N-[(E)-2-Chloro­benzyl­idene]-3-(4-methyl­benzyl­sulfan­yl)-5-(3,4,5-trimethoxy­phen­yl)-4H-1,2,4-triazol-4-amine

Qian-Zhu Li; Bao-An Song; Song Yang; Yu-Guo Zheng; Qing-Qing Guo

doi:10.1107/S1600536809009842

. 2009 Mar 25;65(Pt 4):o869. doi: 10.1107/S1600536809009842

N-[(E)-2-Chlorobenzylidene]-3-(4-methylbenzylsulfanyl)-5-(3,4,5-trimethoxyphenyl)-4H-1,2,4-triazol-4-amine

Qian-Zhu Li ^a,^b,^*, Bao-An Song ^a, Song Yang ^a, Yu-Guo Zheng ^a, Qing-Qing Guo ^a

PMCID: PMC2968782 PMID: 21582581

Abstract

In the title compound, C₂₆H₂₅ClN₄O₃S, the acyclic imine group exhibits an E configuration. The triazole ring is oriented at dihedral angles of 53.84 (2), 70.77 (1) and 32.59 (3)° with respect to the benzene rings of the 2-chlorobenzylidene, 4-methylbenzylsulfanyl and 3,4,5-trimethoxyphenyl groups, respectively. The crystal packing is stabilized by weak intermolecular C—H⋯N, C—H⋯S and C—H⋯π interactions.

Related literature

For more information on 1,2,4-triazoles, see: He et al. (2006 ▶); Kritsanida et al. (2002 ▶); Demirbas et al. (2002 ▶); Chattopadhyay & Ghosh (1987 ▶, 1989 ▶).

Experimental

Crystal data

C₂₆H₂₅ClN₄O₃S
M _r = 509.01
Monoclinic,
a = 11.283 (4) Å
b = 7.414 (2) Å
c = 31.087 (10) Å
β = 100.961 (14)°
V = 2553.1 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 293 K
0.32 × 0.26 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.932, T _max = 0.956
26288 measured reflections
4590 independent reflections
3809 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.141
S = 1.03
4590 reflections
320 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.65 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: DIAMOND (Brandenburg, 2001 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809009842/gk2192sup1.cif

e-65-0o869-sup1.cif^{(22.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009842/gk2192Isup2.hkl

e-65-0o869-Isup2.hkl^{(224.9KB, 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
C19—H19⋯N4	0.93	2.52	3.000 (3)	112
C10—H10⋯S1	0.93	2.81	3.184 (3)	105
C6—H6⋯N1ⁱ	0.93	2.61	3.409 (3)	144
C8—H8B⋯Cg2ⁱⁱ	0.97	2.70	3.427 (2)	133
C24—H24B⋯Cg1ⁱⁱⁱ	0.96	2.94	3.588 (2)	125

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1 is the centroid of the C9,C17,N1–N3 ring and Cg2 is the centroid of the C2–C7 ring.

Acknowledgments

The authors acknowledge the National Key Technologies R&D Program of China (2006BAE01A01–13) for supporting this work.

supplementary crystallographic information

Comment

The design and synthesis of new 1,2,4-triazole derivatives is an important research field, since these species not only can be used to build polymetallic complexes (He et al., 2006), but also show biological activity (Demirbas et al., 2002; Kritsanida et al., 2002). The biological activity is most probably due to the presence of the –N–C–S unit (Chattopadhyay & Ghosh, 1987, 1989). We are interested in the synthesis and biological activities of 1,2,4-triazole derivatives and report herein the synthesis and crystal structure of the title compound.

As illustrated in Figure 1, the 2-chlorobenzylidene, 4-methylbenzylsulfanyl, 3,4,5-trimethoxyphenyl and 1,2,4-triazole fragments are not coplanar with each other. The triazole ring is oriented with respect to the phenyl rings of 2-chlorobenzylidene, 4-methylbenzylthio and 3,4,5-trimethoxyphenyl units at dihedral angles of 53.84 (2)°, 70.77 (1) ° and 32.59 (3) °, respectively. The molecular packing is consolidated through weak inter- and intramolecular C—H···N, C—H···S and C—H···π interactions. C—H···π interactions of methylene H atoms and methyl H atoms are established towards the π-systems of neighboring aromatic groups from 4-methylbenzylsulfanyl and 1,2,4-triazole units (Table 1, Fig. 2, Cg1 = ring(C9,C17,N1—N3); Cg2 = ring(C2—C7)). ;

Experimental

A mixture of 1-chloromethyl-4-methylbenzene (1.40 g, 0.01 mol) and methanol (5 ml) was added dropwise to a stirred solution of (E)-4-(2-chlorobenzylideneamino)-5-(3,4,5-trimethoxyphenyl) -4H-1,2,4-triazole-3-thiol (4.05 g, 0.01 mol) and sodium hydroxide (0.40 g, 0.01 mol) in water (20 ml). The resulting mixture was stirred at room temperature for 5 h. The precipitate formed was filtered off and recrystallized from ethanol to give pure title compound, which was then dissolved in 30 ml ethanol, and single crystals of the title compound were obtained after several days.