1-Methyl-5-nitro-1H-imidazole

Diao, Y.; Wang, W.-Y.; Wei, Z.-H.; Wang, J.-L.

doi:10.1107/S1600536811041705

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3072

doi:10.1107/S1600536811041705

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1-Methyl-5-nitro-1H-imidazole

Ying Diao,^a Wen-Yan Wang,^a Zhi-Hua Wei ^a and Jian-Long Wang ^a ^*

^aSchool of Chemical Engineering and Environment, North University of China, Taiyuan, People's Republic of China
^*Correspondence e-mail: wangjianlong@nuc.edu.cn

(Received 2 October 2011; accepted 10 October 2011; online 29 October 2011)

In the title compound, C₄H₅N₃O₂, the nitro group is twisted with respect to the imidazole ring by a dihedral angle of 5.60 (2)°. Weak intermolecular C—H⋯O and C—H⋯N hydrogen bonding is present in the crystal structure.

Related literature

For the biological properties of nitroimidazole derivatives, see: Hofmann (1953 ); Breccia et al. (1982 ); Boyer (1986 ). For their detonation properties, see: Storm et al. (1990 ); Katritzky et al. (1993 ); Bulusu et al. (1995 ). For the synthesis, see: Damavarapu et al. (2007 ).

Experimental

Crystal data

C₄H₅N₃O₂
M_r = 127.11
Orthorhombic, P b c a
a = 5.323 (3) Å
b = 12.664 (6) Å
c = 15.993 (8) Å
V = 1078.1 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 113 K
0.30 × 0.26 × 0.10 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.963, T_max = 0.987
10144 measured reflections
1272 independent reflections
1030 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.088
S = 1.01
1272 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯N1ⁱ	0.95	2.54	3.342 (2)	143
C4—H4A⋯O2ⁱⁱ	0.98	2.52	3.335 (2)	140
C4—H4C⋯O2ⁱⁱⁱ	0.98	2.58	3.496 (2)	156
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[-x+{\script{5\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811041705/xu5346sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811041705/xu5346Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811041705/xu5346Isup3.cml

checkCIF report

Comment top

Nitroimidazole derivatives have been investigated extensively owing to their biological activity (Hofmann, 1953; Breccia et al., 1982; Boyer, 1986). Recently, these so called "high energy density materials" have attracted renewed attention in conjunction with their favorable detonation performance (Storm et al., 1990; Katritzky et al., 1993; Bulusu et al., 1995). 1-methyl-2,4,5-trinitroimidazole is a promising candidate, as a intermediate, 1-methyl-5-nitroimidazole was synthesized by the nitration of 1-methylimidazole (Damavarapu et al., 2007). Here we report the crystal structure of the title compound (Fig. 1).

In the crystal structure, for the reason that the interaction of methyl group and nitro group, the nitro group is rotated out the imidazole plane, making dihedral angles of 5.60 (2)°.

Related literature top

For the biological properties of nitroimidazole derivatives, see: Hofmann (1953); Breccia et al. (1982); Boyer (1986). For their detonation properties, see: Storm et al. (1990); Katritzky et al. (1993); Bulusu et al. (1995). For the synthesis, see: Damavarapu et al. (2007).

Experimental top

The title compound was prepared according to literature method (Damavarapu et al., 2007). Single crystals were obtained by evaporation of a solution of the title compound in dichloromethane at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound.

1-Methyl-5-nitro-1H-imidazole top

Crystal data top

C₄H₅N₃O₂	F(000) = 528
M_r = 127.11	D_x = 1.566 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3500 reflections
a = 5.323 (3) Å	θ = 1.6–27.8°
b = 12.664 (6) Å	µ = 0.13 mm⁻¹
c = 15.993 (8) Å	T = 113 K
V = 1078.1 (9) Å³	Prism, colorless
Z = 8	0.30 × 0.26 × 0.10 mm

