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Acta Cryst. (2008). E64, o684    [ doi:10.1107/S1600536808005801 ]

5-Amino-3-methyl-1-phenyl-1H-1,2,4-triazole

F. Allouch, F. Zouari, F. Chabchoub and M. Salem

Abstract top

In the title compound, C9H10N4, the phenyl and triazole rings make a dihedral angle of 38.80 (2)°. N-H...N hydrogen bonds link the molecules, forming centrosymmetric R22(8) rings; these rings are interconnected through a C(5) chain, building up a zigzag layer parallel to the (100) plane.

Comment top

The aminotriazoles are crucial heterocyclic substances which have a great interest thanks to their biological and pharmacological activity (Kanazawa et al., 1988; Hashimoto et al., 1990) such as antitumoral and inhibition of cholesterol activity. In addition they have many applications in agriculture domain (Altman et al., 1993). Aminotriazole are useful binucleophilic agents that lead to polycondensed heterocycles (Genady et al., 2003; Karanik et al., 2003). However, the studies that deal with N1-phenyl-aminotriazole are very limited (Allouch et al., 2004). Until now only a few reactions were reported concerning the addition-cyclizations of bielectrophile compounds with N1-phenyl-aminotriazoles. In fact, these later are not well identified, this can be explicable by the existence of the tautomer equilibrium. That is why we have undertaken a crystallographic study.

In this paper, we report the synthesis of 5-amino-3-méthyl N1-phényl-1,2,4-triazole. The reaction of N-phenyl ethyl acetydrazonate with cyanamidegave aminotriazole could lead to structure (I) or its isomer (II) (Scheme). The structure elucidation was achieved by X-ray diffraction, and proved that the reaction occurs cleanly to form 5-amino-3-méthyl N1-phényl-1,2,4-triazole (I).

In the title compound, the phenyl and the triazole rings remain planar with mean deviations from planarity of 0.0072 and 0.0049Å respectively. However, the two rings are twisted with respect to each other making a dihedral angle of 38.80 (2)° (Fig. 1).

The occurrence of N—H···N hydrogen bonds links the molecules through inversion centre to form R22(8) ring (Etter et al., 1990; Bernstein et al., 1995) and these rings are interconnected through C(5) chain to build up a like zigzag layer developping along the (1 0 0) plane (Table 1, Fig. 2)

Related literature top

For related literature, see: Altman & Solomost (1993); Genady & Gabel (2003); Kanazawa et al. (1988); Karanik et al. (2003); Hashimoto et al. (1990); Allouch et al. (2004). For a discussion of hydrogen-bond patterns, see: Bernstein et al. (1995); Etter et al. (1990).

Experimental top

A mixture containing 3.56 g (0.02 mol) of N-phenyl ethyl acetydrazonateand 0.88 g (0.021 mol) of cyanamidein 20 ml of methanol was stirred and heated to reflux for 12 h. The solvent was removed under rotary evaporation. The crude product was washed with ether then recrystallized from methanol to give analytically pure crystals.

Refinement top

All H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.96 Å (methyl) and 0.93 Å (aromatic) with Uiso(H) = 1.2Ueq(Phenyl) or Uiso(H) = 1.5Ueq(methyl). The methyl was found to be statistically disordered over two positions. H atoms attached to nitrogen were located in difference Fourier maps and included in the subsequent refinement using soft restraints (N—H= 0.90 (1)Å and H···H= 1.59 (2) Å) with Uiso(H) = 1.2Ueq(N).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Partial packing view showing the formation of the R22(8) ring and C(5) chains through N—H···N hydrogen bonds drawn as dashed lines. H atoms not involved in hydrogen bondings have been omitted for clarity. [Symmetry codes: (i) -x + 1, -y, -z + 2; (ii) x, -y + 1/2, z + 1/2]
[Figure 3] Fig. 3. The tautomeric forms of the title compound.
5-Amino-3-methyl-1-phenyl-1H-1,2,4-triazole top
Crystal data top
C9H10N4F000 = 368
Mr = 174.21Dx = 1.222 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2898 reflections
a = 8.5110 (5) Åθ = 2.5–23.3º
b = 11.2490 (8) ŵ = 0.08 mm−1
c = 10.1048 (7) ÅT = 296 (7) K
β = 101.866 (4)ºPrism, colourless
V = 946.76 (11) Å30.49 × 0.14 × 0.08 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		3882 independent reflections
Radiation source: sealed tube1997 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.047
T = 296(2) Kθmax = 34.4º
φ and ω scansθmin = 3.0º
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		h = −11→13
Tmin = 0.984, Tmax = 0.997k = −17→17
16028 measured reflectionsl = −16→16
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)] = 0.050H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.148  w = 1/[σ2(Fo2) + (0.0699P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.94(Δ/σ)max < 0.001
3882 reflectionsΔρmax = 0.19 e Å−3
124 parametersΔρmin = −0.16 e Å−3
3 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C9H10N4V = 946.76 (11) Å3
Mr = 174.21Z = 4
Monoclinic, P21/cMo Kα
a = 8.5110 (5) ŵ = 0.08 mm−1
b = 11.2490 (8) ÅT = 296 (7) K
c = 10.1048 (7) Å0.49 × 0.14 × 0.08 mm
β = 101.866 (4)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3882 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		1997 reflections with I > 2σ(I)
Tmin = 0.984, Tmax = 0.997Rint = 0.047
16028 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0503 restraints
wR(F2) = 0.148H atoms treated by a mixture of
independent and constrained refinement
S = 0.94Δρmax = 0.19 e Å−3
3882 reflectionsΔρmin = −0.16 e Å−3
124 parameters
Special details top

