Ethyl 1-[(2-chloro-1,3-thia­zol-5-yl)methyl]-5-methyl-1H-1,2,3-triazole-4-carboxylate

Xiao-Bao Chen; Feng-Mei Sun; Jing Xu; Zuan Ma; Ai-Hua Zheng

doi:10.1107/S1600536808037914

. 2008 Nov 20;64(Pt 12):o2402–o2403. doi: 10.1107/S1600536808037914

Ethyl 1-[(2-chloro-1,3-thiazol-5-yl)methyl]-5-methyl-1H-1,2,3-triazole-4-carboxylate

Xiao-Bao Chen ^a,^*, Feng-Mei Sun ^b, Jing Xu ^a, Zuan Ma ^a, Ai-Hua Zheng ^a

PMCID: PMC2960093 PMID: 21581372

Abstract

In the title compound, C₁₀H₁₁ClN₄O₂S, the triazole ring carries methyl and ethoxycarbonyl groups and is bound via a methylene bridge to a chlorothiazole unit. There is also evidence for significant electron delocalization in the triazolyl system. Intra- and intermolecular C—H⋯O hydrogen bonds together with strong π–π stacking interactions [centroid–centroid distance 3.620 (1) Å] stabilize the structure.

Related literature

Many derivatives of triazole have been prepared, and their biological activities have been studied by Ogura et al. (2000 ▶), Najim et al. (2004 ▶), Abu-Orabi et al. (1989 ▶), Shuto et al. (1995 ▶), Fan & Katritsky (1996 ▶), Chen et al. (2005 ▶) and Liu et al. (2001 ▶). For the synthesis, see: Chen et al. (2007 ▶); Chen & Shi (2008 ▶). For bond-length data, see: Sasada (1984 ▶); Wang et al. (1998 ▶). For related literature, see: Chen et al. (2007 ▶); Tian et al. (2008 ▶); Chen et al. (2008 ▶); Knox & Rogers (1989 ▶); Rogers et al. (1985 ▶); Shuto et al. (1995 ▶).

Experimental

Crystal data

C₁₀H₁₁ClN₄O₂S
M _r = 286.74
Triclinic,
a = 7.9692 (14) Å
b = 9.1656 (16) Å
c = 10.4430 (18) Å
α = 65.892 (2)°
β = 67.938 (2)°
γ = 80.641 (2)°
V = 645.23 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 291 (2) K
0.50 × 0.40 × 0.30 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: none
4630 measured reflections
2332 independent reflections
2005 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.118
S = 1.04
2332 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808037914/at2677sup1.cif

e-64-o2402-sup1.cif^{(17.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037914/at2677Isup2.hkl

e-64-o2402-Isup2.hkl^{(114.6KB, 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
C2—H2⋯O1ⁱ	0.93	2.47	3.375 (4)	164
C7—H7B⋯O2	0.96	2.43	3.033 (4)	121

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors gratefully acknowledge financial support of this work by Yunyang Medical College, and acknowledge the Sophisticated Analytical Instrument Facility, Central China Normal University, Whuhan, for the data collection.

supplementary crystallographic information

Comment

It is well known that many triazole-related molecules play an important role in the development of agrochemicals such as insecticides, nematocides, acaricide and plant growth regulators (Ogura et al., 2000; Najim et al., 2004; Abu-Orabi et al., 1989; Shuto et al.,1995; Fan & Katritsky, 1996; Chen et al., 2005; Richard & Ben, 1985; Ingrid et al., 1989 and Liu et al., 2001). Since the structure-activity relationship is very useful in the rational design of pharmaceuticals and agrochemicals. We report here the crystal structure of the title compound, (I) (Fig. 1), which was synthesized by introducing pyridine rings into a 1,2,3-triazole molecular framework.

In the title compound, the C5—N2 and C6—N4 bonds are significantly shorter than that of the single bond of C—N (1.47 Å; Sasada, 1984) and close to the value of the double bond of C—N (1.28 Å; Wang et al., 1998). This indicates significant electron delocalization in the triazolyl system.

Inter and intramolecular C—H···O hydrogen bonds contribute strongly to the stability of the molecular configuration (Fig.2). Strong π—π stacking interactions are also found between adjacent S1—C1/N1/C2—C3 rings with centroid-centroid distances 3.620 (1) Å, dihedral angles of 0.03 (1)°, and a shortest interplanar distance of 3.573 Å.

Experimental

Ethyl acetylacetate (2 mmol) and 5-azidomethyl-2-chlorothiazole (2 mmol) were added to a suspension of milled potassium carbonate (2 mmol) in DMSO (10 ml). The mixture was stirred at room temperature for 6 h (monitored by thin-layer chromatography) and poured to water (50 ml). The solid was collected by filtration, washed with water and diethyl ether, respectively, and dried to give 0.52 g of the title compound (yield 91%). Colourless crystals of (I) suitable for X-ray structure analysis were grown from acetone and petroleum ether (1:1, v/v).