PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 April 1; 64(Pt 4): o684.
Published online 2008 March 7. doi:  10.1107/S1600536808005801
PMCID: PMC2961023

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

Abstract

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 R 2 2(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 [triangle]); Genady & Gabel (2003 [triangle]); Kanazawa et al. (1988 [triangle]); Karanik et al. (2003 [triangle]); Hashimoto et al. (1990 [triangle]); Allouch et al. (2004 [triangle]). For a discussion of hydrogen-bond patterns, see: Bernstein et al. (1995 [triangle]); Etter et al. (1990 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o684-scheme1.jpg

Experimental

Crystal data

  • C9H10N4
  • M r = 174.21
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o684-efi3.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.148
  • S = 0.94
  • 3882 reflections
  • 124 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.17 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

supplementary crystallographic information

Comment

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)

Experimental

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

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).

Figures

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

Crystal data

C9H10N4F000 = 368
Mr = 174.21Dx = 1.222 Mg m3
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 mm1
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

Bruker SMART CCD area-detector diffractometer3882 independent reflections
Radiation source: sealed tube1997 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.047
T = 296(2) Kθmax = 34.4º
[var phi] 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

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 Å3
124 parametersΔρmin = −0.16 e Å3
3 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

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)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DN2319).

References

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

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography