Crystal structure of (E)-1-methyl-2-[2-(2-methoxphen­yl)ethen­yl]-4-nitro-1H-imidazole

Hayette Alliouche; Abdelmalek Bouraiou; Sofiane Bouacida; Hocine Merazig; Ali Belfaitah

doi:10.1107/S1600536814017206

. 2014 Aug 1;70(Pt 9):o966–o967. doi: 10.1107/S1600536814017206

Crystal structure of (E)-1-methyl-2-[2-(2-methoxphenyl)ethenyl]-4-nitro-1H-imidazole

Hayette Alliouche ^a, Abdelmalek Bouraiou ^a, Sofiane Bouacida ^b,^c,^*, Hocine Merazig ^b, Ali Belfaitah ^a

PMCID: PMC4186069 PMID: 25309283

Abstract

In the asymmetric unit of the title compound, C₁₃H₁₃N₃O₃, the 2-(2-methoxphenyl)ethenyl unit is connected to the methyl-nitroimidazole 1-methyl-4-nitro-1H-imidazole moiety. The molecule is quasi-planar and the planes of the two rings form a dihedral angle of 0.92 (11)°. The crystal packing can be described as layers parallel to the (011) plane, stabilized by intermolecular C—H⋯O hydrogen bonding, resulting in the formation of an infinite three-dimensional network linking these layers. Strong π–π stacking interactions are observed, viz. benzene–benzene, imidazole–imidazole and benzene–imidazole rings, with centroid–centroid distances of 3.528 (2), 3.457 (2) and 3.544 (2) Å, respectively. Intensity statistics indicated twinning by non-merohedry, with refined weighs of the twin components of 0.3687:0.6313.

Keywords: crystal structure; hydrogen bonding; π–π stacking interactions; nitroimidazoles,

Related literature

For the synthesis and applications of this important class of compounds, see: Hori et al. (1997 ▶); Bourdin-Trunz et al. (2011 ▶). For our previous work on imidazole derivatives, see: Alliouche et al. (2014 ▶); Zama et al. (2013 ▶); Bahnous et al. (2012 ▶).

Experimental

Crystal data

C₁₃H₁₃N₃O₃
M _r = 259.26
Triclinic,
a = 7.9339 (18) Å
b = 8.1994 (19) Å
c = 10.452 (3) Å
α = 68.877 (17)°
β = 75.037 (17)°
γ = 76.182 (17)°
V = 604.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 150 K
0.19 × 0.12 × 0.08 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▶) T _min = 0.754, T _max = 1.000
5177 measured reflections
5177 independent reflections
3712 reflections with I > 2σ(I)

Refinement

R[F ² > 2σ(F ²)] = 0.088
wR(F ²) = 0.282
S = 1.06
5171 reflections
176 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg & Berndt, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814017206/hg5400sup1.cif

e-70-0o966-sup1.cif^{(22.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814017206/hg5400Isup2.hkl

e-70-0o966-Isup2.hkl^{(248.4KB, hkl)}

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S1600536814017206/hg5400fig1.tif

The structure of the title compound with the atomic labelling scheme. Displacement are drawn at the 50% probability level.

Click here for additional data file.^{(2.1MB, tif)}

a . DOI: 10.1107/S1600536814017206/hg5400fig2.tif

A diagram of the layered crystal packing of (I) viewed down the a axis and showing hydrogen bond [C—H⋯O] as dashed line.

CCDC reference: 1015965

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
C3—H3⋯O2ⁱ	0.93	2.45	3.271 (4)	147
C4—H4B⋯O1ⁱⁱ	0.96	2.53	3.465 (5)	165
C6—H6⋯O3	0.93	2.31	2.685 (4)	103
C6—H6⋯N2	0.93	2.60	2.935 (4)	102

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

Acknowledgments

We are grateful to the personnel of the PHYSYNOR Laboratory, Universite Constantine 1, Algeria, for their assistance. Thanks are due to the MESRS (Ministére de l’Enseignement Supérieur et de la Recherche Scientifique, Algérie) for financial support.

supplementary crystallographic information

S1. Comment

Nitroimidazoles are a class of N-heterocyclic compounds which have a wide range of applications in the drug synthesis (Hori, et al., 1997) In fact, Metronidazole (Flagyl) and related N-1 substituted 5-nitroimidazoles such as Tinidazole (Fasigyne), Ornidazole (Tiberal) and Secnidazole (Secnol) still commonly used in medicine. Despite their fewer biological activities compared with 5-nitroimidazoles, a number of 4-nitroimidazoles were reported to exhibit antileishmanial, antiamebic and anti-parasitic activities (Bourdin-Trunz, et al. 2011). However, only some limited investigations have been carried out using methyl iodide (Alliouche, et al. 2014). In previous work, we have reported the synthesis and structure determination of some new heterocyclic compounds bearing an imidazole unit (Zama, et al., 2013; Bahnous, et al., 2012). Herein, we describe the synthesis and the structure determination of (E)-1-methyl-2-[(2-methoxphenyl)-1-ethenyl]-4-nitroimidazole resulting from the intramolecular transposition reaction of its 5-nitro isomer in the presence of catalytic amounts of methyl iodide in nitrobenzene. The molecular geometry and the atom-numbering scheme of (I) are shown in Fig. 1. In the asymmetric unit of title compound the methoxphenyl-1-ethenyl unit is linked to methyl-nitroimidazole moiety. The molecule is quasi-planar and the two rings of phenyl and imidazol form a dihedral angle of 0.92 (11)°. The crystal packing can be described as layers parallel to (011) plane, along the a axis (Fig. 2). It is stabilized by intermolecular hydrogen bond C—H···O, resulting in the formation of an infinite three-dimensional network linking these layers together and reinforcing cohesion in the structure (Fig. 2). Hydrogen-bonding parameters are listed in Table 1. Strong π-π stacking interactions are observed between phenyl-phenyl, imidazol-imidazol and phenyl-imidazol rings, distances centroid-centroid are Cg—Cg = 3.528 (2), 3.457 (2) and 3.544 (2) Å respetively. The crystal used was a non-merohedral twin, the refined ratio of twin components being 0.3687:0.6313.

S2. Experimental

The title compound was obtained as a yellow-green solid in 83% of yield by heating a solution of (E)-1-methyl-2-[(2-methoxphenyl)-1-ethenyl]-5-nitroimidazole in nitrobenzene at 160°C during 24 h in the presence of catalytic amount of CH₃I. Suitable crystal of compound (I) was obtained by slow evaporation from a water/methanol solution at room temperature, and X-ray crystallographic analysis confirmed the structural assignment (Fig. 1).