5-Methyl-3-(3-methyl-phen-yl)-7-phenyl-1,2,4-triazolo[4,3-c]pyrimidine.

The title compound, C(19)H(16)N(4), 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 π-π stacking inter-actions [centroid-centroid distance = 3.7045 (8) Å] stabilize the crystal packing.

Related literature

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

Crystal data

C19H16N4

M = 300.36

Triclinic,

a = 6.4270 (4) Å

b = 11.1706 (6) Å

c = 11.3672 (7) Å

α = 79.963 (5)°

β = 74.894 (5)°

γ = 81.877 (5)°

V = 771.88 (8) Å3

Z = 2

Cu Kα radiation

μ = 0.63 mm−1

T = 193 K

0.45 × 0.40 × 0.25 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

3207 measured reflections

2924 independent reflections

2573 reflections with I > 2σ(I)

R int = 0.088

3 standard reflections every 60 min intensity decay: 2%

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.119

S = 1.03

2924 reflections

211 parameters

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.21 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811010683/bt5497sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811010683/bt5497Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C19H16N4	Z = 2
Mr = 300.36	F(000) = 316
Triclinic, P1	Dx = 1.292 Mg m−3
Hall symbol: -P 1	Melting point: 412 K
a = 6.4270 (4) Å	Cu Kα radiation, λ = 1.54178 Å
b = 11.1706 (6) Å	Cell parameters from 25 reflections
c = 11.3672 (7) Å	θ = 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) Å3	0.45 × 0.40 × 0.25 mm

Enraf–Nonius CAD-4 diffractometer	Rint = 0.088
Radiation source: rotating anode	θmax = 69.9°, θmin = 4.0°
graphite	h = −7→0
ω/2θ scans	k = −13→13
3207 measured reflections	l = −13→13
2924 independent reflections	3 standard reflections every 60 min
2573 reflections with I > 2σ(I)	intensity decay: 2%

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042	H-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 reflections	Δρmax = 0.25 e Å−3
211 parameters	Δρmin = −0.21 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0261 (19)

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.

	x	y	z	Uiso*/Ueq
C1	0.4291 (2)	0.07105 (12)	0.69733 (11)	0.0279 (3)
N2	0.35695 (17)	0.15861 (10)	0.60994 (9)	0.0269 (3)
C3	0.3949 (2)	0.27979 (12)	0.56152 (12)	0.0295 (3)
N4	0.30230 (19)	0.33877 (10)	0.47760 (10)	0.0322 (3)
C5	0.1646 (2)	0.28265 (12)	0.43301 (12)	0.0291 (3)
C6	0.1357 (2)	0.16223 (12)	0.46841 (12)	0.0300 (3)
H6	0.0468	0.1239	0.4343	0.036*
C7	0.2419 (2)	0.09577 (12)	0.55754 (12)	0.0275 (3)
N8	0.24802 (18)	−0.02029 (10)	0.60599 (10)	0.0317 (3)
N9	0.36567 (18)	−0.03428 (10)	0.69480 (10)	0.0318 (3)
C10	0.5391 (2)	0.09494 (12)	0.78900 (12)	0.0284 (3)
C11	0.4254 (2)	0.16174 (12)	0.88241 (12)	0.0315 (3)
H11	0.2792	0.1931	0.8849	0.038*
C12	0.5209 (2)	0.18358 (12)	0.97209 (12)	0.0334 (3)
C13	0.7358 (2)	0.13693 (13)	0.96559 (13)	0.0371 (3)
H13	0.8051	0.1516	1.0252	0.045*
C14	0.8494 (2)	0.06977 (15)	0.87386 (14)	0.0404 (4)
H14	0.9956	0.0384	0.8713	0.049*
C15	0.7522 (2)	0.04762 (14)	0.78542 (13)	0.0355 (3)
H15	0.8305	0.0006	0.7230	0.043*
C16	0.3970 (3)	0.25436 (16)	1.07371 (15)	0.0502 (4)
H16A	0.4322	0.3392	1.0529	0.075*
H16B	0.4366	0.2176	1.1507	0.075*
H16C	0.2413	0.2525	1.0838	0.075*
C17	0.5494 (3)	0.33769 (13)	0.60606 (13)	0.0379 (3)
H17A	0.5796	0.4161	0.5543	0.057*
H17B	0.6845	0.2838	0.6018	0.057*
H17C	0.4855	0.3513	0.6915	0.057*
C18	0.0596 (2)	0.36189 (12)	0.34111 (12)	0.0316 (3)
C19	0.1311 (3)	0.47490 (14)	0.28749 (15)	0.0450 (4)
H19	0.2440	0.5028	0.3121	0.054*
C20	0.0393 (3)	0.54751 (16)	0.19826 (17)	0.0555 (5)
H20	0.0908	0.6243	0.1615	0.067*
C21	−0.1258 (3)	0.50869 (16)	0.16287 (16)	0.0522 (4)
H21	−0.1885	0.5584	0.1017	0.063*
C22	−0.2000 (3)	0.39726 (16)	0.21656 (16)	0.0476 (4)
H22	−0.3149	0.3707	0.1926	0.057*
C23	−0.1088 (2)	0.32384 (14)	0.30495 (14)	0.0383 (3)
H23	−0.1610	0.2472	0.3412	0.046*

