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Acta Cryst. (2011). E67, o987    [ doi:10.1107/S1600536811010683 ]

5-Methyl-3-(3-methylphenyl)-7-phenyl-1,2,4-triazolo[4,3-c]pyrimidine

J. Preis, D. Schollmeyer and H. Detert

Abstract top

The title compound, C19H16N4, is one of the few known 3,7-diaryl-1,2,4-triazolo[4,3-c]pyrimidines. The triazolopyrimidine unit is essentially planar (r.m.s. deviation = 0.048 Å). The phenyl ring and the heterocyclic core subtend a dihedral angle of only 15.09 (6)°, whereas the m-tolyl ring is twisted by 71.80 (6)° out of the plane of the triazole ring. Two C-H...N hydrogen bonds and [pi]-[pi] stacking interactions [centroid-centroid distance = 3.7045 (8) Å] stabilize the crystal packing.

Comment top

The title compound was synthesized as part of a larger project focusing on the synthesis of higher conjugated and annulated heterocyclic π-systems see Detert & Schollmeyer (1999), Sugiono & Detert (2001). The acylation of tetrazoles followed by thermal ring transformation is a highly efficient route for the synthesis of 1,3,4-oxadiazoles and triazoles (Huisgen, Sauer & Seidel 1960; Huisgen, Sturm & Markgraf, 1960) and can also be applied to 2-chloroazines to yield triazolo-annulated azines. In the crystals of the title compound, the phenyl ring is only slightly turned out of the plane of the heterocyclic core [dihedral angle of 15.09 (6)°], the angle between the mean planes of the core and the m-tolyl ring amounts to 71.80 (6)°. Two molecules of the title compound form a dimer connected via hydrogen bonds C6—H6···N8 (2.53 Å) and C23—H23···N8 (2.61 Å). In the crystal, the dimers are connected via π-π-interactions between the rings with a distance of the triazoles (C1—N2, C7—N9) of 3.5404 (8) Å and of the pyrimidines (N2—C7) of 3.7045 (8) Å.

Related literature top

For the synthesis of higher conjugated and annulated heterocyclic π-systems, see: Detert & Schollmeyer (1999); Sugiono & Detert (2001). The acylation of tetrazoles with chloroazines and thermal ring transformation leads to triazolo annulated azines, see: Huisgen, Sauer & Seidel (1960); Huisgen, Sturm & Markgraf (1960); Huisgen et al. (1961); Glang et al. (2008). Whereas a broad variety of triazolopyrimidines are known, only two further [1,2,4]triazolo[4,3-c]pyrimidines with a 3,7-diaryl substitution have been reported so far, see: Seada et al. (1992).

Experimental top

The title compound was prepared by adding 2,4,6-collidine (0.54 g, 4.5 mmol) to a solution of 4-chloro-2-methyl-6-phenylpyrimidine (0.61 g, 3 mmol) and 5-(3-methyl- phenyl)tetrazole in xylenes (60 ml) and heating until gas was evolved (363 K). Stirring and heating was continued for 6 h, the solvent removed in vacuo and the residue purified by chromatography (SiO2 /toluene/ethyl acetate = 1 / 1, Rf = 0.28). The title compound was isolated as a yellowish powder with m.p. = 412–413 K. Crystals were obtained by slow evaporation of a solution of the title compound in chloroform/hexanes. All spectrocopic data were in accordance with the assumed structure, but an unique proton-proton coupling over 6 bonds from the pyrimidine-H across the heterocycle to the methyl group was observed.

