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

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

doi:10.1107/S1600536808005801

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o684

doi:10.1107/S1600536808005801

Open

access

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

Fatma Allouch,^a Fatma Zouari,^b ^* Fakher Chabchoub ^a and Mansour Salem ^a

^aLaboratoire de Chimie Appliquée: Hétérocycles, Corps gras et Polymères, Faculté des Sciences de Sfax, BP 802, 3018 Sfax, Tunisia, and ^bLaboratoire de Sciences de Matériaux et d'Environnement, Faculté des Sciences de SFAX, BP 802, 3018 SFAX, Tunisia
^*Correspondence e-mail: fatmazouari2003@yahoo.fr

(Received 16 February 2008; accepted 1 March 2008; online 7 March 2008)

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.

Related literature

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

Crystal data

C₉H₁₀N₄
M_r = 174.21
Monoclinic, P 2₁ /c
a = 8.5110 (5) Å
b = 11.2490 (8) Å
c = 10.1048 (7) Å
β = 101.866 (4)°
V = 946.76 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 (7) K
0.49 × 0.14 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.984, T_max = 0.997
16028 measured reflections
3882 independent reflections
1997 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.148
S = 0.94
3882 reflections
124 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯N3ⁱ	0.886 (8)	2.110 (8)	2.9923 (13)	173.1 (12)
N4—H4B⋯N2ⁱⁱ	0.917 (8)	2.210 (10)	3.0415 (14)	150.4 (10)
Symmetry codes: (i) -x+1, -y, -z+2; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808005801/dn2319sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808005801/dn2319Isup2.hkl

checkCIF report

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.

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

	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.
	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]
	Fig. 3. The tautomeric forms of the title compound.

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

Crystal data top

C₉H₁₀N₄	F(000) = 368
M_r = 174.21	D_x = 1.222 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2898 reflections
a = 8.5110 (5) Å	θ = 2.5–23.3°
b = 11.2490 (8) Å	µ = 0.08 mm⁻¹
c = 10.1048 (7) Å	T = 296 K
β = 101.866 (4)°	Prism, colourless
V = 946.76 (11) Å³	0.49 × 0.14 × 0.08 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3882 independent reflections
Radiation source: sealed tube	1997 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ϕ and ω scans	θ_max = 34.4°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −11→13
T_min = 0.984, T_max = 0.997	k = −17→17
16028 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	w = 1/[σ²(F_o²) + (0.0699P)²] where P = (F_o² + 2F_c²)/3
3882 reflections	(Δ/σ)_max < 0.001
124 parameters	Δρ_max = 0.19 e Å⁻³
3 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₉H₁₀N₄	V = 946.76 (11) Å³
M_r = 174.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.5110 (5) Å	µ = 0.08 mm⁻¹
b = 11.2490 (8) Å	T = 296 K
c = 10.1048 (7) Å	0.49 × 0.14 × 0.08 mm
β = 101.866 (4)°

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)
T_min = 0.984, T_max = 0.997	R_int = 0.047
16028 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	3 restraints
wR(F²) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	Δρ_max = 0.19 e Å⁻³
3882 reflections	Δρ_min = −0.17 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

