A second ortho-rhom-bic polymorph of 3,5-diphenyl-4H-1,2,4-triazol-4-amine.

The present crystal structure is the second ortho-rhom-bic polymorph of the title compound, C(14)H(12)N(4). Whereas the structure in Pnma with Z' = 0.5 is already known [Ikemi et al. (2002 ▶). 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 mol-ecules are linked by N-H⋯N hydrogen bonds.

Related literature

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

Experimental

Crystal data

C14H12N4

M = 236.28

Orthorhombic,

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

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

C14H12N4	F(000) = 992
Mr = 236.28	Dx = 1.309 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1617 reflections
a = 7.5521 (9) Å	θ = 2.9–27.7°
b = 11.2309 (14) Å	µ = 0.08 mm−1
c = 28.278 (3) Å	T = 293 K
V = 2398.4 (5) Å3	Block, colorless
Z = 8	0.30 × 0.28 × 0.25 mm

Bruker SMART CCD diffractometer	2307 independent reflections
Radiation source: fine-focus sealed tube	1613 reflections with I > 2σ(I)
graphite	Rint = 0.029
φ and ω scans	θmax = 26.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −8→8
Tmin = 0.976, Tmax = 0.980	k = −8→13
9495 measured reflections	l = −34→34

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

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.

	x	y	z	Uiso*/Ueq
C1	0.1186 (4)	0.1019 (2)	0.34391 (9)	0.0903 (8)
H1A	0.1495	0.0470	0.3671	0.108*
C2	0.0906 (5)	0.0634 (3)	0.29855 (10)	0.1183 (11)
H2A	0.1035	−0.0168	0.2912	0.142*
C3	0.0438 (5)	0.1425 (5)	0.26392 (13)	0.1355 (13)
H3A	0.0215	0.1166	0.2333	0.163*
C4	0.0307 (6)	0.2600 (4)	0.27534 (14)	0.1452 (16)
H4A	0.0020	0.3147	0.2519	0.174*
C5	0.0585 (5)	0.2991 (3)	0.32027 (12)	0.1164 (11)
H5A	0.0482	0.3799	0.3270	0.140*
C6	0.1018 (3)	0.2208 (2)	0.35588 (9)	0.0750 (7)
C7	0.1304 (3)	0.26686 (18)	0.40343 (9)	0.0672 (6)
C8	0.1462 (2)	0.28566 (15)	0.48031 (9)	0.0646 (6)
C9	0.1367 (2)	0.26276 (16)	0.53087 (8)	0.0623 (6)
C10	0.0670 (3)	0.35010 (19)	0.56046 (10)	0.0766 (7)
H10A	0.0238	0.4206	0.5476	0.092*
C11	0.0618 (3)	0.3326 (2)	0.60841 (11)	0.0893 (8)
H11A	0.0159	0.3914	0.6280	0.107*
C12	0.1239 (3)	0.2287 (2)	0.62747 (10)	0.0901 (8)
H12A	0.1197	0.2171	0.6600	0.108*
C13	0.1924 (3)	0.1416 (2)	0.59877 (10)	0.0839 (7)
H13A	0.2339	0.0711	0.6120	0.101*
C14	0.1998 (3)	0.15788 (18)	0.55063 (9)	0.0694 (6)
H14A	0.2471	0.0988	0.5313	0.083*
N1	0.1804 (3)	0.37701 (15)	0.41296 (9)	0.0858 (7)
N2	0.1900 (3)	0.38864 (15)	0.46152 (9)	0.0816 (6)
N3	0.1098 (2)	0.20701 (13)	0.44473 (6)	0.0597 (5)
N4	0.0340 (2)	0.09288 (13)	0.44985 (6)	0.0639 (5)
H4B	0.1214	0.0327	0.4533	0.077*
H4C	−0.0467	0.0933	0.4756	0.077*

