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

Fun, H.-K.; Goh, J.H.; Chandrakantha, B.; Isloor, A.M.; Shetty, P.

doi:10.1107/S1600536810024542

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Pages o1828-o1829

doi:10.1107/S1600536810024542

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

Hoong-Kun Fun,^a ^*‡ Jia Hao Goh,^a § B. Chandrakantha,^b Arun M. Isloor ^c and Prakash Shetty ^d

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bSyngene International Ltd, Biocon Park, Plot Nos. 2 & 3, Bommasandra 4th Phase, Jigani Link Road, Bangalore 560 100, India, ^cOrganic Chemistry Division, Department of Chemistry, National Institute of Technology-Karnataka, Surathkal, Mangalore 575 025, India, and ^dDepartment of Printing, Manipal Institute of Technology, Manipal University, Manipal 576 104, India
^*Correspondence e-mail: hkfun@usm.my

(Received 18 June 2010; accepted 23 June 2010; online 26 June 2010)

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 R₂²(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 ); Clark & Macquarrie (1996 ); Jadhav et al. (2008 ); Kolavi et al. (2006 ); Susanta et al. (2000 ). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995 ). For related 4-nitroimidazole crystal structures, see: Ségalas et al. (1992 ); De Bondt et al. (1993 ). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₃H₂ClN₃O₂
M_r = 147.53
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.037
wR(F²) = 0.097
S = 1.11
1509 reflections
90 parameters
All H-atom parameters refined
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯N2ⁱ	0.86 (3)	2.07 (3)	2.900 (2)	163 (2)
C2—H2⋯O1ⁱⁱ	0.92 (3)	2.48 (3)	3.317 (3)	151 (2)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z+1.

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 ).

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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).

Computing details top

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

Figures top

	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.

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

Crystal data top

C₃H₂ClN₃O₂	F(000) = 296
M_r = 147.53	D_x = 1.873 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2073 reflections
a = 5.905 (2) Å	θ = 3.6–30.0°
b = 10.033 (4) Å	µ = 0.64 mm⁻¹
c = 9.150 (3) Å	T = 100 K
β = 105.180 (8)°	Plate, yellow
V = 523.2 (3) Å³	0.29 × 0.19 × 0.04 mm
Z = 4

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	1509 independent reflections
Radiation source: fine-focus sealed tube	1195 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 30.0°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −6→8
T_min = 0.837, T_max = 0.977	k = −13→14
5484 measured reflections	l = −12→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	All H-atom parameters refined
S = 1.11	w = 1/[σ²(F_o²) + (0.0453P)² + 0.1822P] where P = (F_o² + 2F_c²)/3
1509 reflections	(Δ/σ)_max = 0.001
90 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₃H₂ClN₃O₂	V = 523.2 (3) Å³
M_r = 147.53	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.905 (2) Å	µ = 0.64 mm⁻¹
b = 10.033 (4) Å	T = 100 K
c = 9.150 (3) Å	0.29 × 0.19 × 0.04 mm
β = 105.180 (8)°