	U11	U22	U33	U12	U13	U23
C1	0.0275 (6)	0.0296 (6)	0.0261 (6)	−0.0006 (5)	−0.0059 (5)	−0.0052 (5)
N2	0.0276 (5)	0.0283 (6)	0.0264 (5)	−0.0024 (4)	−0.0077 (4)	−0.0067 (4)
C3	0.0327 (7)	0.0293 (7)	0.0279 (6)	−0.0057 (5)	−0.0075 (5)	−0.0054 (5)
N4	0.0381 (6)	0.0315 (6)	0.0301 (6)	−0.0064 (5)	−0.0125 (5)	−0.0040 (5)
C5	0.0292 (6)	0.0320 (7)	0.0275 (6)	−0.0024 (5)	−0.0072 (5)	−0.0084 (5)
C6	0.0306 (7)	0.0320 (7)	0.0307 (7)	−0.0019 (5)	−0.0106 (5)	−0.0096 (5)
C7	0.0264 (6)	0.0292 (6)	0.0290 (6)	−0.0031 (5)	−0.0064 (5)	−0.0099 (5)
N8	0.0349 (6)	0.0293 (6)	0.0344 (6)	−0.0021 (4)	−0.0137 (5)	−0.0067 (5)
N9	0.0337 (6)	0.0311 (6)	0.0329 (6)	−0.0014 (4)	−0.0121 (5)	−0.0059 (5)
C10	0.0305 (7)	0.0288 (7)	0.0265 (6)	−0.0035 (5)	−0.0088 (5)	−0.0022 (5)
C11	0.0319 (7)	0.0317 (7)	0.0317 (7)	0.0031 (5)	−0.0124 (5)	−0.0046 (5)
C12	0.0431 (8)	0.0293 (7)	0.0297 (7)	0.0017 (6)	−0.0144 (6)	−0.0046 (5)
C13	0.0426 (8)	0.0393 (8)	0.0344 (7)	−0.0020 (6)	−0.0209 (6)	−0.0029 (6)
C14	0.0307 (7)	0.0510 (9)	0.0410 (8)	0.0011 (6)	−0.0143 (6)	−0.0061 (7)
C15	0.0311 (7)	0.0423 (8)	0.0320 (7)	0.0010 (6)	−0.0062 (5)	−0.0088 (6)
C16	0.0641 (11)	0.0504 (9)	0.0417 (9)	0.0153 (8)	−0.0249 (8)	−0.0206 (7)
C17	0.0474 (8)	0.0352 (7)	0.0368 (7)	−0.0144 (6)	−0.0187 (6)	0.0008 (6)
C18	0.0355 (7)	0.0321 (7)	0.0285 (7)	0.0013 (5)	−0.0104 (5)	−0.0081 (5)
C19	0.0572 (10)	0.0350 (8)	0.0494 (9)	−0.0071 (7)	−0.0261 (8)	−0.0021 (7)
C20	0.0750 (12)	0.0369 (9)	0.0590 (11)	−0.0055 (8)	−0.0320 (9)	0.0051 (8)
C21	0.0667 (11)	0.0456 (9)	0.0472 (9)	0.0101 (8)	−0.0299 (8)	−0.0028 (7)
C22	0.0493 (9)	0.0526 (10)	0.0486 (9)	0.0026 (7)	−0.0275 (7)	−0.0101 (7)
C23	0.0395 (8)	0.0395 (8)	0.0395 (8)	−0.0025 (6)	−0.0162 (6)	−0.0065 (6)