	x	y	z	U_iso*/U_eq	Occ. (<1)
N1	0.22326 (10)	0.20008 (8)	0.83687 (9)	0.0445 (2)
N2	0.28380 (11)	0.22738 (9)	0.72310 (10)	0.0530 (3)
N3	0.43302 (11)	0.08529 (9)	0.84645 (9)	0.0500 (3)
N4	0.29094 (12)	0.06921 (9)	1.02612 (10)	0.0528 (3)
H4A	0.3772 (12)	0.0290 (10)	1.0662 (12)	0.063*
H4B	0.2503 (14)	0.1219 (9)	1.0797 (11)	0.063*
C4	0.08173 (12)	0.25677 (10)	0.85950 (12)	0.0454 (3)
C3	0.31616 (12)	0.11612 (9)	0.90899 (11)	0.0424 (3)
C2	0.40669 (14)	0.15538 (11)	0.73467 (12)	0.0535 (3)
C9	−0.03152 (14)	0.19287 (12)	0.90944 (15)	0.0606 (3)
H9	−0.0159	0.1124	0.9286	0.073*
C5	0.05851 (16)	0.37569 (12)	0.82934 (14)	0.0663 (4)
H5	0.1354	0.4193	0.7968	0.080*
C1	0.51079 (17)	0.15076 (16)	0.63304 (15)	0.0792 (5)
H1A	0.5936	0.0925	0.6601	0.119*	0.50
H1B	0.5588	0.2273	0.6270	0.119*	0.50
H1C	0.4471	0.1295	0.5464	0.119*	0.50
H1D	0.4727	0.2070	0.5623	0.119*	0.50
H1E	0.5076	0.0722	0.5953	0.119*	0.50
H1F	0.6192	0.1700	0.6760	0.119*	0.50
C7	−0.19460 (19)	0.36600 (17)	0.89769 (18)	0.0921 (6)
H7	−0.2890	0.4028	0.9085	0.111*
C6	−0.0814 (2)	0.42885 (14)	0.84843 (18)	0.0877 (5)
H6	−0.0991	0.5089	0.8274	0.105*
C8	−0.16821 (16)	0.24917 (14)	0.93076 (18)	0.0797 (5)
H8	−0.2428	0.2072	0.9679	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0431 (4)	0.0488 (5)	0.0457 (5)	0.0065 (4)	0.0189 (4)	0.0059 (4)
N2	0.0492 (5)	0.0649 (6)	0.0499 (6)	0.0084 (4)	0.0218 (5)	0.0126 (5)
N3	0.0474 (5)	0.0574 (6)	0.0487 (6)	0.0104 (4)	0.0181 (4)	0.0014 (4)
N4	0.0584 (6)	0.0544 (6)	0.0507 (6)	0.0157 (5)	0.0228 (5)	0.0088 (5)
C4	0.0414 (5)	0.0509 (6)	0.0457 (6)	0.0077 (4)	0.0130 (5)	0.0019 (5)
C3	0.0439 (5)	0.0418 (6)	0.0437 (6)	0.0034 (4)	0.0140 (5)	−0.0003 (5)
C2	0.0480 (6)	0.0669 (7)	0.0500 (7)	0.0048 (5)	0.0200 (5)	0.0064 (6)
C9	0.0476 (6)	0.0612 (8)	0.0777 (9)	0.0036 (5)	0.0243 (6)	0.0070 (7)
C5	0.0711 (8)	0.0611 (8)	0.0754 (10)	0.0174 (6)	0.0353 (7)	0.0164 (7)
C1	0.0679 (8)	0.1133 (12)	0.0673 (10)	0.0214 (8)	0.0392 (7)	0.0151 (8)
C7	0.0709 (9)	0.1057 (13)	0.1108 (14)	0.0396 (9)	0.0445 (9)	0.0214 (10)
C6	0.0926 (11)	0.0767 (10)	0.1056 (13)	0.0420 (8)	0.0481 (10)	0.0290 (9)
C8	0.0534 (8)	0.0923 (11)	0.1032 (12)	0.0100 (7)	0.0385 (8)	0.0146 (9)

Geometric parameters (Å, º) top

N1—C3	1.3459 (14)	C5—C6	1.3811 (18)
N1—N2	1.3874 (11)	C5—H5	0.9300
N1—C4	1.4224 (12)	C1—H1A	0.9600
N2—C2	1.3090 (14)	C1—H1B	0.9600
N3—C3	1.3294 (12)	C1—H1C	0.9600
N3—C2	1.3577 (15)	C1—H1D	0.9600
N4—C3	1.3528 (14)	C1—H1E	0.9600
N4—H4A	0.886 (8)	C1—H1F	0.9600
N4—H4B	0.917 (8)	C7—C8	1.363 (2)
C4—C5	1.3773 (17)	C7—C6	1.369 (2)
C4—C9	1.3785 (15)	C7—H7	0.9300
C2—C1	1.4888 (15)	C6—H6	0.9300
C9—C8	1.3799 (17)	C8—H8	0.9300
C9—H9	0.9300

