Crystal structure of 4,5-di-nitro-1H-imidazole.

The title compound, C3H2N4O4, forms crystals with two mol-ecules in the asymmetric unit which are conformationally similar. With the exception of the O atoms of the nitro groups, the mol-ecules are essentially planar. In the crystal, adjacent mol-ecules are associated by N-H⋯N hydrogen bonds involving the imidazole N-H donors and N-atom acceptors of the unsaturated nitro-gen of neighboring rings, forming layers parallel to (010).

Related literature

For background to imidazoles and the title compound, see: Windaus & Vogt (1907 ▸); Cooper (1996 ▸); Epishina et al. (1967 ▸). For the preparation, see: Novikov et al. (1970 ▸). For similar structures, see: Parrish et al. (2015 ▸); Windler et al. (2015 ▸).

Experimental

Crystal data

C3H2N4O4

M = 158.09

Monoclinic,

a = 11.4797 (9) Å

b = 8.8205 (7) Å

c = 11.802 (1) Å

β = 107.827 (1)°

V = 1137.65 (16) Å3

Z = 8

Mo Kα radiation

μ = 0.17 mm−1

T = 100 K

0.12 × 0.06 × 0.06 mm

Data collection

Bruker D8 Quest with CMOS diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T min = 0.971, T max = 0.995

25837 measured reflections

4868 independent reflections

4216 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.118

S = 1.60

4868 reflections

211 parameters

All H-atom parameters refined

Δρmax = 0.54 e Å−3

Δρmin = −0.33 e Å−3

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸), Mercury (Macrae et al., 2008 ▸) and PLATON (Spek, 2009 ▸); software used to prepare material for publication: CHEMDRAW Ultra (Cambridge Soft, 2014 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015013432/zs2338sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015013432/zs2338Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015013432/zs2338Isup3.cdx

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015013432/zs2338Isup4.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015013432/zs2338fig1.tif

The mol­ecular structure of the title compound with atom labeling. Ellipsoids are drawn at the 50% probability level and the hydrogen atoms are drawn as spheres of arbitrary size.

Click here for additional data file.

b . DOI: 10.1107/S2056989015013432/zs2338fig2.tif

A crystal packing diagram for the title compound viewed along the b axis. The N—H⋯N hydrogen bonds are shown as dashed lines.

CCDC reference: 1412685

Additional supporting information: crystallographic information; 3D view; checkCIF report

C3H2N4O4	F(000) = 640
Mr = 158.09	Dx = 1.846 Mg m−3
Monoclinic, P21/n	Melting point = 460–461 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 11.4797 (9) Å	Cell parameters from 4868 reflections
b = 8.8205 (7) Å	θ = 2.9–35.4°
c = 11.802 (1) Å	µ = 0.17 mm−1
β = 107.827 (1)°	T = 100 K
V = 1137.65 (16) Å3	Block, colorless
Z = 8	0.12 × 0.06 × 0.06 mm

Bruker D8 Quest with CMOS diffractometer	4868 independent reflections
Radiation source: fine-focus sealed tube	4216 reflections with I > 2σ(I)
Bruker Triumph curved graphite monochromator	Rint = 0.024
ω scans	θmax = 35.4°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −17→18
Tmin = 0.971, Tmax = 0.995	k = −14→13
25837 measured reflections	l = −18→18

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) = 0.118	All H-atom parameters refined
S = 1.60	w = 1/[σ2(Fo2) + (0.0548P)2] where P = (Fo2 + 2Fc2)/3
4868 reflections	(Δ/σ)max = 0.001
211 parameters	Δρmax = 0.54 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

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.