Data collection top

Rigaku Saturn724 CCD diffractometer	1272 independent reflections
Radiation source: rotating anode	1030 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.059
Detector resolution: 14.22 pixels mm^-1	θ_max = 27.8°, θ_min = 2.6°
ω and ϕ scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −16→16
T_min = 0.963, T_max = 0.987	l = −21→21
10144 measured reflections

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)] = 0.036	Hydrogen site location: difference Fourier map
wR(F²) = 0.088	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0505P)²] where P = (F_o² + 2F_c²)/3
1272 reflections	(Δ/σ)_max < 0.001
83 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₄H₅N₃O₂	V = 1078.1 (9) Å³
M_r = 127.11	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 5.323 (3) Å	µ = 0.13 mm⁻¹
b = 12.664 (6) Å	T = 113 K
c = 15.993 (8) Å	0.30 × 0.26 × 0.10 mm

Data collection top

Rigaku Saturn724 CCD diffractometer	1272 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1030 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.987	R_int = 0.059
10144 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.01	Δρ_max = 0.17 e Å⁻³
1272 reflections	Δρ_min = −0.32 e Å⁻³
83 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
O1	1.21610 (15)	0.62227 (7)	0.20073 (5)	0.0222 (2)
O2	1.10195 (15)	0.47117 (7)	0.14851 (6)	0.0272 (3)
N1	0.54173 (19)	0.64301 (8)	0.03187 (6)	0.0201 (3)
N2	0.80463 (17)	0.72006 (7)	0.12271 (6)	0.0150 (2)
N3	1.07644 (17)	0.56758 (8)	0.15745 (6)	0.0175 (2)
C1	0.6053 (2)	0.73142 (10)	0.07171 (7)	0.0179 (3)
H1	0.5183	0.7963	0.0648	0.021*
C2	0.7109 (2)	0.56985 (9)	0.05864 (7)	0.0184 (3)
H2	0.7152	0.4980	0.0416	0.022*
C3	0.87376 (19)	0.61580 (9)	0.11396 (7)	0.0154 (3)
C4	0.9175 (2)	0.80490 (9)	0.17239 (7)	0.0194 (3)
H4A	1.0842	0.8217	0.1501	0.029*
H4B	0.9332	0.7819	0.2307	0.029*
H4C	0.8105	0.8678	0.1696	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0187 (5)	0.0260 (5)	0.0220 (5)	−0.0025 (4)	−0.0049 (3)	−0.0034 (4)
O2	0.0288 (5)	0.0155 (5)	0.0373 (6)	0.0058 (4)	−0.0066 (4)	−0.0020 (4)
N1	0.0223 (6)	0.0185 (6)	0.0196 (5)	−0.0001 (4)	−0.0043 (4)	0.0009 (4)
N2	0.0164 (5)	0.0132 (5)	0.0153 (5)	−0.0020 (4)	−0.0003 (4)	0.0010 (4)
N3	0.0170 (5)	0.0176 (5)	0.0179 (5)	0.0002 (4)	0.0003 (4)	0.0000 (4)
C1	0.0165 (6)	0.0183 (6)	0.0188 (6)	0.0003 (5)	0.0000 (4)	0.0028 (5)
C2	0.0208 (6)	0.0157 (6)	0.0186 (6)	−0.0012 (5)	−0.0016 (5)	−0.0007 (5)
C3	0.0159 (6)	0.0142 (6)	0.0161 (5)	0.0002 (4)	0.0002 (4)	0.0006 (4)
C4	0.0217 (6)	0.0150 (6)	0.0215 (6)	−0.0037 (5)	−0.0003 (5)	−0.0028 (5)

Geometric parameters (Å, º) top

O1—N3	1.2294 (12)	N3—C3	1.4215 (14)
O2—N3	1.2368 (14)	C1—H1	0.9500
N1—C1	1.3319 (16)	C2—C3	1.3687 (16)
N1—C2	1.3610 (15)	C2—H2	0.9500
N2—C1	1.3459 (15)	C4—H4A	0.9800
N2—C3	1.3778 (16)	C4—H4B	0.9800
N2—C4	1.4651 (15)	C4—H4C	0.9800

