2-Methyl-4-nitro-1-(4-nitro­phen­yl)-1H-imidazole

In the title compound, C₁₀H₈N₄O₄, two planar fragments, viz. the imidazole and nitro­phenyl rings, are tilted at a dihedral of 57.89 (7)°. The nitro groups are twisted with respect to the neighbouring ring planes; the dihedral angle is 7.0 (3)° for imidazole and 9.68 (8)° for benzene. The crystal structure consists of centrosymmetric dimers generated by C—H...O hydrogen bonds, which are connected by C—H...N hydrogen bonds into rows along the [001] direction. The neighbouring rows are connected via C—H...O inter­actions into a two-dimensional network in the bc plane.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.038
• wR factor = 0.099
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.92 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N14    -   C14     ..       6.33 su

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Simple 4-nitroimidzoles are convenient compounds for studying weak interactions in molecular crystals. The molecules are relatively simple, with few degrees of conformational freedom, and the appropriate choice of substituents can highlight certain kind of interaction. Here, in 1-(4-nitrophenyl)-2-methyl-4-nitroimidazole the available specific interactions range from π-π interactions, through weak hydrogen bonds to nitro-nitro interactions. It turned out that the crystal packing is determined by relatively short and directional C—H···N and C—H···O hydrogen bonds. The first level of organization is the centrosymmetric C—H···O bonded dimer. These dimers are connected by C—H···N hydrogen bonds along [001] direction producing the tapes which are connected into two-dimensional network in the bc plane. The plane of imidazole ring makes the angle of 57.89° with the benzene ring.

Related literature

This is a part of our studies of intermolecular interactions on 4-nitroimidazole derivatives (Kubicki, 2004). The crystal structures of other 1-aryl-2-methyl-4-nitroimidazoles were described by Kowalski (1995, 1996), Kubicki (2004) and Kubicki & Wagner (2007). For related literature, see: Suwiński et al. (1993).

S2. Experimental

The title compound has been synthesized by aromatic nucleophilic substitution by 4(5)-nitro-2-methylimidazole to 4-fluoronitrobenzene catalysed by sodium hydroxide [Suwiński et al., (1993)].

S3. Refinement

Hydrogen atoms were freely refined, and then, for the last cycles of refinement, both the refined geometry and displacement parameters were restrained to keep the refined values.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Molecular structure of (I) with dispalcement parameters scalled at the 50% probability level (Siemens, 1989) and numbering scheme. The hydrogen atoms are drawn as spheres of arbitrary radii.
	Fig. 2. The two-dimensional hydrogen-bonded network of (I) along a axis. Hydrogen bonds are drawn as dashed lines.

2-Methyl-4-nitro-1-(4-nitrophenyl)-1H-imidazole

Crystal data

C10H8N4O4	F(000) = 1024
Mr = 248.20	Dx = 1.533 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3523 reflections
a = 8.1416 (9) Å	θ = 4–22°
b = 12.7121 (10) Å	µ = 0.12 mm^−1
c = 20.7789 (13) Å	T = 100 K
V = 2150.6 (3) Å^3	Needle, colourless
Z = 8	0.4 × 0.15 × 0.05 mm

Data collection

Kuma KM-4-CCD four-circle diffractometer	2092 independent reflections
Radiation source: fine-focus sealed tube	1442 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
ω scan	θmax = 26.0°, θmin = 3.2°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	h = −9→10
Tmin = 0.918, Tmax = 1.000	k = −15→14
11596 measured reflections	l = −25→25

