Ethyl 5-methyl-1-(4-nitro­phen­yl)-1H-1,2,3-triazole-4-carboxyl­ate

Hoong-Kun Fun; Ching Kheng Quah; Nithinchandra; Balakrishna Kalluraya

doi:10.1107/S1600536811033940

. 2011 Aug 27;67(Pt 9):o2416. doi: 10.1107/S1600536811033940

Ethyl 5-methyl-1-(4-nitrophenyl)-1H-1,2,3-triazole-4-carboxylate

Hoong-Kun Fun ^a,^*,^‡, Ching Kheng Quah ^a,^§, Nithinchandra ^b, Balakrishna Kalluraya ^b

PMCID: PMC3200591 PMID: 22059001

Abstract

In the title compound, C₁₂H₁₂N₄O₄, the 1,2,3-triazole ring and the nitro group form dihedral angles of 37.93 (5) and 8.97 (12)°, respectively, with the phenyl ring. The molecular structure is stabilized by an intramolecular C—H⋯O hydrogen bond, which generates an S(6) ring motif. In the crystal, molecules are linked by C—H⋯N hydrogen bonds into layers lying parallel to (100). The crystal structure is further consolidated by π–π [centroid–centroid distance = 3.6059 (6) Å] interactions.

Related literature

For general background to and the biological activity of 1,2,3-triazole derivatives, see: Sherement et al. (2004 ▶); Danoun et al. (1998 ▶); Manfredini et al. (2000 ▶); Biagi et al. (2004 ▶). For standard bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶). For related structures, see: Fun, Quah, Chandrakantha et al. (2011 ▶); Fun, Quah, Nithinchandra et al. (2011 ▶).

Experimental

Crystal data

C₁₂H₁₂N₄O₄
M _r = 276.26
Monoclinic,
a = 13.5309 (3) Å
b = 7.3014 (2) Å
c = 12.6058 (3) Å
β = 99.574 (1)°
V = 1228.04 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 100 K
0.50 × 0.16 × 0.16 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.944, T _max = 0.982
16800 measured reflections
4469 independent reflections
3699 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.114
S = 1.03
4469 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811033940/hb6375sup1.cif

e-67-o2416-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811033940/hb6375Isup2.hkl

e-67-o2416-Isup2.hkl^{(219KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811033940/hb6375Isup3.cml

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
C1—H1A⋯N3ⁱ	0.95	2.59	3.5243 (12)	168
C5—H5A⋯N2ⁱⁱ	0.95	2.60	3.2347 (12)	125
C5—H5A⋯N3ⁱⁱ	0.95	2.54	3.4127 (12)	154
C10—H10B⋯O4	0.98	2.48	3.0936 (12)	120

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

Acknowledgments

HKF and CKQ thank Universiti Sains Malaysia for the Research University Grant (No. 1001/PFIZIK/811160).

supplementary crystallographic information

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 (Sherement et al., 2004) 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 (Biagi et al., 2004). Prompted by the chemotherapeutic importance of 1,2,3-triazoles and its derivatives, we synthesized the title compound.

In the title molecule, Fig. 1, the 1,2,3-triazole ring (N1-N3/C7/C8, maximum deviation of 0.003 (1) Å at atoms N2 and N3) and the nitro group (O2/O3/N4) form dihedral angles of 37.93 (5) and 8.97 (12)°, respectively, with the phenyl ring (C1-C6). Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to related structures (Fun, Quah, Chandrakantha et al., 2011; Fun, Quah, Nithinchandra et al., 2011). The molecular structure is stabilized by an intramolecular C41-H10B···O4 hydrogen bond (Table 1), which generates an S(6) ring motif (Fig. 1, Bernstein et al., 1995).

In the crystal structure, Fig. 2, molecules are linked via intermolecular C1–H1A···N3, C5–H5A···N2 and C5–H5A···N3 hydrogen bonds (Table 1) into two-dimensional planes parallel to (100). π-π stacking interactions between the centroids of C1-C6 phenyl ring (Cg1) and N1-N3/C7/C8 triazole ring (Cg2), with Cg1···Cg2ⁱⁱⁱ distance of 3.6059 (6) Å [symmetry code: (iii) 1-X,-1/2+Y,1/2-Z] are observed.

Experimental

1-Azido-4-nitrobenzene (15 g) was treated with ethyl acetoacetate (8.3 g) in methanol (75 ml) and the mixture was cooled to 273 K. Sodium methoxide (3.5 g) was added under inert atmosphere to the above mixture and stirred at ambient temperature for 8 h. Progress of the reaction was monitored by TLC (ethyl acetate/n-hexane, 2:3, v/v). 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. Colourless plates of (I) were obtained from DMF by slow evaporation.