7-Dimethyl­amino-2-phenyl-1,2,4-triazolo[1,5-a][1,3,5]triazin-5-amine methanol solvate

Anton V Dolzhenko; Geok Kheng Tan; Lip Lin Koh; Su Fen Woo; Wai Keung Chui

doi:10.1107/S1600536808030481

. 2008 Sep 27;64(Pt 10):o2021. doi: 10.1107/S1600536808030481

7-Dimethylamino-2-phenyl-1,2,4-triazolo[1,5-a][1,3,5]triazin-5-amine methanol solvate¹

Anton V Dolzhenko ^a,^*, Geok Kheng Tan ^b, Lip Lin Koh ^b, Su Fen Woo ^b, Wai Keung Chui ^a

PMCID: PMC2959306 PMID: 21201215

Abstract

7-Dimethylamino-2-phenyl-1,2,4-triazolo[1,5-a][1,3,5]triazin-5-amine crystallized with one molecule of methanol to give the title compound, C₁₂H₁₃N₇·CH₃OH. The triazolo[1,5-a][1,3,5]triazine heterocyclic core is essentially planar as are both amino groups that are involved in π-electron delocalization with the triazolo[1,5-a][1,3,5]triazine nucleus. The methyl groups of the dimethylamino fragment are involved in the formation of weak intramolecular C—H⋯N hydrogen bonds with the N atoms of the heterocyclic system. The crystal packing is stabilized by intermolecular N—H⋯N hydrogen bonds between the triazolo[1,5-a][1,3,5]triazine molecules. The methanol solvent molecule also participates in the formation of the crystal structure via intermolecular O—H⋯N, N—H⋯O and weak C—H⋯O hydrogen bonds, linking the layers of triazolo[1,5-a][1,3,5]triazine molecules.

Related literature

The 1,2,4-triazolo[1,5-a][1,3,5]triazine (5-azapurine) heterocyclic system has been reviewed by Dolzhenko et al. (2006 ▶). For investigations on 5,7-diamino-1,2,4-triazolo[1,5-a][1,3,5]triazines, see Dolzhenko et al. (2007 ▶). For a similar structure, see: Gilardi (1973 ▶). For related literature, see: Dolzhenko et al. (2008 ▶)

Experimental

Crystal data

C₁₂H₁₃N₇·CH₄O
M _r = 287.34
Triclinic,
a = 6.9963 (5) Å
b = 8.0435 (5) Å
c = 13.0942 (9) Å
α = 93.493 (1)°
β = 93.972 (1)°
γ = 102.883 (1)°
V = 714.39 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 223 (2) K
0.74 × 0.68 × 0.40 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.935, T _max = 0.964
9183 measured reflections
3256 independent reflections
2870 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.139
S = 1.07
3256 reflections
205 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030481/fb2109sup1.cif

e-64-o2021-sup1.cif^{(19.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808030481/fb2109Isup2.hkl

e-64-o2021-Isup2.hkl^{(159.7KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1S—H1S⋯N1	0.92 (2)	1.97 (2)	2.8861 (16)	172.8 (18)
N6—H6NB⋯N4ⁱ	0.86 (2)	2.11 (2)	2.9679 (17)	178.8 (18)
N6—H6NA⋯O1Sⁱ	0.89 (2)	2.398 (19)	3.0280 (18)	128.3 (16)
C6—H6C⋯N2	0.97	2.08	2.8753 (18)	138
C6—H6C⋯N3	0.97	2.54	2.9484 (17)	105
C7—H7A⋯N5	0.97	2.22	2.6788 (18)	108
C7—H7C⋯O1Sⁱⁱ	0.97	2.48	3.4438 (19)	176

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work was supported by the Academic Research Fund of the National University of Singapore (WBS R-148-000-069-112) and the National Medical Research Council, Singapore (NMRC/NIG/0019/2008 and NMRC/NIG/0020/2008).

supplementary crystallographic information

Comment

1,2,4-Triazolo[1,5-a][1,3,5]triazine system is known as 5-aza-isostere of the purine core. Compounds based on this skeleton have been shown to possess a wide range of biological activities (Dolzhenko et al., 2006). In continuation of our investigations on 5,7-diamino-1,2,4-triazolo[1,5-a][1,3,5]triazines (Dolzhenko et al., 2007), we report herein the structural study of 7-dimethylamino-2-phenyl-1,2,4-triazolo[1,5-a][1,3,5]triazin-5-amine (Fig. 1).

The fused triazine and triazole rings are located practically in the same plane (the angle between the mean planes of these rings makes 1.66 (4)°). The phenyl ring makes a dihedral angle of 22.70 (5)° with the mean plane of the 1,2,4-triazolo[1,5-a][1,3,5]triazine core. Similarity of the lengths of C3—N4, C3—N5, C3—N6, C4—N3, C4—N5 and C4—N7 makes evidence for π-electron delocalization of the amino groups with the 1,2,4-triazolo[1,5-a][1,3,5]triazine core.

The dimethylamino group (C6—N7—C7) has an out-of-plane twist (4.3 (8)°). The nitrogen atom of dimethylamino group (N7) has a slightly pyramidal stereochemistry [C6-N7-C7 = 115.0 (1)°] and it is located 0.039 (1) Å above the C4/C6/C7 plane. These data are in good agreement with previously reported results on the similar structure of 5,7-bis(dimethylamino)-2-methylthio-1,2,4-triazolo[1,5-a][1,3,5]triazine (Gilardi, 1973).

The methyl groups of dimethylamino fragment are involved in the formation of weak C-H···N intramolecular hydrogen-bonds with the nitrogen atoms of the heterocyclic system (Tab. 1).

7-Dimethylamino-2-phenyl-1,2,4-triazolo[1,5-a][1,3,5]triazin-5-amine crystallizes together with one molecule of methanol (Fig. 1). The methanol molecule participates in the formation of the crystalline structure via intermolecular O-H···N, N-H···O and weak C-H···O hydrogen-bonds linking the layers of the molecules of 7-dimethylamino-2-phenyl-1,2,4-triazolo[1,5-a][1,3,5]triazin-5-amine (Tab. 1, Fig. 2).

Experimental

2-Phenyl-7-trichloromethyl-1,2,4-triazolo[1,5-a][1,3,5]triazin-5-amine (0.66 g, 2.0 mmol) was added to cold (0–5 °C) dimethylamine (5 ml). The mixture was stirred first in ice-bath for 20 min and then for another 60 min at room temperature. Cold water (20 ml) was added and the product was filtered and recrystallized from methanol (m.p. 521 K).