	U11	U22	U33	U12	U13	U23
C1	0.109 (2)	0.0712 (17)	0.0906 (18)	−0.0055 (14)	−0.0115 (14)	0.0118 (13)
C2	0.157 (3)	0.103 (2)	0.095 (2)	−0.014 (2)	−0.0136 (18)	0.0066 (18)
C3	0.147 (3)	0.166 (4)	0.094 (2)	0.000 (3)	−0.009 (2)	0.014 (2)
C4	0.180 (4)	0.142 (4)	0.114 (3)	0.052 (3)	0.017 (2)	0.053 (3)
C5	0.143 (3)	0.094 (2)	0.112 (2)	0.0370 (19)	0.033 (2)	0.0354 (19)
C6	0.0566 (13)	0.0589 (13)	0.1096 (18)	0.0088 (10)	0.0127 (11)	0.0270 (13)
C7	0.0547 (13)	0.0442 (12)	0.1026 (17)	0.0067 (9)	0.0109 (10)	0.0087 (11)
C8	0.0410 (11)	0.0299 (10)	0.1228 (18)	−0.0006 (7)	0.0057 (10)	−0.0089 (10)
C9	0.0407 (11)	0.0405 (10)	0.1057 (16)	−0.0069 (8)	0.0007 (9)	−0.0121 (10)
C10	0.0526 (13)	0.0444 (12)	0.133 (2)	−0.0024 (9)	0.0074 (12)	−0.0186 (12)
C11	0.0712 (16)	0.0771 (18)	0.120 (2)	−0.0073 (13)	0.0126 (14)	−0.0343 (16)
C12	0.0805 (18)	0.0828 (18)	0.1069 (19)	−0.0079 (14)	0.0000 (13)	−0.0208 (15)
C13	0.0754 (16)	0.0659 (15)	0.110 (2)	−0.0029 (12)	−0.0134 (13)	−0.0073 (13)
C14	0.0521 (13)	0.0455 (12)	0.1107 (19)	−0.0004 (9)	−0.0064 (11)	−0.0167 (11)
N1	0.0767 (14)	0.0379 (10)	0.143 (2)	−0.0021 (9)	0.0250 (12)	0.0139 (11)
N2	0.0750 (14)	0.0409 (10)	0.1290 (18)	−0.0081 (8)	0.0187 (11)	−0.0036 (10)
N3	0.0452 (9)	0.0324 (8)	0.1015 (13)	0.0009 (6)	0.0045 (8)	0.0037 (8)
N4	0.0606 (11)	0.0310 (8)	0.1000 (13)	−0.0052 (7)	0.0100 (8)	0.0013 (7)

C1—C2	1.370 (4)	C8—C9	1.454 (3)
C1—C6	1.383 (3)	C9—C14	1.388 (3)
C1—H1A	0.9300	C9—C10	1.393 (3)
C2—C3	1.368 (5)	C10—C11	1.371 (4)
C2—H2A	0.9300	C10—H10A	0.9300
C3—C4	1.362 (5)	C11—C12	1.368 (4)
C3—H3A	0.9300	C11—H11A	0.9300
C4—C5	1.361 (5)	C12—C13	1.373 (3)
C4—H4A	0.9300	C12—H12A	0.9300
C5—C6	1.377 (3)	C13—C14	1.375 (3)
C5—H5A	0.9300	C13—H13A	0.9300
C6—C7	1.457 (3)	C14—H14A	0.9300
C7—N1	1.321 (3)	N1—N2	1.381 (3)
C7—N3	1.356 (3)	N3—N4	1.411 (2)
C8—N2	1.315 (2)	N4—H4B	0.9499
C8—N3	1.367 (3)	N4—H4C	0.9498
C2—C1—C6	121.3 (3)	C14—C9—C8	121.92 (18)
C2—C1—H1A	119.4	C10—C9—C8	119.0 (2)
C6—C1—H1A	119.4	C11—C10—C9	120.3 (2)
C3—C2—C1	120.4 (3)	C11—C10—H10A	119.9
C3—C2—H2A	119.8	C9—C10—H10A	119.9
C1—C2—H2A	119.8	C12—C11—C10	120.1 (2)
C4—C3—C2	118.6 (4)	C12—C11—H11A	119.9
C4—C3—H3A	120.7	C10—C11—H11A	119.9
C2—C3—H3A	120.7	C11—C12—C13	120.3 (3)
C5—C4—C3	121.5 (3)	C11—C12—H12A	119.9
C5—C4—H4A	119.2	C13—C12—H12A	119.9
C3—C4—H4A	119.2	C12—C13—C14	120.4 (2)
C4—C5—C6	120.9 (3)	C12—C13—H13A	119.8
C4—C5—H5A	119.6	C14—C13—H13A	119.8
C6—C5—H5A	119.6	C13—C14—C9	119.8 (2)
C5—C6—C1	117.4 (3)	C13—C14—H14A	120.1
C5—C6—C7	118.9 (3)	C9—C14—H14A	120.1
C1—C6—C7	123.7 (2)	C7—N1—N2	107.83 (19)
N1—C7—N3	108.7 (2)	C8—N2—N1	107.78 (18)
N1—C7—C6	124.3 (2)	C7—N3—C8	106.89 (17)
N3—C7—C6	126.98 (19)	C7—N3—N4	125.81 (18)
N2—C8—N3	108.8 (2)	C8—N3—N4	126.36 (17)
N2—C8—C9	124.41 (19)	N3—N4—H4B	112.0
N3—C8—C9	126.83 (17)	N3—N4—H4C	109.5
C14—C9—C10	119.1 (2)	H4B—N4—H4C	111.8

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···N2i	0.95	2.17	3.117 (2)	177

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4B⋯N2i	0.95	2.17	3.117 (2)	177

Symmetry code: (i) .