−177.8 (2)
C6—C1—C2—C3	0.4 (4)	O1—C7—N2—C8	178.3 (3)
F2—C2—C3—F3	−1.1 (4)	N1—C7—N2—C8	−1.4 (4)
C1—C2—C3—F3	178.3 (2)	O1—C7—N2—C11	−3.6 (4)
F2—C2—C3—C4	−178.8 (3)	N1—C7—N2—C11	176.7 (2)
C1—C2—C3—C4	0.6 (4)	N4—C9—N3—C8	−1.2 (4)
F3—C3—C4—C5	−178.0 (3)	C12—C9—N3—C8	−178.8 (2)
C2—C3—C4—C5	−0.4 (4)	N2—C8—N3—C9	−179.4 (2)
C3—C4—C5—C6	−0.8 (4)	N5—C8—N3—C9	1.4 (4)
C4—C5—C6—C1	1.8 (4)	O2—C10—N4—C9	178.9 (3)
C4—C5—C6—N1	178.2 (3)	N5—C10—N4—C9	−0.9 (4)
F1—C1—C6—C5	−178.7 (2)	N3—C9—N4—C10	1.0 (4)
C2—C1—C6—C5	−1.6 (4)	C12—C9—N4—C10	178.5 (3)
F1—C1—C6—N1	4.4 (3)	O2—C10—N5—C8	−178.7 (3)
C2—C1—C6—N1	−178.4 (2)	N4—C10—N5—C8	1.2 (4)
O1—C7—N1—C6	0.5 (5)	N2—C8—N5—C10	179.5 (2)
N2—C7—N1—C6	−179.8 (2)	N3—C8—N5—C10	−1.4 (4)
C5—C6—N1—C7	−6.4 (4)	N4—C10—O2—C13	172.1 (3)
C1—C6—N1—C7	170.2 (3)	N5—C10—O2—C13	−8.0 (5)
N5—C8—N2—C7	179.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1E···F1	0.81 (4)	2.05 (4)	2.687 (3)	135 (3)
N1—H1E···N3	0.81 (4)	2.14 (4)	2.575 (3)	114 (3)
C5—H5A···O1	0.93	2.29	2.872 (3)	120
C11—H11A···N5	0.96	2.19	2.688 (4)	111