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Acta Crystallogr Sect E Struct Rep Online. 2009 September 1; 65(Pt 9): o2261.
Published online 2009 August 29. doi:  10.1107/S1600536809033807
PMCID: PMC2970008

A second ortho­rhom­bic polymorph of 3,5-diphenyl-4H-1,2,4-triazol-4-amine

Abstract

The present crystal structure is the second ortho­rhom­bic polymorph of the title compound, C14H12N4. Whereas the structure in Pnma with Z′ = 0.5 is already known [Ikemi et al. (2002 [triangle]). Heterocycl. Commun. 8, 439–442], the present structure crystallizes in the space group Pbca with Z′ = 1. The dihedral angle between the two phenyl rings is 23.5 (4)° and the dihedral angles between central ring and the phenyl rings are 41.0 (3) and 26.3 (5)°. In the 4-amino-1,2,4-trizole fragment, the C=N distances are 1.321 (3) and 1.315 (3) Å, which are much shorter than the C—N distances of 1.367 (3) and 1.357 (3) Å. In the crystal, adjacent mol­ecules are linked by N—H(...)N hydrogen bonds.

Related literature

For 4-amino-1,2,4-triazoles derivatives, see: Beckmann & Brooker (2003 [triangle]); Collin et al. (2003 [triangle]). For the other polymorph, see: Ikemi et al. (2002 [triangle]).

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Object name is e-65-o2261-scheme1.jpg

Experimental

Crystal data

  • C14H12N4
  • M r = 236.28
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2261-efi1.jpg
  • a = 7.5521 (9) Å
  • b = 11.2309 (14) Å
  • c = 28.278 (3) Å
  • V = 2398.4 (5) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 293 K
  • 0.30 × 0.28 × 0.25 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2000 [triangle]) T min = 0.976, T max = 0.980
  • 9495 measured reflections
  • 2307 independent reflections
  • 1613 reflections with I > 2σ(I)
  • R int = 0.029

Refinement

  • R[F 2 > 2σ(F 2)] = 0.056
  • wR(F 2) = 0.161
  • S = 1.07
  • 2307 reflections
  • 164 parameters
  • H-atom parameters constrained
  • Δρmax = 0.16 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809033807/bt5044sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033807/bt5044Isup2.hkl

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

Acknowledgments

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

supplementary crystallographic information

Comment

The derivatives of 4-amino-1,2,4-triazoles have been extensively investigated in in medicinal chemistry and agricultural chemistry (Collin et al., 2003). They are a type of multidentate ligands in coordination chemistry (Beckmann et al. 2003). Herein, we report the crystal structure of 3,5-diphenyl-4H-1,2,4-triazol-4-amine.

The title compound, C14H12N4, is a 4-amino-3,5-disubstituted-1,2,4-trizole compound and with a dihedral angle between the two phenyl rings of 23.5 (4) °. In the 4-amino-1,2,4-trizole fragment, the C=N distance is 1.321 (3) and 1.315 (3) Å, which are much shorter than the C—N distances of 1.367 (3) and 1.357 (3) Å. In the crystal, adjacent molecules are linked by N—H···N hydrogen bonds into a one-dimensional chain with N···N distance 3.117 (3) Å. The crystal structure of the title compound is a second orthorhombic polymorph. Whereas the structure in Pnma with Z'=0.5 is already known(Ikemi et al. 2002), the present structure has the space group Pbca with Z'=1.

Experimental

A mixture solution of the benzonitrile (0.103 g, 1.0 mmol), 50% NH2NH2.H2O (3 ml) and ethanol (2 ml) was heated in a 15 ml Teflon-lined autoclave at 100 ° for 3 days, followed by slow cooling (5 ° h-1) to room temperature. The colorless block crystals were collected by filtration washed with water, then dried and collected in 11.9% yield (0.014 g) based on benzonitrile.

Refinement

H atoms bonded to N atoms were located in a difference map with the restraint of N—H = 0.95 Å. Other H atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å and with Uiso(H) = 1.2 Uiso(C).

Figures

Fig. 1.
Structure of the title compound with 30% thermal ellipsoids.
Fig. 2.
The one-dimensional hydrogen bonding network of the title compound.

