1-Methyl-4,5-dinitro-1H-imidazole

Li, Y.-X.; Wang, X.-J.; Wang, J.-L.

doi:10.1107/S1600536809047126

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3073

doi:10.1107/S1600536809047126

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1-Methyl-4,5-dinitro-1H-imidazole

Yong-Xiang Li,^a Xiao-Jun Wang ^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 7 October 2009; accepted 7 November 2009; online 14 November 2009)

In the title compound, C₄H₄N₄O₄, the two nitro groups are twisted with respect to the imidazole plane, making dihedral angles of 24.2 (3) and 33.4 (4)°. In the crystal structure, the molecules are linked through non-classical intermolecular C—H⋯O hydrogen bonds.

Related literature

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

Experimental

Crystal data

C₄H₄N₄O₄
M_r = 172.11
Orthorhombic, P n a 2₁
a = 8.412 (2) Å
b = 12.646 (3) Å
c = 6.563 (1) Å
V = 698.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 293 K
0.40 × 0.30 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.944, T_max = 0.971
3573 measured reflections
871 independent reflections
648 reflections with I > 2σ(I)
R_int = 0.097

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.112
S = 0.95
871 reflections
111 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1ⁱ	0.93	2.49	3.150 (4)	128
C4—H4A⋯O4ⁱⁱ	0.96	2.48	3.428 (5)	170
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-1]$ .

Data collection: RAPID-AUTO (Rigaku, 2000 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809047126/lx2116sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809047126/lx2116Isup2.hkl

checkCIF report

Comment top

Polynitroimidazole systems 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). As a promising candidate, 1-methyl-4,5- dinitroimidazole was synthesized by the nitration of N-methyl- imidazole (Damavarapu et al., 2007). Here we reprot the crystal structure of the title compound (Fig. 1).

In the crystal structure, the two nitro groups are twisted with respect to the imidazole plane, making dihedral angles of 24.2 (3)° (N3/O1, O2) and 33.4 (4)° (N4/O3, O4). The molecular packing (Fig. 2) is stabilized by non-classical intermolecular C–H···O hydrogen bonds; the first between the imidazole H atom and an oxygen of the nitro group, with C1–H1···Oⁱ, the second between the methyl H atom and an oxygen of the nitro group, with C4–H4A···O4ⁱⁱ, respectively (Table 1).

Related literature top

For the synthesis, see: Damavarapu et al. (2007). For th biological activity of polynitroimidazole systems, see: Hofmann (1953); Breccia et al. (1982); Boyer (1986). For their detonation performance, see: Storm et al. (1990); Katritzky et al. (1993); Bulusu et al. (1995).

Experimental top

The title compound was prepared according to literature method (Damavarapu et al., 2007). Single crystals suitable for X-ray diffraction were obtained by evaporation of a solution of the title compound in methanol at room temperature.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2000); cell refinement: RAPID-AUTO (Rigaku, 2000); data reduction: CrystalStructure (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (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. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. C–H···O interactions (dotted lines) in the crystal structure of the title compound. [Symmetry codes: (i) - x + 1/2, y + 1/2, z - 1/2; (ii) x + 1/2, - y + 3/2, z - 1; (iii) - x + 1/2, y - 1/2, z + 1/2; (iv) x - 1/2, - y + 3/2, z + 1.]

1-Methyl-4,5-dinitro-1H-imidazole top

Crystal data top

C₄H₄N₄O₄	F(000) = 352
M_r = 172.11	D_x = 1.637 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 3573 reflections
a = 8.412 (2) Å	θ = 2.9–27.6°
b = 12.646 (3) Å	µ = 0.15 mm⁻¹
c = 6.563 (1) Å	T = 293 K
V = 698.2 (3) Å³	Block, colorless
Z = 4	0.40 × 0.30 × 0.20 mm

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	871 independent reflections
Radiation source: fine-focus sealed tube	648 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.097
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.6°, θ_min = 2.9°
ω scans	h = −10→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −16→16
T_min = 0.944, T_max = 0.971	l = −8→8
3573 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.075P)²] where P = (F_o² + 2F_c²)/3
S = 0.95	(Δ/σ)_max = 0.001
871 reflections	Δρ_max = 0.22 e Å⁻³
111 parameters	Δρ_min = −0.18 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.147 (18)

Crystal data top

C₄H₄N₄O₄	V = 698.2 (3) Å³
M_r = 172.11	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 8.412 (2) Å	µ = 0.15 mm⁻¹
b = 12.646 (3) Å	T = 293 K
c = 6.563 (1) Å	0.40 × 0.30 × 0.20 mm

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	871 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	648 reflections with I > 2σ(I)
T_min = 0.944, T_max = 0.971	R_int = 0.097
3573 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	1 restraint
wR(F²) = 0.112	H-atom parameters constrained
S = 0.95	Δρ_max = 0.22 e Å⁻³
871 reflections	Δρ_min = −0.18 e Å⁻³
111 parameters

