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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1828–o1829.
Published online 2010 June 26. doi:  10.1107/S1600536810024542
PMCID: PMC3006860

2-Chloro-4-nitro-1H-imidazole

Abstract

The mol­ecule of the title compound, C3H2ClN3O2, is almost planar; the dihedral angle between the imidazole ring and the nitro group is 1.7 (2)°. In the crystal structure, pairs of inter­molecular C—H(...)O hydrogen bonds link inversion-related mol­ecules into dimers, generating R 2 2(10) ring motifs. The dimers are inter­connected into two-dimensional networks parallel to (102) via inter­molecular N—H(...)N hydrogen bonds. Further stabilization is provided by short inter­molecular Cl(...)O inter­actions [3.142 (2) and 3.1475 (19) Å].

Related literature

For general background to and applications of imidazole derivatives, see: Anuradha et al. (2006 [triangle]); Clark & Macquarrie (1996 [triangle]); Jadhav et al. (2008 [triangle]); Kolavi et al. (2006 [triangle]); Susanta et al. (2000 [triangle]). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995 [triangle]). For related 4-nitro­imidazole crystal structures, see: Ségalas et al. (1992 [triangle]); De Bondt et al. (1993 [triangle]). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1828-scheme1.jpg

Experimental

Crystal data

  • C3H2ClN3O2
  • M r = 147.53
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1828-efi1.jpg
  • a = 5.905 (2) Å
  • b = 10.033 (4) Å
  • c = 9.150 (3) Å
  • β = 105.180 (8)°
  • V = 523.2 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.64 mm−1
  • T = 100 K
  • 0.29 × 0.19 × 0.04 mm

Data collection

  • Bruker APEXII DUO CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.837, T max = 0.977
  • 5484 measured reflections
  • 1509 independent reflections
  • 1195 reflections with I > 2σ(I)
  • R int = 0.037

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.097
  • S = 1.11
  • 1509 reflections
  • 90 parameters
  • All H-atom parameters refined
  • Δρmax = 0.42 e Å−3
  • Δρmin = −0.44 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810024542/ci5106sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810024542/ci5106Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

HKF and JHG thank Universiti Sains Malaysia (USM) for the Research University Golden Goose grant (No. 1001/PFIZIK/811012). JHG also thanks USM for the award of a USM fellowship. AMI is grateful to the Director, National Institute of Technology-Karnataka and the Head of the Chemistry Department for their encouragement. BC is thankful to Dr John Kallikat of Syngene Inter­national Ltd for the research encouragement. AMI also thanks USM for a partially sponsored research visit to the X-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia.

supplementary crystallographic information

Comment

The nitro aromatic compounds are used as key substrates for the preparation of useful materials such as dyes, pharmaceuticals, perfumes and plastics (Susanta et al., 2000). Therefore, nitration of hydrocarbons particularly of aromatic compounds is probably one of the most widely studied organic reactions (Jadhav et al., 2008). In addition, they have proven to be valuable reagents for the synthesis of complex target molecules (Kolavi et al., 2006). Most of the substituted imidazoles are widely used in pharmaceutical ingredients (Clark & Macquarrie, 1996). The imidazole nucleus is one of the important heterocyclic groups due to its presence in a large number of bioactive pharmaceutical and agrochemicals (Anuradha et al., 2006). It was also reported that a large number of compounds containing the imidazole ring possess some moderately useful activities. The environmentally friendly nitration reaction has been the focus of recent research.

In the title imidazole derivative, the 1H-imidazole ring with atom sequence C1/N1/C2/C3/N2 is essentially planar, with a maximum deviation of 0.003 (2) Å at atom N1. The nitro group is coplanar with the attached 1H-imidazole ring, as indicated by the dihedral angle of 1.7 (2)°. The geometric parameters agree well with those reported for related 4-nitroimidazole structures (Ségalas et al., 1992; De Bondt et al., 1993).

In the crystal structure, (Fig. 2), pairs of intermolecular C2—H2···O1 hydrogen bonds (Table 1) link inversion-related molecules into dimers, generating R22(10) hydrogen bond ring motifs (Bernstein et al., 1995). These dimers are further interconnected into two-dimensional arrays parallel to the (102) plane via intermolecular N1—H1N1···N2 hydrogen bonds (Table 1). The interesting features of the crystal structure are the intermolecular short Cl···O interactions [Cl1···O1iii = 3.143 (2) and Cl1···O2i = 3.148 (2) Å; (i) 1-x, y-1/2, 1/2-z and (iii) 1+x, 3/2-y, z-1/2 ] which are shorter than the sum of the van der Waals radii of the relavant atoms and help to further stabilize the crystal structure.

Experimental

Nitronium tetrafluoroborate (1.42 g, 0.0107 mol) was dissolved in nitromethane (10 ml) and 2-chloroimidazole (1 g, 0.0097 mol) was then added in lot-wise. The reaction mixture was stirred at room temperature for 3 h. The reaction mixture was then neutrallized with an aqueous solution of sodium bicarbonate. The separated solid was then filtered. The crude product was purified by column chromatography using 60–120 silica gel. The fraction eluted at 10 % ethyl acetate in hexane was concentrated to afford the title compound as pale yellow single crystals (Yield 0.9 g, 62.93 %; m.p. 363–366 K).