C1—N9	1.3057 (17)	C18—C23	1.3939 (19)
C1—N2	1.3899 (16)	C19—C20	1.387 (2)
C1—C10	1.4802 (17)	C20—C21	1.375 (2)
N2—C7	1.3846 (15)	C21—C22	1.379 (3)
N2—C3	1.3995 (17)	C22—C23	1.382 (2)
C3—N4	1.2901 (17)	C6—H6	0.9500
C3—C17	1.4890 (18)	C11—H11	0.9500
N4—C5	1.3909 (16)	C13—H13	0.9500
C5—C6	1.3598 (19)	C14—H14	0.9500
C5—C18	1.4854 (18)	C15—H15	0.9500
C6—C7	1.4136 (18)	C16—H16A	0.9800
C7—N8	1.3167 (17)	C16—H16B	0.9800
N8—N9	1.3873 (15)	C16—H16C	0.9800
C10—C15	1.3896 (19)	C17—H17A	0.9800
C10—C11	1.3914 (18)	C17—H17B	0.9800
C11—C12	1.3894 (18)	C17—H17C	0.9800
C12—C13	1.393 (2)	C19—H19	0.9500
C12—C16	1.502 (2)	C20—H20	0.9500
C13—C14	1.380 (2)	C21—H21	0.9500
C14—C15	1.385 (2)	C22—H22	0.9500
C18—C19	1.388 (2)	C23—H23	0.9500
N9—C1—N2	109.46 (11)	C21—C22—C23	120.60 (15)
N9—C1—C10	124.55 (12)	C22—C23—C18	120.25 (14)
N2—C1—C10	125.66 (11)	C5—C6—H6	121.00
C7—N2—C1	104.30 (10)	C7—C6—H6	121.00
C7—N2—C3	120.16 (11)	C10—C11—H11	119.00
C1—N2—C3	135.10 (11)	C12—C11—H11	119.00
N4—C3—N2	120.52 (12)	C12—C13—H13	119.00
N4—C3—C17	120.83 (12)	C14—C13—H13	120.00
N2—C3—C17	118.63 (11)	C13—C14—H14	120.00
C3—N4—C5	120.57 (12)	C15—C14—H14	120.00
C6—C5—N4	121.74 (12)	C10—C15—H15	120.00
C6—C5—C18	122.78 (12)	C14—C15—H15	120.00
N4—C5—C18	115.43 (11)	C12—C16—H16A	109.00
C5—C6—C7	117.99 (12)	C12—C16—H16B	109.00
N8—C7—N2	110.52 (11)	C12—C16—H16C	109.00
N8—C7—C6	131.23 (12)	H16A—C16—H16B	109.00
N2—C7—C6	118.22 (12)	H16A—C16—H16C	109.00
C7—N8—N9	106.71 (10)	H16B—C16—H16C	109.00
C1—N9—N8	108.99 (11)	C3—C17—H17A	109.00
C15—C10—C11	119.64 (12)	C3—C17—H17B	109.00
C15—C10—C1	120.71 (12)	C3—C17—H17C	109.00
C11—C10—C1	119.62 (11)	H17A—C17—H17B	110.00
C12—C11—C10	121.45 (12)	H17A—C17—H17C	109.00
C11—C12—C13	117.93 (13)	H17B—C17—H17C	109.00
C11—C12—C16	121.36 (13)	C18—C19—H19	120.00
C13—C12—C16	120.71 (13)	C20—C19—H19	120.00
C14—C13—C12	121.05 (13)	C19—C20—H20	120.00
C13—C14—C15	120.59 (13)	C21—C20—H20	120.00
C14—C15—C10	119.32 (13)	C20—C21—H21	120.00
C19—C18—C23	118.62 (13)	C22—C21—H21	120.00
C19—C18—C5	120.26 (12)	C21—C22—H22	120.00
C23—C18—C5	121.10 (13)	C23—C22—H22	120.00
C20—C19—C18	120.64 (14)	C18—C23—H23	120.00
C21—C20—C19	120.20 (16)	C22—C23—H23	120.00
C20—C21—C22	119.68 (15)
N9—C1—N2—C7	1.13 (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—C11	67.00 (17)
C10—C1—N2—C3	15.5 (2)	C15—C10—C11—C12	0.7 (2)
C7—N2—C3—N4	8.25 (18)	C1—C10—C11—C12	178.35 (12)
C1—N2—C3—N4	179.34 (13)	C10—C11—C12—C13	0.3 (2)
C7—N2—C3—C17	−169.90 (12)	C10—C11—C12—C16	−179.23 (13)
C1—N2—C3—C17	1.2 (2)	C11—C12—C13—C14	−0.8 (2)
N2—C3—N4—C5	−0.57 (19)	C16—C12—C13—C14	178.73 (15)
C17—C3—N4—C5	177.53 (12)	C12—C13—C14—C15	0.3 (2)
C3—N4—C5—C6	−5.2 (2)	C13—C14—C15—C10	0.7 (2)
C3—N4—C5—C18	177.12 (12)	C11—C10—C15—C14	−1.2 (2)
N4—C5—C6—C7	3.13 (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—C19	12.39 (19)
C3—N2—C7—N8	171.93 (11)	C6—C5—C18—C23	13.4 (2)
C1—N2—C7—C6	176.47 (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—C20	177.61 (15)
C5—C6—C7—N2	4.38 (18)	C18—C19—C20—C21	0.7 (3)
N2—C7—N8—N9	1.43 (14)	C19—C20—C21—C22	0.1 (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—C18	0.1 (2)
C10—C1—N9—N8	173.38 (11)	C19—C18—C23—C22	0.7 (2)
C7—N8—N9—C1	−0.69 (14)	C5—C18—C23—C22	−178.02 (13)
N9—C1—C10—C15	71.96 (18)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N8i	0.95	2.53	3.4597 (17)	166
C23—H23···N8i	0.95	2.61	3.5374 (19)	167

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯N8i	0.95	2.53	3.4597 (17)	166
C23—H23⋯N8i	0.95	2.61	3.5374 (19)	167

Symmetry code: (i) .