Crystal data

C14H12N4F(000) = 992
Mr = 236.28Dx = 1.309 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 1617 reflections
a = 7.5521 (9) Åθ = 2.9–27.7°
b = 11.2309 (14) ŵ = 0.08 mm1
c = 28.278 (3) ÅT = 293 K
V = 2398.4 (5) Å3Block, colorless
Z = 80.30 × 0.28 × 0.25 mm

Data collection

Bruker SMART CCD diffractometer2307 independent reflections
Radiation source: fine-focus sealed tube1613 reflections with I > 2σ(I)
graphiteRint = 0.029
[var phi] and ω scansθmax = 26.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)h = −8→8
Tmin = 0.976, Tmax = 0.980k = −8→13
9495 measured reflectionsl = −34→34

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.056H-atom parameters constrained
wR(F2) = 0.161w = 1/[σ2(Fo2) + (0.075P)2 + 0.3879P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
2307 reflectionsΔρmax = 0.16 e Å3
164 parametersΔρmin = −0.18 e Å3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0018 (7)

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*/Ueq
C10.1186 (4)0.1019 (2)0.34391 (9)0.0903 (8)
H1A0.14950.04700.36710.108*
C20.0906 (5)0.0634 (3)0.29855 (10)0.1183 (11)
H2A0.1035−0.01680.29120.142*
C30.0438 (5)0.1425 (5)0.26392 (13)0.1355 (13)
H3A0.02150.11660.23330.163*
C40.0307 (6)0.2600 (4)0.27534 (14)0.1452 (16)
H4A0.00200.31470.25190.174*
C50.0585 (5)0.2991 (3)0.32027 (12)0.1164 (11)
H5A0.04820.37990.32700.140*
C60.1018 (3)0.2208 (2)0.35588 (9)0.0750 (7)
C70.1304 (3)0.26686 (18)0.40343 (9)0.0672 (6)
C80.1462 (2)0.28566 (15)0.48031 (9)0.0646 (6)
C90.1367 (2)0.26276 (16)0.53087 (8)0.0623 (6)
C100.0670 (3)0.35010 (19)0.56046 (10)0.0766 (7)
H10A0.02380.42060.54760.092*
C110.0618 (3)0.3326 (2)0.60841 (11)0.0893 (8)
H11A0.01590.39140.62800.107*
C120.1239 (3)0.2287 (2)0.62747 (10)0.0901 (8)
H12A0.11970.21710.66000.108*
C130.1924 (3)0.1416 (2)0.59877 (10)0.0839 (7)
H13A0.23390.07110.61200.101*
C140.1998 (3)0.15788 (18)0.55063 (9)0.0694 (6)
H14A0.24710.09880.53130.083*
N10.1804 (3)0.37701 (15)0.41296 (9)0.0858 (7)
N20.1900 (3)0.38864 (15)0.46152 (9)0.0816 (6)
N30.1098 (2)0.20701 (13)0.44473 (6)0.0597 (5)
N40.0340 (2)0.09288 (13)0.44985 (6)0.0639 (5)
H4B0.12140.03270.45330.077*
H4C−0.04670.09330.47560.077*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.109 (2)0.0712 (17)0.0906 (18)−0.0055 (14)−0.0115 (14)0.0118 (13)
C20.157 (3)0.103 (2)0.095 (2)−0.014 (2)−0.0136 (18)0.0066 (18)
C30.147 (3)0.166 (4)0.094 (2)0.000 (3)−0.009 (2)0.014 (2)
C40.180 (4)0.142 (4)0.114 (3)0.052 (3)0.017 (2)0.053 (3)
C50.143 (3)0.094 (2)0.112 (2)0.0370 (19)0.033 (2)0.0354 (19)
C60.0566 (13)0.0589 (13)0.1096 (18)0.0088 (10)0.0127 (11)0.0270 (13)
C70.0547 (13)0.0442 (12)0.1026 (17)0.0067 (9)0.0109 (10)0.0087 (11)
C80.0410 (11)0.0299 (10)0.1228 (18)−0.0006 (7)0.0057 (10)−0.0089 (10)
C90.0407 (11)0.0405 (10)0.1057 (16)−0.0069 (8)0.0007 (9)−0.0121 (10)
C100.0526 (13)0.0444 (12)0.133 (2)−0.0024 (9)0.0074 (12)−0.0186 (12)
C110.0712 (16)0.0771 (18)0.120 (2)−0.0073 (13)0.0126 (14)−0.0343 (16)
C120.0805 (18)0.0828 (18)0.1069 (19)−0.0079 (14)0.0000 (13)−0.0208 (15)
C130.0754 (16)0.0659 (15)0.110 (2)−0.0029 (12)−0.0134 (13)−0.0073 (13)
C140.0521 (13)0.0455 (12)0.1107 (19)−0.0004 (9)−0.0064 (11)−0.0167 (11)
N10.0767 (14)0.0379 (10)0.143 (2)−0.0021 (9)0.0250 (12)0.0139 (11)
N20.0750 (14)0.0409 (10)0.1290 (18)−0.0081 (8)0.0187 (11)−0.0036 (10)
N30.0452 (9)0.0324 (8)0.1015 (13)0.0009 (6)0.0045 (8)0.0037 (8)
N40.0606 (11)0.0310 (8)0.1000 (13)−0.0052 (7)0.0100 (8)0.0013 (7)