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*/UeqOcc. (<1)
N10.22326 (10)0.20008 (8)0.83687 (9)0.0445 (2)
N20.28380 (11)0.22738 (9)0.72310 (10)0.0530 (3)
N30.43302 (11)0.08529 (9)0.84645 (9)0.0500 (3)
N40.29094 (12)0.06921 (9)1.02612 (10)0.0528 (3)
H4A0.3772 (12)0.0290 (10)1.0662 (12)0.063*
H4B0.2503 (14)0.1219 (9)1.0797 (11)0.063*
C40.08173 (12)0.25677 (10)0.85950 (12)0.0454 (3)
C30.31616 (12)0.11612 (9)0.90899 (11)0.0424 (3)
C20.40669 (14)0.15538 (11)0.73467 (12)0.0535 (3)
C9−0.03152 (14)0.19287 (12)0.90944 (15)0.0606 (3)
H9−0.01590.11240.92860.073*
C50.05851 (16)0.37569 (12)0.82934 (14)0.0663 (4)
H50.13540.41930.79680.080*
C10.51079 (17)0.15076 (16)0.63304 (15)0.0792 (5)
H1A0.59360.09250.66010.119*0.50
H1B0.55880.22730.62700.119*0.50
H1C0.44710.12950.54640.119*0.50
H1D0.47270.20700.56230.119*0.50
H1E0.50760.07220.59530.119*0.50
H1F0.61920.17000.67600.119*0.50
C7−0.19460 (19)0.36600 (17)0.89769 (18)0.0921 (6)
H7−0.28900.40280.90850.111*
C6−0.0814 (2)0.42885 (14)0.84843 (18)0.0877 (5)
H6−0.09910.50890.82740.105*
C8−0.16821 (16)0.24917 (14)0.93076 (18)0.0797 (5)
H8−0.24280.20720.96790.096*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0431 (4)0.0488 (5)0.0457 (5)0.0065 (4)0.0189 (4)0.0059 (4)
N20.0492 (5)0.0649 (6)0.0499 (6)0.0084 (4)0.0218 (5)0.0126 (5)
N30.0474 (5)0.0574 (6)0.0487 (6)0.0104 (4)0.0181 (4)0.0014 (4)
N40.0584 (6)0.0544 (6)0.0507 (6)0.0157 (5)0.0228 (5)0.0088 (5)
C40.0414 (5)0.0509 (6)0.0457 (6)0.0077 (4)0.0130 (5)0.0019 (5)
C30.0439 (5)0.0418 (6)0.0437 (6)0.0034 (4)0.0140 (5)−0.0003 (5)
C20.0480 (6)0.0669 (7)0.0500 (7)0.0048 (5)0.0200 (5)0.0064 (6)
C90.0476 (6)0.0612 (8)0.0777 (9)0.0036 (5)0.0243 (6)0.0070 (7)
C50.0711 (8)0.0611 (8)0.0754 (10)0.0174 (6)0.0353 (7)0.0164 (7)
C10.0679 (8)0.1133 (12)0.0673 (10)0.0214 (8)0.0392 (7)0.0151 (8)
C70.0709 (9)0.1057 (13)0.1108 (14)0.0396 (9)0.0445 (9)0.0214 (10)
C60.0926 (11)0.0767 (10)0.1056 (13)0.0420 (8)0.0481 (10)0.0290 (9)
C80.0534 (8)0.0923 (11)0.1032 (12)0.0100 (7)0.0385 (8)0.0146 (9)
Geometric parameters (Å, °) top
N1—C31.3459 (14)C5—C61.3811 (18)
N1—N21.3874 (11)C5—H50.9300
N1—C41.4224 (12)C1—H1A0.9600
N2—C21.3090 (14)C1—H1B0.9600
N3—C31.3294 (12)C1—H1C0.9600
N3—C21.3577 (15)C1—H1D0.9600
N4—C31.3528 (14)C1—H1E0.9600
N4—H4A0.886 (8)C1—H1F0.9600
N4—H4B0.917 (8)C7—C81.363 (2)
C4—C51.3773 (17)C7—C61.369 (2)
C4—C91.3785 (15)C7—H70.9300
C2—C11.4888 (15)C6—H60.9300
C9—C81.3799 (17)C8—H80.9300
C9—H90.9300
C3—N1—N2109.09 (7)H1A—C1—H1C109.5
C3—N1—C4130.56 (8)H1B—C1—H1C109.5
N2—N1—C4120.33 (9)C2—C1—H1D109.5
C2—N2—N1102.42 (9)H1A—C1—H1D141.1
C3—N3—C2103.43 (9)H1B—C1—H1D56.3
C3—N4—H4A109.5 (8)H1C—C1—H1D56.3
C3—N4—H4B114.3 (8)C2—C1—H1E109.5
H4A—N4—H4B115.9 (11)H1A—C1—H1E56.3
C5—C4—C9120.55 (10)H1B—C1—H1E141.1
C5—C4—N1119.18 (9)H1C—C1—H1E56.3
C9—C4—N1120.27 (10)H1D—C1—H1E109.5
N3—C3—N1109.84 (9)C2—C1—H1F109.5
N3—C3—N4125.66 (10)H1A—C1—H1F56.3
N1—C3—N4124.49 (9)H1B—C1—H1F56.3
N2—C2—N3115.20 (9)H1C—C1—H1F141.1
N2—C2—C1122.54 (11)H1D—C1—H1F109.5
N3—C2—C1122.26 (11)H1E—C1—H1F109.5
C4—C9—C8119.55 (13)C8—C7—C6119.63 (12)
C4—C9—H9120.2C8—C7—H7120.2
C8—C9—H9120.2C6—C7—H7120.2
C4—C5—C6118.57 (12)C7—C6—C5121.25 (14)
C4—C5—H5120.7C7—C6—H6119.4
C6—C5—H5120.7C5—C6—H6119.4
C2—C1—H1A109.5C7—C8—C9120.39 (13)
C2—C1—H1B109.5C7—C8—H8119.8
H1A—C1—H1B109.5C9—C8—H8119.8
C2—C1—H1C109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···N3i0.886 (8)2.110 (8)2.9923 (13)173.1 (12)
N4—H4B···N2ii0.917 (8)2.210 (10)3.0415 (14)150.4 (10)
Symmetry codes: (i) −x+1, −y, −z+2; (ii) x, −y+1/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···N3i0.886 (8)2.110 (8)2.9923 (13)173.1 (12)
N4—H4B···N2ii0.917 (8)2.210 (10)3.0415 (14)150.4 (10)
Symmetry codes: (i) −x+1, −y, −z+2; (ii) x, −y+1/2, z+1/2.
references
References top

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