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	1509 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1195 reflections with I > 2σ(I)
T_min = 0.837, T_max = 0.977	R_int = 0.037
5484 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.097	All H-atom parameters refined
S = 1.11	Δρ_max = 0.42 e Å⁻³
1509 reflections	Δρ_min = −0.44 e Å⁻³
90 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Cl1	0.72178 (8)	0.63986 (4)	0.10842 (5)	0.01869 (15)
O1	0.0169 (3)	0.65199 (14)	0.47907 (19)	0.0268 (4)
O2	0.1231 (3)	0.84048 (13)	0.40048 (18)	0.0250 (3)
N1	0.4713 (3)	0.49414 (15)	0.25596 (19)	0.0157 (3)
N2	0.4212 (3)	0.71387 (14)	0.26450 (18)	0.0151 (3)
N3	0.1318 (3)	0.71851 (16)	0.41138 (19)	0.0190 (3)
C1	0.5304 (3)	0.61677 (16)	0.2149 (2)	0.0149 (4)
C2	0.3104 (3)	0.51281 (17)	0.3371 (2)	0.0164 (4)
C3	0.2845 (3)	0.64762 (17)	0.3405 (2)	0.0150 (4)
H1N1	0.525 (4)	0.417 (3)	0.240 (3)	0.025 (6)*
H2	0.246 (4)	0.441 (3)	0.375 (3)	0.025 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0218 (2)	0.0162 (2)	0.0214 (3)	−0.00093 (16)	0.01140 (19)	0.00052 (17)
O1	0.0311 (8)	0.0228 (7)	0.0340 (9)	−0.0028 (6)	0.0221 (7)	−0.0015 (6)
O2	0.0308 (8)	0.0120 (6)	0.0351 (9)	0.0043 (5)	0.0140 (7)	−0.0022 (6)
N1	0.0193 (8)	0.0096 (7)	0.0196 (8)	0.0010 (6)	0.0078 (7)	−0.0003 (6)
N2	0.0179 (8)	0.0107 (6)	0.0184 (8)	0.0001 (5)	0.0075 (6)	0.0000 (6)
N3	0.0206 (8)	0.0151 (7)	0.0231 (9)	0.0008 (6)	0.0090 (7)	−0.0017 (6)
C1	0.0174 (9)	0.0113 (8)	0.0163 (9)	−0.0013 (6)	0.0053 (7)	−0.0004 (6)
C2	0.0186 (9)	0.0114 (8)	0.0208 (10)	−0.0010 (6)	0.0082 (8)	0.0001 (7)
C3	0.0167 (9)	0.0122 (8)	0.0170 (9)	−0.0007 (6)	0.0060 (7)	−0.0019 (7)

Geometric parameters (Å, º) top

Cl1—C1	1.690 (2)	N2—C1	1.313 (2)
O1—N3	1.228 (2)	N2—C3	1.368 (2)
O2—N3	1.228 (2)	N3—C3	1.430 (2)
N1—C1	1.359 (2)	C2—C3	1.362 (2)
N1—C2	1.363 (3)	C2—H2	0.93 (3)
N1—H1N1	0.86 (3)

C1—N1—C2	107.01 (15)	N2—C1—Cl1	124.11 (14)
C1—N1—H1N1	129.2 (17)	N1—C1—Cl1	122.87 (14)
C2—N1—H1N1	123.7 (17)	C3—C2—N1	104.32 (16)
C1—N2—C3	102.95 (15)	C3—C2—H2	135.0 (16)
O2—N3—O1	124.46 (17)	N1—C2—H2	120.7 (16)
O2—N3—C3	118.46 (16)	C2—C3—N2	112.71 (17)
O1—N3—C3	117.08 (16)	C2—C3—N3	126.29 (18)
N2—C1—N1	113.01 (17)	N2—C3—N3	120.99 (16)

C3—N2—C1—N1	−0.4 (2)	C1—N2—C3—C2	0.0 (2)
C3—N2—C1—Cl1	178.70 (15)	C1—N2—C3—N3	−179.05 (17)
C2—N1—C1—N2	0.6 (2)	O2—N3—C3—C2	−177.8 (2)
C2—N1—C1—Cl1	−178.52 (14)	O1—N3—C3—C2	1.9 (3)
C1—N1—C2—C3	−0.5 (2)	O2—N3—C3—N2	1.1 (3)
N1—C2—C3—N2	0.3 (2)	O1—N3—C3—N2	−179.10 (18)
N1—C2—C3—N3	179.32 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N2ⁱ	0.86 (3)	2.07 (3)	2.900 (2)	163 (2)
C2—H2···O1ⁱⁱ	0.92 (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.

Experimental details

Crystal data
Chemical formula	C₃H₂ClN₃O₂
M_r	147.53
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	5.905 (2), 10.033 (4), 9.150 (3)
β (°)	105.180 (8)
V (Å³)	523.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.64
Crystal size (mm)	0.29 × 0.19 × 0.04

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.837, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	5484, 1509, 1195
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.097, 1.11
No. of reflections	1509
No. of parameters	90
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.44

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N2ⁱ	0.86 (3)	2.07 (3)	2.900 (2)	163 (2)
C2—H2···O1ⁱⁱ	0.92 (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

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: C-7576-2009.

Acknowledgements

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.

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