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0481P)^2 + 0.1988P] where P = (Fo^2 + 2Fc^2)/3
2092 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.24 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
N1	0.88142 (17)	0.07302 (11)	0.63572 (7)	0.0169 (4)
C11	0.7321 (2)	0.09541 (14)	0.60164 (8)	0.0157 (4)
C12	0.5883 (2)	0.11064 (14)	0.63618 (9)	0.0179 (4)
H12	0.5884	0.1074	0.6814	0.022*
C13	0.4431 (2)	0.13081 (13)	0.60316 (9)	0.0190 (4)
H13	0.3489	0.1428	0.6262	0.013*
C14	0.4484 (2)	0.13426 (13)	0.53655 (9)	0.0166 (4)
N14	0.29294 (19)	0.14829 (11)	0.50133 (8)	0.0205 (4)
O141	0.29927 (17)	0.16023 (10)	0.44276 (6)	0.0265 (3)
O142	0.16320 (16)	0.14491 (10)	0.53195 (7)	0.0287 (4)
C15	0.5904 (2)	0.12051 (13)	0.50162 (9)	0.0171 (4)
H15	0.5864	0.1234	0.4579	0.018*
C16	0.7355 (2)	0.10102 (14)	0.53454 (8)	0.0176 (4)
H16	0.8411	0.0954	0.5120	0.025*
C2	0.9542 (2)	0.13460 (13)	0.68233 (9)	0.0172 (4)
C21	0.8855 (2)	0.23579 (14)	0.70574 (9)	0.0204 (4)
H21A	0.8362	0.2761	0.6711	0.051*
H21B	0.9711	0.2734	0.7232	0.036*
H21C	0.8029	0.2243	0.7389	0.028*
N3	1.09046 (17)	0.09022 (12)	0.70367 (7)	0.0174 (3)
C4	1.1017 (2)	−0.00159 (14)	0.66976 (8)	0.0160 (4)
N4	1.23301 (18)	−0.07395 (12)	0.68067 (7)	0.0200 (4)
O41	1.32853 (17)	−0.05715 (11)	0.72537 (6)	0.0293 (4)
O42	1.24362 (16)	−0.15076 (10)	0.64383 (6)	0.0258 (3)
C5	0.9775 (2)	−0.01455 (14)	0.62716 (8)	0.0184 (4)
H5	0.9442	−0.0686	0.5998	0.019*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0150 (8)	0.0190 (8)	0.0167 (8)	−0.0009 (6)	0.0001 (6)	0.0012 (6)
C11	0.0159 (9)	0.0134 (9)	0.0177 (9)	−0.0014 (7)	−0.0023 (8)	0.0006 (8)
C12	0.0179 (9)	0.0220 (10)	0.0138 (9)	−0.0015 (8)	−0.0004 (8)	0.0009 (8)
C13	0.0169 (10)	0.0185 (10)	0.0216 (10)	−0.0025 (7)	0.0054 (8)	−0.0007 (8)
C14	0.0145 (9)	0.0134 (9)	0.0219 (10)	−0.0012 (7)	−0.0063 (8)	0.0000 (8)
N14	0.0214 (9)	0.0147 (8)	0.0255 (9)	−0.0013 (6)	−0.0036 (7)	0.0008 (7)
O141	0.0332 (9)	0.0256 (8)	0.0207 (7)	−0.0006 (6)	−0.0100 (6)	0.0030 (6)
O142	0.0209 (7)	0.0293 (8)	0.0360 (9)	−0.0005 (6)	−0.0024 (7)	0.0065 (7)
C15	0.0224 (10)	0.0146 (9)	0.0143 (9)	−0.0033 (8)	−0.0016 (8)	0.0010 (7)
C16	0.0187 (9)	0.0158 (10)	0.0181 (10)	−0.0018 (7)	0.0020 (8)	0.0000 (8)
C2	0.0191 (10)	0.0174 (9)	0.0151 (9)	−0.0046 (7)	0.0016 (8)	0.0006 (8)
C21	0.0188 (10)	0.0218 (10)	0.0206 (10)	−0.0026 (8)	−0.0009 (8)	−0.0025 (8)
N3	0.0190 (8)	0.0193 (8)	0.0141 (8)	−0.0037 (7)	−0.0001 (6)	0.0007 (6)
C4	0.0144 (9)	0.0171 (9)	0.0165 (10)	−0.0007 (7)	0.0015 (8)	0.0017 (7)
N4	0.0186 (8)	0.0223 (9)	0.0192 (8)	−0.0031 (7)	0.0000 (7)	0.0019 (7)
O41	0.0266 (8)	0.0300 (8)	0.0312 (8)	0.0016 (6)	−0.0140 (7)	−0.0031 (6)
O42	0.0278 (8)	0.0229 (7)	0.0266 (8)	0.0022 (6)	0.0009 (6)	−0.0056 (6)
C5	0.0232 (10)	0.0157 (9)	0.0162 (9)	−0.0005 (8)	0.0018 (8)	−0.0008 (8)

Geometric parameters (Å, º)

