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

Abstract

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,

• a = 5.323 (3) Å

• b = 12.664 (6) Å

• c = 15.993 (8) Å

• V = 1078.1 (9) ų

• 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[F ² > 2σ(F ²)] = 0.036

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811041705/xu5346Isup3.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
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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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)°.

Experimental

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.

Refinement

All H atoms were positioned geometrically and treated as riding, with C—H = 0.95 ° for imidazole ring H and 0.98 ° for methyl H atoms, and with U_iso(H) = 1.2U_eq(C) for imidazole ring H atom and 1.5U_eq(C) for methyl H atoms.

Figures

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.

Crystal data

C4H5N3O2	F(000) = 528
Mr = 127.11	Dx = 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

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

Refinement

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(Fo2) + (0.0505P)2] where P = (Fo2 + 2Fc2)/3
1272 reflections	(Δ/σ)max < 0.001
83 parameters	Δρmax = 0.17 e Å−3
0 restraints	Δρmin = −0.32 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.