Refinement top

Hydrogen atoms were placed at calculated positions with C—H = 0.95 Å (aromatic) or 0.98–0.99 Å (sp3 C-atom). All H atoms were refined in the riding-model approximation with isotropic displacement parameters set at 1.2–1.5 times of the Ueq of the parent atom.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: CORINC (Dräger & Gattow, 1971); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. View of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Part of the packing diagram showing the hydrogen bonds and the π-π-interactions. View along a axis.
5-Methyl-3-(3-methylphenyl)-7-phenyl-1,2,4-triazolo[4,3-c]pyrimidine top
Crystal data top
C19H16N4Z = 2
Mr = 300.36F(000) = 316
Triclinic, P1Dx = 1.292 Mg m−3
Hall symbol: -P 1Melting point: 412 K
a = 6.4270 (4) ÅCu Kα radiation, λ = 1.54178 Å
b = 11.1706 (6) ÅCell parameters from 25 reflections
c = 11.3672 (7) Åθ = 61–70°
α = 79.963 (5)°µ = 0.63 mm−1
β = 74.894 (5)°T = 193 K
γ = 81.877 (5)°Plate, yellow
V = 771.88 (8) Å30.45 × 0.40 × 0.25 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.088
Radiation source: rotating anodeθmax = 69.9°, θmin = 4.0°
graphiteh = −7→0
ω/2θ scansk = −13→13
3207 measured reflectionsl = −13→13
2924 independent reflections3 standard reflections every 60 min
2573 reflections with I > 2σ(I) intensity decay: 2%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.119 w = 1/[σ2(Fo2) + (0.0657P)2 + 0.1681P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2924 reflectionsΔρmax = 0.25 e Å−3
211 parametersΔρmin = −0.21 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0261 (19)
Crystal data top
C19H16N4γ = 81.877 (5)°
Mr = 300.36V = 771.88 (8) Å3
Triclinic, P1Z = 2
a = 6.4270 (4) ÅCu Kα radiation
b = 11.1706 (6) ŵ = 0.63 mm−1
c = 11.3672 (7) ÅT = 193 K
α = 79.963 (5)°0.45 × 0.40 × 0.25 mm
β = 74.894 (5)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.088
3207 measured reflectionsθmax = 69.9°
2924 independent reflections3 standard reflections every 60 min
2573 reflections with I > 2σ(I) intensity decay: 2%
Refinement top
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.119Δρmax = 0.25 e Å−3
S = 1.03Δρmin = −0.21 e Å−3
2924 reflectionsAbsolute structure: ?
211 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. 1H-NMR (CDCl3): 8.06 (d, 1 H), 8.03 (d 1 H), 7.90 (s, 1H, H-5 pyrimidin), 7.45 (m, 7 H), 2.47 (S, 3 H, CH3), 2.43 (3, 3 H, CH3); 13C-NMR (CDCl3): 151.4, 149.2, 147.1, 146.3, 138.3, 136.1, 131.5, 131.4, 129.9, 128.9, 128.2, 128.0, 127.9, 103.0, 23.6, 21.4; MS (FD): 300.1 (100%, M+), 600.3 (8% M2+), 900.3 (M3+). UV-vis: λmax =393nm (CH2Cl2), fluorescence: λmax =503nm (CH2Cl2).

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
xyzUiso*/Ueq
C10.4291 (2)0.07105 (12)0.69733 (11)0.0279 (3)
N20.35695 (17)0.15861 (10)0.60994 (9)0.0269 (3)
C30.3949 (2)0.27979 (12)0.56152 (12)0.0295 (3)
N40.30230 (19)0.33877 (10)0.47760 (10)0.0322 (3)
C50.1646 (2)0.28265 (12)0.43301 (12)0.0291 (3)
C60.1357 (2)0.16223 (12)0.46841 (12)0.0300 (3)
H60.04680.12390.43430.036*
C70.2419 (2)0.09577 (12)0.55754 (12)0.0275 (3)
N80.24802 (18)−0.02029 (10)0.60599 (10)0.0317 (3)
N90.36567 (18)−0.03428 (10)0.69480 (10)0.0318 (3)
C100.5391 (2)0.09494 (12)0.78900 (12)0.0284 (3)
C110.4254 (2)0.16174 (12)0.88241 (12)0.0315 (3)
H110.27920.19310.88490.038*
C120.5209 (2)0.18358 (12)0.97209 (12)0.0334 (3)
C130.7358 (2)0.13693 (13)0.96559 (13)0.0371 (3)
H130.80510.15161.02520.045*
C140.8494 (2)0.06977 (15)0.87386 (14)0.0404 (4)
H140.99560.03840.87130.049*
C150.7522 (2)0.04762 (14)0.78542 (13)0.0355 (3)
H150.83050.00060.72300.043*
C160.3970 (3)0.25436 (16)1.07371 (15)0.0502 (4)
H16A0.43220.33921.05290.075*
H16B0.43660.21761.15070.075*
H16C0.24130.25251.08380.075*
C170.5494 (3)0.33769 (13)0.60606 (13)0.0379 (3)
H17A0.57960.41610.55430.057*
H17B0.68450.28380.60180.057*
H17C0.48550.35130.69150.057*
C180.0596 (2)0.36189 (12)0.34111 (12)0.0316 (3)
C190.1311 (3)0.47490 (14)0.28749 (15)0.0450 (4)
H190.24400.50280.31210.054*
C200.0393 (3)0.54751 (16)0.19826 (17)0.0555 (5)
H200.09080.62430.16150.067*
C21−0.1258 (3)0.50869 (16)0.16287 (16)0.0522 (4)
H21−0.18850.55840.10170.063*
C22−0.2000 (3)0.39726 (16)0.21656 (16)0.0476 (4)
H22−0.31490.37070.19260.057*
C23−0.1088 (2)0.32384 (14)0.30495 (14)0.0383 (3)
H23−0.16100.24720.34120.046*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0275 (6)0.0296 (6)0.0261 (6)−0.0006 (5)−0.0059 (5)−0.0052 (5)
N20.0276 (5)0.0283 (6)0.0264 (5)−0.0024 (4)−0.0077 (4)−0.0067 (4)
C30.0327 (7)0.0293 (7)0.0279 (6)−0.0057 (5)−0.0075 (5)−0.0054 (5)
N40.0381 (6)0.0315 (6)0.0301 (6)−0.0064 (5)−0.0125 (5)−0.0040 (5)
C50.0292 (6)0.0320 (7)0.0275 (6)−0.0024 (5)−0.0072 (5)−0.0084 (5)
C60.0306 (7)0.0320 (7)0.0307 (7)−0.0019 (5)−0.0106 (5)−0.0096 (5)
C70.0264 (6)0.0292 (6)0.0290 (6)−0.0031 (5)−0.0064 (5)−0.0099 (5)
N80.0349 (6)0.0293 (6)0.0344 (6)−0.0021 (4)−0.0137 (5)−0.0067 (5)
N90.0337 (6)0.0311 (6)0.0329 (6)−0.0014 (4)−0.0121 (5)−0.0059 (5)
C100.0305 (7)0.0288 (7)0.0265 (6)−0.0035 (5)−0.0088 (5)−0.0022 (5)
C110.0319 (7)0.0317 (7)0.0317 (7)0.0031 (5)−0.0124 (5)−0.0046 (5)
C120.0431 (8)0.0293 (7)0.0297 (7)0.0017 (6)−0.0144 (6)−0.0046 (5)
C130.0426 (8)0.0393 (8)0.0344 (7)−0.0020 (6)−0.0209 (6)−0.0029 (6)
C140.0307 (7)0.0510 (9)0.0410 (8)0.0011 (6)−0.0143 (6)−0.0061 (7)
C150.0311 (7)0.0423 (8)0.0320 (7)0.0010 (6)−0.0062 (5)−0.0088 (6)
C160.0641 (11)0.0504 (9)0.0417 (9)0.0153 (8)−0.0249 (8)−0.0206 (7)
C170.0474 (8)0.0352 (7)0.0368 (7)−0.0144 (6)−0.0187 (6)0.0008 (6)
C180.0355 (7)0.0321 (7)0.0285 (7)0.0013 (5)−0.0104 (5)−0.0081 (5)
C190.0572 (10)0.0350 (8)0.0494 (9)−0.0071 (7)−0.0261 (8)−0.0021 (7)
C200.0750 (12)0.0369 (9)0.0590 (11)−0.0055 (8)−0.0320 (9)0.0051 (8)
C210.0667 (11)0.0456 (9)0.0472 (9)0.0101 (8)−0.0299 (8)−0.0028 (7)
C220.0493 (9)0.0526 (10)0.0486 (9)0.0026 (7)−0.0275 (7)−0.0101 (7)
C230.0395 (8)0.0395 (8)0.0395 (8)−0.0025 (6)−0.0162 (6)−0.0065 (6)
Geometric parameters (Å, °) top
C1—N91.3057 (17)C18—C231.3939 (19)
C1—N21.3899 (16)C19—C201.387 (2)
C1—C101.4802 (17)C20—C211.375 (2)
N2—C71.3846 (15)C21—C221.379 (3)
N2—C31.3995 (17)C22—C231.382 (2)