Refinement

Atoms H1N1 and H2 were located in a difference Fourier map and allowed to refine freely [N1—H1N1 = 0.86 (3) and C2—H2A = 0.93 (3) Å].

Figures

Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme.
Fig. 2.
The crystal structure of the title compound, showing a two-dimensional network. Intermolecular interactions are shown as dashed lines.

Crystal data

C3H2ClN3O2F(000) = 296
Mr = 147.53Dx = 1.873 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2073 reflections
a = 5.905 (2) Åθ = 3.6–30.0°
b = 10.033 (4) ŵ = 0.64 mm1
c = 9.150 (3) ÅT = 100 K
β = 105.180 (8)°Plate, yellow
V = 523.2 (3) Å30.29 × 0.19 × 0.04 mm
Z = 4

Data collection

Bruker APEXII DUO CCD area-detector diffractometer1509 independent reflections
Radiation source: fine-focus sealed tube1195 reflections with I > 2σ(I)
graphiteRint = 0.037
[var phi] and ω scansθmax = 30.0°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −6→8
Tmin = 0.837, Tmax = 0.977k = −13→14
5484 measured reflectionsl = −12→12

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097All H-atom parameters refined
S = 1.11w = 1/[σ2(Fo2) + (0.0453P)2 + 0.1822P] where P = (Fo2 + 2Fc2)/3
1509 reflections(Δ/σ)max = 0.001
90 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = −0.44 e Å3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1)K.
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cl10.72178 (8)0.63986 (4)0.10842 (5)0.01869 (15)
O10.0169 (3)0.65199 (14)0.47907 (19)0.0268 (4)
O20.1231 (3)0.84048 (13)0.40048 (18)0.0250 (3)
N10.4713 (3)0.49414 (15)0.25596 (19)0.0157 (3)
N20.4212 (3)0.71387 (14)0.26450 (18)0.0151 (3)
N30.1318 (3)0.71851 (16)0.41138 (19)0.0190 (3)
C10.5304 (3)0.61677 (16)0.2149 (2)0.0149 (4)
C20.3104 (3)0.51281 (17)0.3371 (2)0.0164 (4)
C30.2845 (3)0.64762 (17)0.3405 (2)0.0150 (4)
H1N10.525 (4)0.417 (3)0.240 (3)0.025 (6)*
H20.246 (4)0.441 (3)0.375 (3)0.025 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0218 (2)0.0162 (2)0.0214 (3)−0.00093 (16)0.01140 (19)0.00052 (17)
O10.0311 (8)0.0228 (7)0.0340 (9)−0.0028 (6)0.0221 (7)−0.0015 (6)
O20.0308 (8)0.0120 (6)0.0351 (9)0.0043 (5)0.0140 (7)−0.0022 (6)
N10.0193 (8)0.0096 (7)0.0196 (8)0.0010 (6)0.0078 (7)−0.0003 (6)
N20.0179 (8)0.0107 (6)0.0184 (8)0.0001 (5)0.0075 (6)0.0000 (6)
N30.0206 (8)0.0151 (7)0.0231 (9)0.0008 (6)0.0090 (7)−0.0017 (6)
C10.0174 (9)0.0113 (8)0.0163 (9)−0.0013 (6)0.0053 (7)−0.0004 (6)
C20.0186 (9)0.0114 (8)0.0208 (10)−0.0010 (6)0.0082 (8)0.0001 (7)
C30.0167 (9)0.0122 (8)0.0170 (9)−0.0007 (6)0.0060 (7)−0.0019 (7)

Geometric parameters (Å, °)

Cl1—C11.690 (2)N2—C11.313 (2)
O1—N31.228 (2)N2—C31.368 (2)
O2—N31.228 (2)N3—C31.430 (2)
N1—C11.359 (2)C2—C31.362 (2)
N1—C21.363 (3)C2—H20.93 (3)
N1—H1N10.86 (3)
C1—N1—C2107.01 (15)N2—C1—Cl1124.11 (14)
C1—N1—H1N1129.2 (17)N1—C1—Cl1122.87 (14)
C2—N1—H1N1123.7 (17)C3—C2—N1104.32 (16)
C1—N2—C3102.95 (15)C3—C2—H2135.0 (16)
O2—N3—O1124.46 (17)N1—C2—H2120.7 (16)
O2—N3—C3118.46 (16)C2—C3—N2112.71 (17)
O1—N3—C3117.08 (16)C2—C3—N3126.29 (18)
N2—C1—N1113.01 (17)N2—C3—N3120.99 (16)
C3—N2—C1—N1−0.4 (2)C1—N2—C3—C20.0 (2)
C3—N2—C1—Cl1178.70 (15)C1—N2—C3—N3−179.05 (17)
C2—N1—C1—N20.6 (2)O2—N3—C3—C2−177.8 (2)
C2—N1—C1—Cl1−178.52 (14)O1—N3—C3—C21.9 (3)
C1—N1—C2—C3−0.5 (2)O2—N3—C3—N21.1 (3)
N1—C2—C3—N20.3 (2)O1—N3—C3—N2−179.10 (18)
N1—C2—C3—N3179.32 (18)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N1···N2i0.86 (3)2.07 (3)2.900 (2)163 (2)
C2—H2···O1ii0.92 (3)2.48 (3)3.317 (3)151 (2)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI5106).

References

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