Methyl 5-methyl-1-(1H-pyrazol-3-yl)-1H-1,2,3-triazole-4-carboxyl­ate

Xiao-Guang Bai; Chao Feng

doi:10.1107/S1600536814012380

. 2014 Jun 7;70(Pt 7):o755. doi: 10.1107/S1600536814012380

Methyl 5-methyl-1-(1H-pyrazol-3-yl)-1H-1,2,3-triazole-4-carboxylate

Xiao-Guang Bai ^a, Chao Feng ^b,^*

PMCID: PMC4120607 PMID: 25161549

Abstract

The asymmetric unit of the title compound, C₈H₉N₅O₂, contains two independent molecules (A and B) in which the dihedral angles between the triazole and pyrazole rings are 4.80 (14) and 8.45 (16)°. In the crystal, molecules are linked by N—H⋯N hydrogen bonds into supramolecular independent A and B chains propagating along the b-axis direction. The crystal structure also features π–π stacking between the aromatic rings of adjacent chains, the centroid–centroid separations being 3.8001 (15), 3.8078 (17), 3.8190 (14) and 3.8421 (15) Å.

Related literature

For applications of 1,2,3-triazole and its derivatives, see: Danoun et al. (1998 ▶); Manfredini et al. (2000 ▶). graphic file with name e-70-0o755-scheme1.jpg

Experimental

Crystal data

C₈H₉N₅O₂
M _r = 207.20
Monoclinic,
a = 15.4576 (6) Å
b = 16.0945 (9) Å
c = 7.5348 (3) Å
β = 90.079 (4)°
V = 1874.52 (15) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.15 × 0.12 × 0.10 mm

Data collection

Bruker MWPC area-detector diffractometer
5457 measured reflections
3247 independent reflections
2312 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.153
S = 1.08
3247 reflections
275 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: FRAMBO (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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.

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814012380/xu5793sup1.cif

e-70-0o755-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814012380/xu5793Isup2.hkl

e-70-0o755-Isup2.hkl^{(156.1KB, hkl)}

CCDC reference: 1005571

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4N⋯N3ⁱ	0.86	2.17	3.022 (3)	170
N9—H9N⋯N8ⁱⁱ	0.86	2.20	3.044 (3)	169

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

We are grateful for financial support from the National Natural Science Foundation of China (No. 81302644) and Jiangsu Ainaji Neo Energy Science & Technology Co. Ltd (No. 8507040091).

supplementary crystallographic information

S1. Comment

1,2,3-Triazole and its derivatives had attracted considerable attention for the past few decades due to their chemotherapeutical value. Many 1,2,3-triazoles are found to be potent antimicrobial and antiviral agents. Some of them have exhibited antiproliferative and anticancer activities (Danoun et al., 1998). Some 1,2,3-triazoles are used as DNA cleaving agents (Manfredini et al., 2000) and potassium channel activators. Prompted by the chemotherapeutic importance of 1,2,3-triazoles and its derivatives, we have synthesized the title compound and report its crystal structure herein.

The title compound, contains two crystallographically independent molecules and bond lengths and angles are in the normal range(Fig. 1). The dihedral angle between the triazole and pyrazole rings is 4.80 (14)° and 8.45 (16)° respectively. The crystal structure is stabilized by N–H···N hydrogen bonds linking molecules into one-dimensional chains running parallel to the b axis (Fig. 2). The structure is further stabilized by π···π stacking interactions, with centroid-to-centroid separations of 3.8001 (15)–3.8421 (15) Å.

S2. Experimental

3-Azido-1H-pyrazole (20 mmol) was treated with ethyl acetoacetate (24 mmol) in methanol (75 ml) and the mixture was cooled to 273 K. Sodium methoxide (24 mmol) was added to the above mixture and stirred at ambient temperature for 24 h. After completion of the reaction, the mixture was poured on to ice cold water. The precipitated solid was filtered, washed with water and recrystallized from methanol, then 5-methyl-1-(1H-pyrazol-3-yl)-1H-1,2,3-triazole-4- carboxylic acid were obtained. A mixture of 5-methyl-1-(1H-pyrazol-3-yl)-1H-1,2,3-triazole-4- carboxylic acid (0.1 mmol) and Et₃N(0.2 mmol) in methanol (15 ml) was stirred at room temperature until the starting material disappeared. The resulting mixture was filtered and let the filtrate still for 24 h, colorless needle-like crystals were obtained.