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

Zhang, Y.-W.; Wang, J.-Q.; Cheng, L.

doi:10.1107/S1600536809033807

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2261

doi:10.1107/S1600536809033807

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

Ya-Wen Zhang,^a Jian-Quan Wang ^a and Lin Cheng ^b ^*

^aDepartment of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 211189, People's Republic of China, and ^bDepartment of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: cep02chl@yahoo.com.cn

(Received 21 August 2009; accepted 24 August 2009; online 29 August 2009)

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 ). 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 ); Collin et al. (2003 ). For the other polymorph, see: Ikemi et al. (2002).

Experimental

Crystal data

C₁₄H₁₂N₄
M_r = 236.28
Orthorhombic, P b c a
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[F² > 2σ(F²)] = 0.056
wR(F²) = 0.161
S = 1.07
2307 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.18 e Å⁻³

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) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

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

Figures top

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

3,5-diphenyl-4H-1,2,4-triazol-4-amine top

Crystal data top

C₁₄H₁₂N₄	F(000) = 992
M_r = 236.28	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.075P)² + 0.3879P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2307 reflections	Δρ_max = 0.16 e Å⁻³
164 parameters	Δρ_min = −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)

Crystal data top

C₁₄H₁₂N₄	V = 2398.4 (5) Å³
M_r = 236.28	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 7.5521 (9) Å	µ = 0.08 mm⁻¹
b = 11.2309 (14) Å	T = 293 K
c = 28.278 (3) Å	0.30 × 0.28 × 0.25 mm

Data collection top

Bruker SMART CCD diffractometer	2307 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	1613 reflections with I > 2σ(I)
T_min = 0.976, T_max = 0.980	R_int = 0.029
9495 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.161	H-atom parameters constrained
S = 1.07	Δρ_max = 0.16 e Å⁻³
2307 reflections	Δρ_min = −0.18 e Å⁻³
164 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
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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) −x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₄
M_r	236.28
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	7.5521 (9), 11.2309 (14), 28.278 (3)
V (Å³)	2398.4 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.28 × 0.25

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2000)
T_min, T_max	0.976, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	9495, 2307, 1613
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.161, 1.07
No. of reflections	2307
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.18

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···N2ⁱ	0.95	2.17	3.117 (2)	177.1

Symmetry code: (i) −x+1/2, y−1/2, z.

Acknowledgements

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

References

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