2-Amino-4-[1-(2-chloro­phen­yl)-5-methyl-1H-1,2,3-triazol-4-yl]-6-(4-methyl­phen­yl)benzene-1,3-dicarbonitrile

Wang-Jun Dong; Hui-Cheng Wang; Zhong-Liang Gao; Rong-Shan Li; Heng-Shan Dong

doi:10.1107/S1600536809014032

. 2009 Apr 25;65(Pt 5):o1126. doi: 10.1107/S1600536809014032

2-Amino-4-[1-(2-chlorophenyl)-5-methyl-1H-1,2,3-triazol-4-yl]-6-(4-methylphenyl)benzene-1,3-dicarbonitrile

Wang-Jun Dong ^a, Hui-Cheng Wang ^a, Zhong-Liang Gao ^a, Rong-Shan Li ^a, Heng-Shan Dong ^a,^*

PMCID: PMC2977799 PMID: 21583936

Abstract

In the title compound, C₂₄H₁₇ClN₆, the dihedral angles between the triazolyl ring and its adjacent chlorobenzene and trisubstituted benzene rings are 90.6 (2) and 55.7 (3)°, respectively. The dihedral angle between the trisubstituted ring and the attached tolyl ring of the biphenyl unit is 45.9 (3)°. Intra- and intermolecular N—H⋯N hydrogen bonds are present.

Related literature

For the synthesis, see: Victory et al. (1991 ▶).

Experimental

Crystal data

C₂₄H₁₇ClN₆
M _r = 424.89
Monoclinic,
a = 13.623 (6) Å
b = 7.792 (4) Å
c = 20.608 (10) Å
β = 103.502 (6)°
V = 2127.0 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 293 K
0.33 × 0.31 × 0.29 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.935, T _max = 0.943
11092 measured reflections
4169 independent reflections
3263 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.120
S = 1.03
4169 reflections
282 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809014032/ng2572sup1.cif

e-65-o1126-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014032/ng2572Isup2.hkl

e-65-o1126-Isup2.hkl^{(204.3KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5B⋯N6ⁱ	0.86	2.56	3.221 (2)	134
N5—H5A⋯N4	0.86	2.91	3.540 (2)	125

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Symmetry code: (i) Inline graphic .

Acknowledgments

This project is supported by the State Key Laboratory of Applied Organic Chemistry, Lanzhou University.

supplementary crystallographic information

Comment

The title compound, C₂₄H₁₇N₆Cl (I) (Figuer 1) was synthesized by the reaction of (E)-1-[1-(2-chlorophenyl)-5-methyl-1H-1,2,3-triazol-4-yl]-3-(4-methylphenyl)prop-2-en-1-ones and malononitrile in the presence of piperindine at 25°C. The consists plane of subsituted triazolyl ring and 2-chlorophenyl ring, subsituted triazolyl ring and 2-amino-1,3-dinitrilphenyl ring, 2-amino-1,3-dinitrilphenyl ring and 4-methylphenyl ring is not co-planar [The dihedral angle of C1—C6—N1—N2 is 90.6 (2)°, C7—C8—C10—C11 is 55.7 (3)°, C13—C14—C18—C19 is 45.9 (3)° in stable conformation of the crystal].

On 2-amino-1,3-dinitrilphenyl ring, the p-π conjugation was indicated the between amino N5 and ring C12, bond length of C12—N5 is 1.361 (2)Å which is shorter than non-conjugation Csp2-Nsp2 bond C6—N1 1.430 Å(Table 1), angle of C12—N5—H5A, H5A—N5—H5B is 120°, the dihedral angle of N5—C12—C13—C14 is 177.3°, the dihedral angle of N5—C12—C13—C17 is 0.9°, N5 is sp2 hybridized atom.

On 2-amino-1,3-dinitrilphenyl ring, 2-amino has two N—H bond, and two intermolecular hydrogen bonds as the supramolecular structure in the crystal. The intermolecular N6···H5B—N5 hydrogen bond between the N6 atoms of C≡N group and N5—H5B, intermolecular N6···H'5B-N'5 hydrogen bond between the N6 atoms of the C≡N group and N5-H5B (Figure 2; Table 2). One 12 members ring is consisted of two intermolecular H-bonds. The orderly range of the structure forms stratification polymer in the crystal. The intermolecular hydrogen bond connect the translated molecules into an infinite chain on a layer.

Experimental

2-Amino-4-[1-(4-chlorophenyl)-5-methyl-1H-1,2,3-triazol-4-yl]-6-(4-methylphenyl)benzene-1,3-dinitrile, which was synthesized by a modification of a published procedure (Victory, et al. 1991). To add 1.6 mL piperidine the mixture liquor of 0.675 g (2 mmol) (E)-1-[1-(2-chlorophenyl)-5-methyl-1H-1,2,3-triazol-4-yl]-3-(4-methylphenyl)prop-2-en-1-one and 0.264 g (4 mmol) malononitrile in 5 mL of absolute ethanol was stirred. The mixture was stirred for 30 h at room temperature. After removal of solvent, the mixture was poured into water, neutrilized with 10% acetic acid. The resulting solid was filtered, washed with water, dried and isolated with petroleum ether/EtOAc(4:1) to give the target compound, mp 470–471 K, in 75% yield. The structure was established by ¹H-NMR, IR and mass spectrosopic data analyses. ¹H NMR(300 MHz, CDCl₃): δ=2.341 (s, 3H, Ar—CH₃), 2.458 (s, 3H, triazolyl-CH₃), 5.408 (s, 2H, NH₂), 7.161 (s, 1H, 5-H), 7.308–7.335 (d, 2H, J = 8.1 Hz, Ar—H), 7.485–7.601 (m, 5H, Ar—H), 7.636–7.663(d, 1H, J = 8.1 Hz, Ar—H) p.p.m.. MS (%): 424 (M^+., 1.35%), 396(19.8), 334(3.5), 320(2.6), 305(1.5), 256 (3.3), 232 (1.2), 205 (3.5), 192 (11.7), 164 (10.6), 178(4.5), 164(10.6), 141(6.9), 138(10.3), 125(10.3), 91(17.5), 85(25.3), 77(10.6), 57(51.4), 43(100.0). IR(KBr, cm^-1): 3442, 3349, 3234(N—H), 2214(C≡N), 1634, 1551, 1495, 823, 766