C3—N41.2901 (17)C6—H60.9500
C3—C171.4890 (18)C11—H110.9500
N4—C51.3909 (16)C13—H130.9500
C5—C61.3598 (19)C14—H140.9500
C5—C181.4854 (18)C15—H150.9500
C6—C71.4136 (18)C16—H16A0.9800
C7—N81.3167 (17)C16—H16B0.9800
N8—N91.3873 (15)C16—H16C0.9800
C10—C151.3896 (19)C17—H17A0.9800
C10—C111.3914 (18)C17—H17B0.9800
C11—C121.3894 (18)C17—H17C0.9800
C12—C131.393 (2)C19—H190.9500
C12—C161.502 (2)C20—H200.9500
C13—C141.380 (2)C21—H210.9500
C14—C151.385 (2)C22—H220.9500
C18—C191.388 (2)C23—H230.9500
N9—C1—N2109.46 (11)C21—C22—C23120.60 (15)
N9—C1—C10124.55 (12)C22—C23—C18120.25 (14)
N2—C1—C10125.66 (11)C5—C6—H6121.00
C7—N2—C1104.30 (10)C7—C6—H6121.00
C7—N2—C3120.16 (11)C10—C11—H11119.00
C1—N2—C3135.10 (11)C12—C11—H11119.00
N4—C3—N2120.52 (12)C12—C13—H13119.00
N4—C3—C17120.83 (12)C14—C13—H13120.00
N2—C3—C17118.63 (11)C13—C14—H14120.00
C3—N4—C5120.57 (12)C15—C14—H14120.00
C6—C5—N4121.74 (12)C10—C15—H15120.00
C6—C5—C18122.78 (12)C14—C15—H15120.00
N4—C5—C18115.43 (11)C12—C16—H16A109.00
C5—C6—C7117.99 (12)C12—C16—H16B109.00
N8—C7—N2110.52 (11)C12—C16—H16C109.00
N8—C7—C6131.23 (12)H16A—C16—H16B109.00
N2—C7—C6118.22 (12)H16A—C16—H16C109.00
C7—N8—N9106.71 (10)H16B—C16—H16C109.00
C1—N9—N8108.99 (11)C3—C17—H17A109.00
C15—C10—C11119.64 (12)C3—C17—H17B109.00
C15—C10—C1120.71 (12)C3—C17—H17C109.00
C11—C10—C1119.62 (11)H17A—C17—H17B110.00
C12—C11—C10121.45 (12)H17A—C17—H17C109.00
C11—C12—C13117.93 (13)H17B—C17—H17C109.00
C11—C12—C16121.36 (13)C18—C19—H19120.00
C13—C12—C16120.71 (13)C20—C19—H19120.00
C14—C13—C12121.05 (13)C19—C20—H20120.00
C13—C14—C15120.59 (13)C21—C20—H20120.00
C14—C15—C10119.32 (13)C20—C21—H21120.00
C19—C18—C23118.62 (13)C22—C21—H21120.00
C19—C18—C5120.26 (12)C21—C22—H22120.00
C23—C18—C5121.10 (13)C23—C22—H22120.00
C20—C19—C18120.64 (14)C18—C23—H23120.00
C21—C20—C19120.20 (16)C22—C23—H23120.00
C20—C21—C22119.68 (15)
N9—C1—N2—C71.13 (13)N2—C1—C10—C15−115.37 (15)
C10—C1—N2—C7−172.48 (12)N9—C1—C10—C11−105.68 (15)
N9—C1—N2—C3−170.93 (13)N2—C1—C10—C1167.00 (17)
C10—C1—N2—C315.5 (2)C15—C10—C11—C120.7 (2)
C7—N2—C3—N48.25 (18)C1—C10—C11—C12178.35 (12)
C1—N2—C3—N4179.34 (13)C10—C11—C12—C130.3 (2)
C7—N2—C3—C17−169.90 (12)C10—C11—C12—C16−179.23 (13)
C1—N2—C3—C171.2 (2)C11—C12—C13—C14−0.8 (2)
N2—C3—N4—C5−0.57 (19)C16—C12—C13—C14178.73 (15)
C17—C3—N4—C5177.53 (12)C12—C13—C14—C150.3 (2)
C3—N4—C5—C6−5.2 (2)C13—C14—C15—C100.7 (2)
C3—N4—C5—C18177.12 (12)C11—C10—C15—C14−1.2 (2)
N4—C5—C6—C73.13 (19)C1—C10—C15—C14−178.84 (13)
C18—C5—C6—C7−179.37 (11)C6—C5—C18—C19−165.26 (14)
C1—N2—C7—N8−1.59 (14)N4—C5—C18—C1912.39 (19)
C3—N2—C7—N8171.93 (11)C6—C5—C18—C2313.4 (2)
C1—N2—C7—C6176.47 (11)N4—C5—C18—C23−168.96 (12)
C3—N2—C7—C6−10.01 (17)C23—C18—C19—C20−1.1 (2)
C5—C6—C7—N8−178.04 (13)C5—C18—C19—C20177.61 (15)
C5—C6—C7—N24.38 (18)C18—C19—C20—C210.7 (3)
N2—C7—N8—N91.43 (14)C19—C20—C21—C220.1 (3)
C6—C7—N8—N9−176.29 (13)C20—C21—C22—C23−0.5 (3)
N2—C1—N9—N8−0.31 (14)C21—C22—C23—C180.1 (2)
C10—C1—N9—N8173.38 (11)C19—C18—C23—C220.7 (2)
C7—N8—N9—C1−0.69 (14)C5—C18—C23—C22−178.02 (13)
N9—C1—C10—C1571.96 (18)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6···N8i0.952.533.4597 (17)166
C23—H23···N8i0.952.613.5374 (19)167
Symmetry codes: (i) −x, −y, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6···N8i0.952.533.4597 (17)166
C23—H23···N8i0.952.613.5374 (19)167
Symmetry codes: (i) −x, −y, −z+1.
references
References top

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