Geometric parameters (Å, °)

C1—C21.370 (4)C8—C91.454 (3)
C1—C61.383 (3)C9—C141.388 (3)
C1—H1A0.9300C9—C101.393 (3)
C2—C31.368 (5)C10—C111.371 (4)
C2—H2A0.9300C10—H10A0.9300
C3—C41.362 (5)C11—C121.368 (4)
C3—H3A0.9300C11—H11A0.9300
C4—C51.361 (5)C12—C131.373 (3)
C4—H4A0.9300C12—H12A0.9300
C5—C61.377 (3)C13—C141.375 (3)
C5—H5A0.9300C13—H13A0.9300
C6—C71.457 (3)C14—H14A0.9300
C7—N11.321 (3)N1—N21.381 (3)
C7—N31.356 (3)N3—N41.411 (2)
C8—N21.315 (2)N4—H4B0.9499
C8—N31.367 (3)N4—H4C0.9498
C2—C1—C6121.3 (3)C14—C9—C8121.92 (18)
C2—C1—H1A119.4C10—C9—C8119.0 (2)
C6—C1—H1A119.4C11—C10—C9120.3 (2)
C3—C2—C1120.4 (3)C11—C10—H10A119.9
C3—C2—H2A119.8C9—C10—H10A119.9
C1—C2—H2A119.8C12—C11—C10120.1 (2)
C4—C3—C2118.6 (4)C12—C11—H11A119.9
C4—C3—H3A120.7C10—C11—H11A119.9
C2—C3—H3A120.7C11—C12—C13120.3 (3)
C5—C4—C3121.5 (3)C11—C12—H12A119.9
C5—C4—H4A119.2C13—C12—H12A119.9
C3—C4—H4A119.2C12—C13—C14120.4 (2)
C4—C5—C6120.9 (3)C12—C13—H13A119.8
C4—C5—H5A119.6C14—C13—H13A119.8
C6—C5—H5A119.6C13—C14—C9119.8 (2)
C5—C6—C1117.4 (3)C13—C14—H14A120.1
C5—C6—C7118.9 (3)C9—C14—H14A120.1
C1—C6—C7123.7 (2)C7—N1—N2107.83 (19)
N1—C7—N3108.7 (2)C8—N2—N1107.78 (18)
N1—C7—C6124.3 (2)C7—N3—C8106.89 (17)
N3—C7—C6126.98 (19)C7—N3—N4125.81 (18)
N2—C8—N3108.8 (2)C8—N3—N4126.36 (17)
N2—C8—C9124.41 (19)N3—N4—H4B112.0
N3—C8—C9126.83 (17)N3—N4—H4C109.5
C14—C9—C10119.1 (2)H4B—N4—H4C111.8

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N4—H4B···N2i0.952.173.117 (2)177

Symmetry codes: (i) −x+1/2, y−1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT5044).

References

  • Beckmann, U. & Brooker, S. (2003). Coord. Chem. Rev.245, 17–29.
  • Bruker (2000). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Collin, X., Sauleau, A. & Coulon, J. (2003). Bioorg. Med. Chem. Lett.13, 2601–2605. [PubMed]
  • Ikemi, Y., Hayashi, N., Kakehi, A. & Matsumoto, K. (2002). Heterocycl. Commun.8, 439–442.
  • Sheldrick, G. M. (2000). SADABS University of Göttingen Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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