C3—N1—N2	109.09 (7)	H1A—C1—H1C	109.5
C3—N1—C4	130.56 (8)	H1B—C1—H1C	109.5
N2—N1—C4	120.33 (9)	C2—C1—H1D	109.5
C2—N2—N1	102.42 (9)	H1A—C1—H1D	141.1
C3—N3—C2	103.43 (9)	H1B—C1—H1D	56.3
C3—N4—H4A	109.5 (8)	H1C—C1—H1D	56.3
C3—N4—H4B	114.3 (8)	C2—C1—H1E	109.5
H4A—N4—H4B	115.9 (11)	H1A—C1—H1E	56.3
C5—C4—C9	120.55 (10)	H1B—C1—H1E	141.1
C5—C4—N1	119.18 (9)	H1C—C1—H1E	56.3
C9—C4—N1	120.27 (10)	H1D—C1—H1E	109.5
N3—C3—N1	109.84 (9)	C2—C1—H1F	109.5
N3—C3—N4	125.66 (10)	H1A—C1—H1F	56.3
N1—C3—N4	124.49 (9)	H1B—C1—H1F	56.3
N2—C2—N3	115.20 (9)	H1C—C1—H1F	141.1
N2—C2—C1	122.54 (11)	H1D—C1—H1F	109.5
N3—C2—C1	122.26 (11)	H1E—C1—H1F	109.5
C4—C9—C8	119.55 (13)	C8—C7—C6	119.63 (12)
C4—C9—H9	120.2	C8—C7—H7	120.2
C8—C9—H9	120.2	C6—C7—H7	120.2
C4—C5—C6	118.57 (12)	C7—C6—C5	121.25 (14)
C4—C5—H5	120.7	C7—C6—H6	119.4
C6—C5—H5	120.7	C5—C6—H6	119.4
C2—C1—H1A	109.5	C7—C8—C9	120.39 (13)
C2—C1—H1B	109.5	C7—C8—H8	119.8
H1A—C1—H1B	109.5	C9—C8—H8	119.8
C2—C1—H1C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N3ⁱ	0.89 (1)	2.11 (1)	2.9923 (13)	173 (1)
N4—H4B···N2ⁱⁱ	0.92 (1)	2.21 (1)	3.0415 (14)	150 (1)

Symmetry codes: (i) −x+1, −y, −z+2; (ii) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₁₀N₄
M_r	174.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.5110 (5), 11.2490 (8), 10.1048 (7)
β (°)	101.866 (4)
V (Å³)	946.76 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.49 × 0.14 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.984, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	16028, 3882, 1997
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.794

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.148, 0.94
No. of reflections	3882
No. of parameters	124
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.17

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N3ⁱ	0.886 (8)	2.110 (8)	2.9923 (13)	173.1 (12)
N4—H4B···N2ⁱⁱ	0.917 (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

Allouch, F., Chabchoub, F., Ben Hassine, B. & Salem, M. (2004). Heterocycl. Commun. 10, 63–66 . Google Scholar
Altman, A. & Solomost, T. (1993). Hortic. Sci. 28, 201–203. CAS Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA. Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Genady, A. & Gabel, D. (2003). Tetrahedron Lett. 44, 2915–2917. Web of Science CrossRef CAS Google Scholar
Hashimoto, F., Sugimoto, C. & Hayashi, H. (1990). Chem. Pharm. Bull. 38, 2532–2536. CrossRef CAS PubMed Web of Science Google Scholar
Kanazawa, S., Driscoll, M. & Struhl, K. (1988). Mol. Cell. Biol. 8, 644–673. Google Scholar
Karanik, M., Paetzel, M. & Liebscher, J. (2003). Synthesis, 8, 1201–1208. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o684

doi:10.1107/S1600536808005801

Open

access