1-(3-Chloro­phen­yl)-2-methyl-4-nitro-1H-imidazole-5-carboxamide

Artur Korzański; Paweł Wagner; Maciej Kubicki

doi:10.1107/S1600536811036609

. 2011 Sep 14;67(Pt 10):o2626. doi: 10.1107/S1600536811036609

1-(3-Chlorophenyl)-2-methyl-4-nitro-1H-imidazole-5-carboxamide

Artur Korzański ^a, Paweł Wagner ^b, Maciej Kubicki ^a,^*

PMCID: PMC3201265 PMID: 22058768

Abstract

In the crystal structure of the title compound, C₁₁H₉ClN₄O₃, pairs of N—H⋯N(imidazole) hydrogen bonds connect the molecules into centrosymmetric dimers, which are further connected by N—H⋯O(carbamoyl) hydrogen bonds into C(4) chains along [010]. Interplay of these two kinds of hydrogen bonds connect the molecules into layers perpendicular to [101]. The imidazole [maximum deviation 0.0069 (9) Å] and phenyl rings are inclined at a dihedral angle of 58.44 (6)°; the nitro group is almost coplanar [dihedral angle 5.8 (2)°] with the imidazole ring while the carbamoyl group is almost perpendicular [70.15 (13)°] to it.

Related literature

For the synthesis, see: Suwiński et al. (1994 ▶). For similar nitroimidazole derivatives, see: Kubicki (2004a ▶,b ▶). For a recent experimental charge density study of a nitroimidazole derivative, see: Paul et al. (2011 ▶).

Experimental

Crystal data

C₁₁H₉ClN₄O₃
M _r = 280.67
Monoclinic,
a = 21.8417 (14) Å
b = 7.3710 (4) Å
c = 16.2467 (10) Å
β = 108.680 (7)°
V = 2477.9 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 295 K
0.25 × 0.2 × 0.08 mm

Data collection

Agilent Xcalibur Sapphire2 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.833, T _max = 1.000
4943 measured reflections
2702 independent reflections
2185 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.104
S = 1.04
2702 reflections
197 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811036609/zk2021sup1.cif

e-67-o2626-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036609/zk2021Isup2.hkl

e-67-o2626-Isup2.hkl^{(130.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811036609/zk2021Isup3.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
N51—H51A⋯N3ⁱ	0.85 (2)	2.29 (2)	3.130 (2)	169.2 (18)
N51—H51B⋯O51ⁱⁱ	0.87 (2)	2.03 (2)	2.8938 (19)	171.3 (18)

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

supplementary crystallographic information

Comment

In the course of our studies on nitroimidazole derivatives (e.g. Kubicki, 2004a, 2004b; Paul et al., 2011) we have determined the crystal structure of another member of the family of 1-aryl-4-nitro substituted imidazole, 1(3-chlorophenyl)-2-methyl-4-nitro-5-carbamoyl-imidazole (1, Scheme 1).

Fig. 1 shows the perspective view of 1. The two main planar fragments, imidazole (maximum deviation 0.0069 (9) Å) and phenyl rings (0.0125 (13) Å), are inclined by 58.44 (6)°. This value is relatively small: for instance, in three polymorphs of 1-phenyl-2-methyl-4-nitro-5-bromoimidazole (Kubicki, 2004a) the twist angle ranges from 86 to 90°, and in 1-(4-chlorophenyl)-2-methyl-4-nitro-1H-imidazole-5-carbonitrile (Kubicki, 2004b) - 87.5°. The nitro group is nearly coplanar with the imidazole ring (dihedral angle of 5.8 (2)°, while the carbamoyl fragment is, on contrary, almost perpendicular and is inclined by 70.15 (13)° with respect to the imidazole ring plane.

The principal motifs of the crystal sructure are constructed by means of N—H···N and N—H···O hydrogen bonds. N51···N3(1/2 - x,3/2 - y,1 - z) hydrogen bonds connect molecules into centrosymmetric dimers (Fig. 2), and these dimers - the graph set symbol R²₂(12) - might be regarded as the building blocks of the structure. The other hydrogen bond, N51···O51(1/2 - x,-1/2 + y,1/2 - z), connect the molecules into C(4) chains along [010] direction. Interplay of these two kinds of hydrogen bonds connect molecules into layers perpendicular to [101], Fig. 3. The neighbouring layers are not connected by any directional intermolecular interactions.

Experimental

The compound, as an intermediate in purine synthesis, was synthesized by alkaline hydrolysis of 5-cyano derivative in the presence of hydrogen peroxide in good yield (Suwiński et al., 1994).