Special details top

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
C1	0.2730 (4)	0.7411 (2)	0.2853 (6)	0.0530 (8)
H1	0.3251	0.7751	0.1789	0.064*
C2	0.1370 (3)	0.7145 (2)	0.5486 (5)	0.0449 (7)
C3	0.1843 (3)	0.61741 (19)	0.4808 (5)	0.0378 (6)
C4	0.3530 (4)	0.5610 (3)	0.1731 (6)	0.0607 (9)
H4A	0.3955	0.5988	0.0585	0.091*
H4B	0.2780	0.5092	0.1262	0.091*
H4C	0.4377	0.5264	0.2447	0.091*
N1	0.2728 (2)	0.63562 (17)	0.3106 (4)	0.0410 (6)
N2	0.1915 (4)	0.79129 (19)	0.4271 (5)	0.0561 (7)
N3	0.1551 (3)	0.51403 (18)	0.5576 (4)	0.0490 (7)
N4	0.0529 (3)	0.7419 (2)	0.7316 (5)	0.0569 (7)
O1	0.2496 (3)	0.44510 (19)	0.5115 (6)	0.0806 (9)
O2	0.0370 (3)	0.5008 (2)	0.6601 (5)	0.0773 (9)
O3	0.0716 (4)	0.6874 (3)	0.8832 (5)	0.0878 (10)
O4	−0.0300 (3)	0.8211 (2)	0.7273 (6)	0.0839 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0718 (17)	0.0401 (15)	0.0470 (18)	−0.0025 (13)	0.0072 (16)	0.0127 (15)
C2	0.0424 (13)	0.0501 (16)	0.0421 (16)	0.0026 (10)	−0.0036 (12)	−0.0010 (13)
C3	0.0393 (12)	0.0394 (13)	0.0346 (13)	−0.0021 (9)	−0.0019 (11)	0.0059 (11)
C4	0.0676 (18)	0.0527 (19)	0.062 (2)	0.0108 (14)	0.0197 (17)	0.0053 (17)
N1	0.0471 (10)	0.0376 (12)	0.0384 (12)	0.0002 (9)	0.0032 (11)	0.0074 (11)
N2	0.0737 (16)	0.0423 (14)	0.0524 (18)	0.0039 (11)	0.0002 (15)	0.0042 (12)
N3	0.0560 (13)	0.0463 (14)	0.0446 (15)	−0.0099 (11)	−0.0002 (13)	0.0116 (12)
N4	0.0537 (13)	0.0690 (17)	0.0479 (16)	−0.0004 (14)	−0.0017 (13)	−0.0132 (15)
O1	0.0872 (16)	0.0502 (13)	0.104 (3)	0.0139 (11)	0.0169 (18)	0.0335 (15)
O2	0.0832 (18)	0.0780 (17)	0.071 (2)	−0.0301 (13)	0.0296 (16)	0.0049 (14)
O3	0.116 (2)	0.098 (2)	0.0499 (17)	0.0005 (17)	0.0167 (17)	0.0044 (15)
O4	0.0717 (14)	0.106 (2)	0.074 (2)	0.0307 (13)	−0.0068 (15)	−0.0273 (19)

Geometric parameters (Å, º) top

C1—N2	1.318 (5)	C4—N1	1.470 (4)
C1—N1	1.344 (4)	C4—H4A	0.9600
C1—H1	0.9300	C4—H4B	0.9600
C2—N2	1.337 (4)	C4—H4C	0.9600
C2—C3	1.365 (4)	N3—O2	1.212 (3)
C2—N4	1.436 (4)	N3—O1	1.218 (4)
C3—N1	1.361 (4)	N4—O3	1.220 (5)
C3—N3	1.423 (3)	N4—O4	1.222 (4)

N2—C1—N1	112.9 (3)	H4A—C4—H4C	109.5
N2—C1—H1	123.5	H4B—C4—H4C	109.5
N1—C1—H1	123.5	C1—N1—C3	105.7 (2)
N2—C2—C3	111.0 (3)	C1—N1—C4	124.1 (3)
N2—C2—N4	119.5 (3)	C3—N1—C4	130.2 (2)
C3—C2—N4	129.2 (3)	C1—N2—C2	104.5 (2)
N1—C3—C2	105.9 (2)	O2—N3—O1	125.1 (3)
N1—C3—N3	122.7 (2)	O2—N3—C3	117.8 (3)
C2—C3—N3	131.3 (3)	O1—N3—C3	117.2 (3)
N1—C4—H4A	109.5	O3—N4—O4	123.8 (4)
N1—C4—H4B	109.5	O3—N4—C2	118.8 (3)
H4A—C4—H4B	109.5	O4—N4—C2	117.3 (3)
N1—C4—H4C	109.5

N2—C2—C3—N1	0.4 (3)	C3—C2—N2—C1	−0.3 (4)
N4—C2—C3—N1	−174.1 (3)	N4—C2—N2—C1	174.8 (3)
N2—C2—C3—N3	−179.5 (3)	N1—C3—N3—O2	−155.1 (3)
N4—C2—C3—N3	6.0 (5)	C2—C3—N3—O2	24.8 (5)
N2—C1—N1—C3	0.2 (4)	N1—C3—N3—O1	23.5 (4)
N2—C1—N1—C4	179.3 (3)	C2—C3—N3—O1	−156.6 (3)
C2—C3—N1—C1	−0.3 (3)	N2—C2—N4—O3	−143.7 (4)
N3—C3—N1—C1	179.6 (3)	C3—C2—N4—O3	30.5 (5)
C2—C3—N1—C4	−179.4 (3)	N2—C2—N4—O4	34.1 (4)
N3—C3—N1—C4	0.5 (5)	C3—C2—N4—O4	−151.8 (3)
N1—C1—N2—C2	0.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.93	2.49	3.150 (4)	128
C4—H4A···O4ⁱⁱ	0.96	2.48	3.428 (5)	170

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

Experimental details

Crystal data
Chemical formula	C₄H₄N₄O₄
M_r	172.11
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	293
a, b, c (Å)	8.412 (2), 12.646 (3), 6.563 (1)
V (Å³)	698.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.944, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	3573, 871, 648
R_int	0.097
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.112, 0.95
No. of reflections	871
No. of parameters	111
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.18

Computer programs: RAPID-AUTO (Rigaku, 2000), CrystalStructure (Rigaku, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.93	2.49	3.150 (4)	127.6
C4—H4A···O4ⁱⁱ	0.96	2.48	3.428 (5)	169.9

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

Acknowledgements

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

References

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