	x	y	z	Uiso*/Ueq
N1	0.29370 (6)	0.50168 (8)	0.81909 (6)	0.01298 (13)
N2	0.15331 (6)	0.38337 (8)	1.01582 (6)	0.01315 (13)
N3	0.11402 (6)	0.37089 (8)	0.70000 (6)	0.01075 (12)
N4	0.01562 (6)	0.30341 (8)	0.82719 (6)	0.01203 (13)
N5	0.51594 (6)	0.79131 (8)	0.14048 (6)	0.01209 (13)
N6	0.33377 (6)	0.62492 (8)	0.27135 (6)	0.01158 (12)
N7	0.31591 (6)	0.85813 (8)	0.01033 (6)	0.01174 (12)
N8	0.19372 (6)	0.75974 (8)	0.10560 (6)	0.01083 (12)
O1	0.31536 (6)	0.52596 (8)	0.72497 (6)	0.02044 (14)
O2	0.35443 (7)	0.54920 (9)	0.91643 (6)	0.02736 (17)
O3	0.25949 (6)	0.41102 (8)	1.07370 (6)	0.01982 (14)
O4	0.06957 (6)	0.36304 (9)	1.05882 (6)	0.02084 (14)
O5	0.55956 (6)	0.80860 (9)	0.05851 (6)	0.02079 (14)
O6	0.57642 (6)	0.78190 (8)	0.24607 (5)	0.01798 (13)
O7	0.43309 (5)	0.56137 (7)	0.30593 (6)	0.01585 (12)
O8	0.24913 (6)	0.60769 (8)	0.31361 (6)	0.01785 (13)
C1	0.18544 (7)	0.41388 (8)	0.81011 (6)	0.01016 (13)
C2	0.01380 (7)	0.30381 (9)	0.71412 (7)	0.01240 (14)
C3	0.12271 (7)	0.37018 (8)	0.88769 (6)	0.01062 (13)
C4	0.38434 (7)	0.78740 (8)	0.11035 (6)	0.01003 (13)
C5	0.20090 (7)	0.83961 (9)	0.01039 (7)	0.01204 (14)
C6	0.31069 (7)	0.72465 (8)	0.17067 (6)	0.00992 (13)
H1	−0.044 (2)	0.259 (3)	0.651 (2)	0.080*
H2	0.129 (2)	0.386 (3)	0.630 (2)	0.080*
H3	0.133 (2)	0.875 (3)	−0.045 (2)	0.080*
H4	0.125 (2)	0.740 (3)	0.1274 (19)	0.080*

	U11	U22	U33	U12	U13	U23
N1	0.0108 (3)	0.0118 (3)	0.0163 (3)	−0.0018 (2)	0.0041 (2)	−0.0016 (2)
N2	0.0163 (3)	0.0130 (3)	0.0101 (3)	0.0017 (2)	0.0039 (2)	0.0008 (2)
N3	0.0099 (3)	0.0133 (3)	0.0102 (3)	−0.0015 (2)	0.0047 (2)	−0.0021 (2)
N4	0.0110 (3)	0.0151 (3)	0.0109 (3)	−0.0013 (2)	0.0047 (2)	−0.0008 (2)
N5	0.0099 (3)	0.0128 (3)	0.0138 (3)	−0.0012 (2)	0.0039 (2)	0.0000 (2)
N6	0.0119 (3)	0.0126 (3)	0.0100 (3)	−0.0010 (2)	0.0031 (2)	0.0009 (2)
N7	0.0108 (3)	0.0154 (3)	0.0098 (3)	0.0015 (2)	0.0042 (2)	0.0018 (2)
N8	0.0089 (3)	0.0147 (3)	0.0096 (3)	0.0004 (2)	0.0038 (2)	0.0005 (2)
O1	0.0205 (3)	0.0243 (3)	0.0221 (3)	−0.0084 (2)	0.0147 (2)	−0.0065 (2)
O2	0.0271 (4)	0.0329 (4)	0.0170 (3)	−0.0173 (3)	−0.0009 (3)	−0.0019 (3)
O3	0.0195 (3)	0.0229 (3)	0.0135 (3)	−0.0047 (2)	−0.0003 (2)	−0.0017 (2)
O4	0.0197 (3)	0.0315 (4)	0.0139 (3)	0.0045 (3)	0.0091 (2)	0.0044 (2)
O5	0.0135 (3)	0.0340 (4)	0.0182 (3)	−0.0032 (2)	0.0097 (2)	−0.0037 (2)
O6	0.0123 (3)	0.0222 (3)	0.0156 (3)	−0.0039 (2)	−0.0014 (2)	0.0056 (2)
O7	0.0114 (2)	0.0170 (3)	0.0171 (3)	0.0014 (2)	0.0013 (2)	0.0044 (2)
O8	0.0166 (3)	0.0229 (3)	0.0173 (3)	0.0010 (2)	0.0099 (2)	0.0062 (2)
C1	0.0093 (3)	0.0104 (3)	0.0113 (3)	−0.0006 (2)	0.0039 (2)	−0.0013 (2)
C2	0.0105 (3)	0.0162 (3)	0.0118 (3)	−0.0022 (2)	0.0053 (2)	−0.0021 (2)
C3	0.0111 (3)	0.0118 (3)	0.0093 (3)	0.0004 (2)	0.0037 (2)	−0.0004 (2)
C4	0.0086 (3)	0.0120 (3)	0.0097 (3)	0.0000 (2)	0.0031 (2)	−0.0006 (2)
C5	0.0109 (3)	0.0157 (3)	0.0100 (3)	0.0021 (2)	0.0040 (2)	0.0016 (2)
C6	0.0095 (3)	0.0121 (3)	0.0080 (3)	0.0000 (2)	0.0025 (2)	0.0005 (2)