N1—C5	1.372 (2)	C15—H15	0.9093
N1—C2	1.379 (2)	C16—H16	0.9824
N1—C11	1.436 (2)	C2—N3	1.321 (2)
C11—C12	1.387 (2)	C2—C21	1.485 (2)
C11—C16	1.396 (2)	C21—H21A	0.9710
C12—C13	1.390 (2)	C21—H21B	0.9201
C12—H12	0.9414	C21—H21C	0.9739
C13—C14	1.386 (2)	N3—C4	1.366 (2)
C13—H13	0.9168	C4—C5	1.354 (2)
C14—C15	1.376 (2)	C4—N4	1.428 (2)
C14—N14	1.473 (2)	N4—O41	1.2301 (19)
N14—O141	1.2274 (19)	N4—O42	1.2436 (19)
N14—O142	1.2339 (19)	C5—H5	0.9323
C15—C16	1.387 (2)
C5—N1—C2	107.85 (15)	C15—C16—H16	121.6
C5—N1—C11	125.42 (15)	C11—C16—H16	119.3
C2—N1—C11	126.72 (15)	N3—C2—N1	110.74 (15)
C12—C11—C16	121.75 (16)	N3—C2—C21	125.22 (16)
C12—C11—N1	119.16 (15)	N1—C2—C21	124.02 (16)
C16—C11—N1	119.08 (15)	C2—C21—H21A	111.8
C11—C12—C13	119.20 (17)	C2—C21—H21B	107.1
C11—C12—H12	120.7	H21A—C21—H21B	109.3
C13—C12—H12	120.1	C2—C21—H21C	111.3
C14—C13—C12	118.21 (16)	H21A—C21—H21C	108.6
C14—C13—H13	122.8	H21B—C21—H21C	108.7
C12—C13—H13	119.0	C2—N3—C4	104.37 (15)
C15—C14—C13	123.28 (16)	C5—C4—N3	113.01 (16)
C15—C14—N14	118.37 (16)	C5—C4—N4	125.75 (16)
C13—C14—N14	118.28 (16)	N3—C4—N4	121.24 (15)
O141—N14—O142	123.47 (16)	O41—N4—O42	123.86 (16)
O141—N14—C14	118.14 (15)	O41—N4—C4	118.76 (15)
O142—N14—C14	118.37 (16)	O42—N4—C4	117.38 (15)
C14—C15—C16	118.56 (17)	C4—C5—N1	104.02 (15)
C14—C15—H15	119.4	C4—C5—H5	134.9
C16—C15—H15	122.0	N1—C5—H5	120.8
C15—C16—C11	118.99 (16)
C5—N1—C11—C12	122.19 (19)	N1—C11—C16—C15	178.68 (15)
C2—N1—C11—C12	−58.0 (2)	C5—N1—C2—N3	−0.3 (2)
C5—N1—C11—C16	−57.6 (2)	C11—N1—C2—N3	179.90 (15)
C2—N1—C11—C16	122.18 (19)	C5—N1—C2—C21	−179.11 (16)
C16—C11—C12—C13	0.8 (3)	C11—N1—C2—C21	1.0 (3)
N1—C11—C12—C13	−179.07 (15)	N1—C2—N3—C4	−0.44 (19)
C11—C12—C13—C14	0.4 (2)	C21—C2—N3—C4	178.40 (17)
C12—C13—C14—C15	−1.1 (3)	C2—N3—C4—C5	1.0 (2)
C12—C13—C14—N14	175.83 (15)	C2—N3—C4—N4	−178.39 (15)
C15—C14—N14—O141	−8.9 (2)	C5—C4—N4—O41	−172.79 (17)
C13—C14—N14—O141	173.95 (15)	N3—C4—N4—O41	6.5 (2)
C15—C14—N14—O142	169.37 (15)	C5—C4—N4—O42	7.3 (3)
C13—C14—N14—O142	−7.8 (2)	N3—C4—N4—O42	−173.35 (15)
C13—C14—C15—C16	0.8 (3)	N3—C4—C5—N1	−1.2 (2)
N14—C14—C15—C16	−176.21 (15)	N4—C4—C5—N1	178.22 (15)
C14—C15—C16—C11	0.4 (2)	C2—N1—C5—C4	0.84 (18)
C12—C11—C16—C15	−1.1 (3)	C11—N1—C5—C4	−179.31 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···N3^i	0.94	2.40	3.338 (2)	177
C15—H15···O42^ii	0.91	2.55	3.333 (2)	145
C21—H21A···O141^iii	0.97	2.52	3.429 (2)	156
C5—H5···O141^iv	0.93	2.46	3.258 (2)	143

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