C1—N1—C2	104.69 (10)	N1—C2—H2	125.3
C1—N2—C3	104.56 (9)	C3—C2—H2	125.3
C1—N2—C4	124.99 (10)	C2—C3—N2	107.69 (10)
C3—N2—C4	130.42 (10)	C2—C3—N3	127.92 (11)
O1—N3—O2	123.70 (10)	N2—C3—N3	124.38 (10)
O1—N3—C3	119.50 (10)	N2—C4—H4A	109.5
O2—N3—C3	116.80 (10)	N2—C4—H4B	109.5
N1—C1—N2	113.60 (10)	H4A—C4—H4B	109.5
N1—C1—H1	123.2	N2—C4—H4C	109.5
N2—C1—H1	123.2	H4A—C4—H4C	109.5
N1—C2—C3	109.45 (11)	H4B—C4—H4C	109.5

C2—N1—C1—N2	−0.13 (13)	C4—N2—C3—C2	−178.47 (10)
C3—N2—C1—N1	0.39 (13)	C1—N2—C3—N3	−179.24 (10)
C4—N2—C1—N1	178.52 (10)	C4—N2—C3—N3	2.77 (18)
C1—N1—C2—C3	−0.19 (12)	O1—N3—C3—C2	174.93 (10)
N1—C2—C3—N2	0.43 (13)	O2—N3—C3—C2	−4.59 (17)
N1—C2—C3—N3	179.13 (10)	O1—N3—C3—N2	−6.56 (16)
C1—N2—C3—C2	−0.48 (12)	O2—N3—C3—N2	173.92 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N1ⁱ	0.95	2.54	3.342 (2)	143
C4—H4A···O2ⁱⁱ	0.98	2.52	3.335 (2)	140
C4—H4C···O2ⁱⁱⁱ	0.98	2.58	3.496 (2)	156

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+5/2, y+1/2, z; (iii) −x+3/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₄H₅N₃O₂
M_r	127.11
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	113
a, b, c (Å)	5.323 (3), 12.664 (6), 15.993 (8)
V (Å³)	1078.1 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.30 × 0.26 × 0.10

Data collection
Diffractometer	Rigaku Saturn724 CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.963, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	10144, 1272, 1030
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.657

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.088, 1.01
No. of reflections	1272
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.32

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N1ⁱ	0.95	2.54	3.342 (2)	143
C4—H4A···O2ⁱⁱ	0.98	2.52	3.335 (2)	140
C4—H4C···O2ⁱⁱⁱ	0.98	2.58	3.496 (2)	156

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+5/2, y+1/2, z; (iii) −x+3/2, y+1/2, z.

Acknowledgements

The authors thank China North Industries Group Corporation for financial support.

References

Boyer, J. H. (1986). Nitroazoles: The C-Nitro Derivatives of Five-Membered N- and N,O-Heterocycles. Deerfield Beach, FL: VCH Google Scholar
Breccia, A., Cavalleri, B. & Adams, G. E. (1982). Nitroimidazoles: Chemistry, Pharmacology, and Clinical Application. New York: Plenum. Google Scholar
Bulusu, S., Damavarapu, R., Autera, J. R., Behrens, R. Jr, Minier, L. M., Villanueva, J., Jayasuriya, K. & Axenrod, T. (1995). J. Phys. Chem. 99, 5009–5015. CrossRef CAS Web of Science Google Scholar
Damavarapu, R., Surapaneni, R. C., Gelber, N., Duddu, R. G., Zhang, M.-J. & Dave, P. R. (2007). US Patent No. 7304164. Google Scholar
Hofmann, K. (1953). Imidazole and Its Derivatives, Part I. New York: Interscience. Google Scholar
Katritzky, A. R., Cundy, D. J. & Chen, J. (1993). J. Energetic Mat. 11, 345–352. CrossRef CAS Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Storm, C. B., Stine, J. R. & Kramer, J. F. (1990). Chemistry and Physics of Energetic Materials. Dordrecht: Kluwer Academic. Google Scholar