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

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

doi:10.1107/S1600536814017243

. 2014 Aug 1;70(Pt 9):o962–o963. doi: 10.1107/S1600536814017243

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

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

PMCID: PMC4186084 PMID: 25309281

Abstract

In the title molecule, C₁₃H₁₃N₃O₂, the planes of the benzene and imidazole rings form a dihedral angle of 7.72 (5)°. In the crystal, molecules are linked by weak C—H⋯N and C—H⋯O hydrogen bonds, forming layers parallel to (100). A weak C—H⋯π interaction connects these layers into a three-dimensional network. A π–π stacking interaction, with a centroid–centroid distance of 3.5373 (9) Å, is also observed.

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

Related literature

For the synthesis and applications of imidazole derivatives, see: Mamedov et al. (2011 ▶); De Luca (2006 ▶); Teimouri & Chermahini (2011 ▶); Achar et al. (2010 ▶); Özkay et al. (2010 ▶); Shingalapur et al. (2009 ▶); Bhatia & Shanbhag (1984 ▶); Hoffer & Grunberg (1974 ▶). For the biological activity of nitroimidazole derivatives, see: Trivedi et al. (2011 ▶); Leitsch et al. (2011 ▶); Luo et al. (2010 ▶); Saadeh et al. (2009 ▶); Thompson et al. (2009 ▶); Carvalho et al. (2006 ▶); Alliouche et al. (2014 ▶); Hunkeler et al. (1981 ▶); Tanigawara et al. (1999 ▶). graphic file with name e-70-0o962-scheme1.jpg

Experimental

Crystal data

C₁₃H₁₃N₃O₂
M _r = 243.26
Monoclinic,
a = 7.1774 (8) Å
b = 15.7931 (16) Å
c = 10.7901 (11) Å
β = 101.798 (6)°
V = 1197.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 150 K
0.16 × 0.06 × 0.05 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▶) T _min = 0.891, T _max = 1.000
9856 measured reflections
2113 independent reflections
1958 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.094
S = 1.05
2113 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.31 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/S1600536814017243/lh5721sup1.cif

e-70-0o962-sup1.cif^{(22.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814017243/lh5721Isup2.hkl

e-70-0o962-Isup2.hkl^{(101.8KB, hkl)}

Click here for additional data file.^{(5.1KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814017243/lh5721Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S1600536814017243/lh5721fig1.tif

The molecular structure structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.^{(1.4MB, tif)}

c . DOI: 10.1107/S1600536814017243/lh5721fig2.tif

The crystal packing of (I) viewed along the c axis showing weak C—H⋯O hydrogen bonds as dashed lines.

Click here for additional data file.^{(1.6MB, tif)}

a . DOI: 10.1107/S1600536814017243/lh5721fig3.tif

The crystal packing of (I) viewed along the a axis showing weak C—H⋯O and C—H⋯N hydrogen bonds as dashed lines.

CCDC reference: 1016150

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

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

Cg is the centroid of the C7–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯N2ⁱ	0.93	2.49	3.3702 (17)	159
C4—H4C⋯O1B ⁱ	0.96	2.54	3.2676 (17)	133
C13—H13B⋯O1A ⁱⁱ	0.96	2.59	3.5347 (19)	168
C4—H4B⋯Cg ⁱⁱⁱ	0.96	2.61	3.4336 (16)	144

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

Acknowledgments

We are grateful to all 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

The imidazole nucleus is an important pharmacophore found in a large number of natural products and synthetic compounds with a wide range of applications which make imidazole derivatives a subject of extensive investigations (Mamedov, et al., 2011; De Luca, 2006; Tanigawara, et al., 1999; Hunkeler, et al., 1981). For example, many synthetic imidazole derivatives are present in a number of bioactive compounds such as fungicides, herbicides, bactericides, anti-inflammators, analgesics and anticancers (Teimouri, et al., 2011; Achar, et al., 2010; Özkay, et al., 2010; Shingalapur, et al., 2009). Nitroimidazoles are a particular class of imidazoles principally composed of bioactive substances where their spectrum of action is closely associated with the position of the nitro group on the imidazole ring. Due to their significant biological activity, 5-nitroimidazoles are widely used in medicine as bactericide and parasiticide agents, some of them possess an original activity spectrum especially towards protozoa and strict anaerobic bacteria (Trivedi, et al., 2011; Bhatia, et al., 1984; Hoffer et al., 1974), and others exhibit cytotoxic and radiosensitization activities in vitro and in vivo (Leitsch, et al., 2011; Luo, et al., 2010). However, only few biological properties of 4-nitroimidazoles have been reported in the literature (Saadeh, et al., 2009; Thompson, et al., 2009; Carvalho, et al., 2006). The transposition of a nitro group in 5-nitroimidazoles is a known reaction and constitutes an efficient synthetic procedure of 4-nitroisomers. However, only few examples of this reaction are described using methyl iodide as catalyst (Alliouche, et al. 2014). We report in this paper, the synthesis and structure determination of (E)-1-methyl-2-[(4-methylphenyl)-1-ethenyl]-5-nitroimidazole (I). The later was easily prepared from its 5-nitro isomer via an intramolecular transposition of the nitro group. The reaction was carried out in nitrobenzene at 433K using catalytic amount of methyl iodide.

The molecular structure of (I) is shown in Fig. 1. The benzene and imidazole ring form a dihedral angle of 7.72 (5)°. The crystal packing can be described as double zig-zag layers parallel to (100) (Fig. 2) which are stabilized by weak C—H···N and C—H···O hydrogen bonds. A weak C—H···π interaction links the layers forming a three-dimensional network (Fig. 2 and Fig. 3). The crystal structure features one π–π stacking interaction: Cg1—Cg2 (-x, -y, 1-z) = 3.5373 (9) Å Where, Cg1 is the centroid of the imidazole ring (C1/C2/N3/C3/N2) and Cg2 is is the centroid of the phenyl ring (C7/C8/C9/C10/C11/C12).

S2. Experimental

The title compound (I) was obtained as yellow solid in 94% yield by heating the corresponding 5-nitroisomer at 433K in nitrobenzene in presence of methyl iodide as catalyst, during 24 h. Suitable crystals were obtained by slow evaporation of a solution of the title compound in water/methanol solution at room temperature.