O1—N1	1.2291 (10)	N4—C3	1.3530 (11)
O2—N1	1.2211 (10)	N3—H2	0.90 (2)
O3—N2	1.2256 (10)	N5—C4	1.4426 (11)
O4—N2	1.2299 (10)	N6—C6	1.4364 (10)
O5—N5	1.2274 (10)	N7—C5	1.3306 (11)
O6—N5	1.2297 (9)	N7—C4	1.3535 (10)
O7—N6	1.2230 (10)	N8—C6	1.3628 (11)
O8—N6	1.2299 (10)	N8—C5	1.3500 (11)
N1—C1	1.4404 (11)	N8—H4	0.92 (2)
N2—C3	1.4486 (10)	C1—C3	1.3817 (11)
N3—C1	1.3610 (10)	C2—H1	0.92 (2)
N3—C2	1.3487 (11)	C4—C6	1.3771 (11)
N4—C2	1.3282 (10)	C5—H3	0.91 (2)
O1—N1—O2	125.12 (8)	C6—N8—H4	125.6 (14)
O1—N1—C1	115.84 (7)	N1—C1—C3	135.58 (7)
O2—N1—C1	119.01 (7)	N3—C1—C3	105.73 (7)
O3—N2—O4	124.66 (7)	N1—C1—N3	118.30 (6)
O3—N2—C3	118.67 (7)	N3—C2—N4	111.94 (7)
O4—N2—C3	116.66 (7)	N2—C3—C1	131.32 (7)
C1—N3—C2	106.95 (7)	N4—C3—C1	110.21 (6)
C2—N4—C3	105.15 (7)	N2—C3—N4	118.47 (7)
C1—N3—H2	127.2 (15)	N3—C2—H1	121.3 (15)
C2—N3—H2	125.9 (15)	N4—C2—H1	126.7 (15)
O5—N5—C4	117.25 (7)	N7—C4—C6	110.60 (7)
O6—N5—C4	118.16 (7)	N5—C4—N7	119.23 (7)
O5—N5—O6	124.55 (8)	N5—C4—C6	130.13 (7)
O8—N6—C6	116.27 (7)	N7—C5—N8	112.21 (7)
O7—N6—C6	118.28 (7)	N8—C6—C4	105.81 (6)
O7—N6—O8	125.42 (7)	N6—C6—N8	120.37 (7)
C4—N7—C5	104.72 (7)	N6—C6—C4	133.38 (7)
C5—N8—C6	106.67 (7)	N7—C5—H3	126.3 (15)
C5—N8—H4	127.5 (14)	N8—C5—H3	121.5 (15)
O1—N1—C1—N3	−2.71 (11)	O7—N6—C6—N8	159.07 (7)
O1—N1—C1—C3	−174.29 (9)	O7—N6—C6—C4	−12.11 (12)
O2—N1—C1—N3	175.41 (8)	O8—N6—C6—N8	−18.96 (10)
O2—N1—C1—C3	3.83 (14)	O8—N6—C6—C4	169.86 (8)
O3—N2—C3—N4	163.63 (7)	C4—N7—C5—N8	−0.32 (9)
O3—N2—C3—C1	−15.76 (12)	C5—N7—C4—N5	−177.47 (7)
O4—N2—C3—N4	−15.16 (11)	C5—N7—C4—C6	0.55 (9)
O4—N2—C3—C1	165.45 (8)	C5—N8—C6—N6	−173.00 (7)
C2—N3—C1—N1	−174.24 (7)	C5—N8—C6—C4	0.35 (8)
C2—N3—C1—C3	−0.35 (8)	C6—N8—C5—N7	−0.02 (9)
C1—N3—C2—N4	1.06 (9)	N3—C1—C3—N4	−0.44 (9)
C3—N4—C2—N3	−1.31 (9)	N1—C1—C3—N2	−8.71 (15)
C2—N4—C3—N2	−178.45 (7)	N1—C1—C3—N4	171.86 (8)
C2—N4—C3—C1	1.06 (9)	N3—C1—C3—N2	178.98 (8)
O6—N5—C4—C6	−25.25 (12)	N5—C4—C6—N6	−10.74 (14)
O5—N5—C4—N7	−25.48 (11)	N5—C4—C6—N8	177.17 (7)
O5—N5—C4—C6	156.95 (8)	N7—C4—C6—N6	171.53 (8)
O6—N5—C4—N7	152.33 (7)	N7—C4—C6—N8	−0.57 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2···N7i	0.90 (2)	1.96 (2)	2.836 (1)	163 (2)
N8—H4···N4ii	0.92 (2)	1.89 (2)	2.807 (1)	179 (3)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N3H2N7i	0.90(2)	1.96(2)	2.836(1)	163(2)
N8H4N4ii	0.92(2)	1.89(2)	2.807(1)	179(3)

Symmetry codes: (i) ; (ii) .