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

Transcription

1 University of Wollongong Research Online Australian Institute for Innovative Materials - Papers Australian Institute for Innovative Materials Methyl-4-nitro-1-(4-nitrophenyl)-1H-imidazole Pawel Wagner University of Wollongong, pawel@uow.edu.au Maciej Kubicki Adam Mickiewicz University Publication Details Wagner, P. & Kubicki, M. (2007). 2-Methyl-4-nitro-1-(4-nitrophenyl)-1H-imidazole. Acta Crystallographica Section E: Structure Reports Online, 63 (7), o3083. Research Online is the open access institutional repository for the University of Wollongong. For further information contact the UOW Library: research-pubs@uow.edu.au

2 2-Methyl-4-nitro-1-(4-nitrophenyl)-1H-imidazole Abstract In the title compound, C 10 H 8 N 4 O 4, two planar fragments, viz. the imidazole and nitrophenyl rings, are tilted at a dihedral of (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. Keywords nitro, 1, 4, nitrophenyl, 2, 1h, imidazole, methyl Disciplines Engineering Physical Sciences and Mathematics Publication Details Wagner, P. & Kubicki, M. (2007). 2-Methyl-4-nitro-1-(4-nitrophenyl)-1H-imidazole. Acta Crystallographica Section E: Structure Reports Online, 63 (7), o3083. This journal article is available at Research Online:

3 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN Methyl-4-nitro-1-(4-nitrophenyl)-1Himidazole Paweł Wagner a and Maciej Kubicki b * a Nanomaterials Research Centre, and MacDiarmid Institute for Advanced Materials and Nanotechnology, Massey University, Private Bag , Palmerston North, New Zealand, and b Department of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, Poznań, Poland Correspondence mkubicki@amu.edu.pl Received 18 May 2007; accepted 29 May 2007 Key indicators: single-crystal X-ray study; T = 100 K; mean (C C) = Å; R factor = 0.038; wr factor = 0.099; data-to-parameter ratio = Experimental Crystal data C 10 H 8 N 4 O 4 M r = Orthorhombic, Pbca a = (9) Å b = (10) Å c = (13) Å Data collection Kuma KM-4-CCD four-circle diffractometer Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) T min = 0.918, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections V = (3) Å 3 Z =8 Mo K radiation = 0.12 mm 1 T = 100 (1) K mm measured reflections 2092 independent reflections 1442 reflections with I > 2(I) R int = parameters H-atom parameters constrained max = 0.23 e Å 3 min = 0.24 e Å 3 In the title compound, C 10 H 8 N 4 O 4, two planar fragments, viz. the imidazole and nitrophenyl rings, are tilted at a dihedral of (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 HO hydrogen bonds, which are connected by C HN hydrogen bonds into rows along the [001] direction. The neighbouring rows are connected via C HO interactions into a twodimensional network in the bc plane. 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). Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA C12 H12N3 i (2) 177 C15 H15O42 ii (2) 145 C21 H21AO141 iii (2) 156 C5 H5O141 iv (2) 143 Symmetry codes: (i) x 1 2 ; y; z þ 3 2 ; (ii) x þ 2; y; z þ 1; (iii) x þ 1 2 ; y þ 1 2 ; z þ 1; (iv) x þ 1; y; z þ 1. 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. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: KP2111). References Kowalski, A. (1995). Acta Cryst. C51, Kowalski, A. (1996). Acta Cryst. C52, Kubicki, M. (2004). Acta Cryst. C60, o341 o343. Kubicki, M. & Wagner, P. (2007). Acta Cryst. E63. In the press. Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Versions Oxford Diffraction, Wrocław, Poland. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Siemens (1989). Stereochemical Workstation Operation Manual. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Suwiński, J., Świerczek, K. & Głowiak, T. (1993). Tetrahedron, 49, Acta Cryst. (2007). E63, o3083 doi: /s # 2007 International Union of Crystallography o3083

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5 Acta Cryst. (2007). E63, o3083 [ doi: /s ] 2-Methyl-4-nitro-1-(4-nitrophenyl)-1H-imidazole P. Wagner and M. Kubicki 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 with the benzene ring. 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)]. 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. 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 C 10 H 8 N 4 O 4 F 000 = 1024 M r = D x = Mg m 3 sup-1

6 Orthorhombic, Pbca Hall symbol: -P 2ac 2ab Mo Kα radiation λ = Å a = (9) Å θ = 4 22º b = (10) Å c = (13) Å V = (3) Å 3 Z = 8 Cell parameters from 3523 reflections µ = 0.12 mm 1 T = 100 (1) K Needle, colourless mm Data collection Kuma KM-4-CCD four-circle diffractometer Radiation source: fine-focus sealed tube Monochromator: graphite R int = T = 100(1) K θ max = 26.0º ω scan θ min = 3.2º Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) T min = 0.918, T max = independent reflections 1442 reflections with I > 2σ(I) h = 9 10 k = measured reflections l = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o 2 ) + (0.0481P) P] where P = (F o 2 + 2F c 2 )/3 S = 1.01 (Δ/σ) max = reflections Δρ max = 0.23 e Å parameters Δρ min = 0.24 e Å 3 Primary atom site location: structure-invariant direct methods Extinction correction: none 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 F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > 2sigma(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R factors based on ALL data will be even larger. sup-2

7 Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq N (17) (11) (7) (4) C (2) (14) (8) (4) C (2) (14) (9) (4) H * C (2) (13) (9) (4) H * C (2) (13) (9) (4) N (19) (11) (8) (4) O (17) (10) (6) (3) O (16) (10) (7) (4) C (2) (13) (9) (4) H * C (2) (14) (8) (4) H * C (2) (13) (9) (4) C (2) (14) (9) (4) H21A * H21B * H21C * N (17) (12) (7) (3) C (2) (14) (8) (4) N (18) (12) (7) (4) O (17) (11) (6) (4) O (16) (10) (6) (3) C (2) (14) (8) (4) H * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 N (8) (8) (8) (6) (6) (6) C (9) (9) (9) (7) (8) (8) C (9) (10) (9) (8) (8) (8) C (10) (10) (10) (7) (8) (8) C (9) (9) (10) (7) (8) (8) N (9) (8) (9) (6) (7) (7) O (9) (8) (7) (6) (6) (6) O (7) (8) (9) (6) (7) (7) C (10) (9) (9) (8) (8) (7) C (9) (10) (10) (7) (8) (8) C (10) (9) (9) (7) (8) (8) C (10) (10) (10) (8) (8) (8) N (8) (8) (8) (7) (6) (6) C (9) (9) (10) (7) (8) (7) sup-3

8 N (8) (9) (8) (7) (7) (7) O (8) (8) (8) (6) (7) (6) O (8) (7) (8) (6) (6) (6) C (10) (9) (9) (8) (8) (8) Geometric parameters (Å, ) N1 C (2) C15 H N1 C (2) C16 H N1 C (2) C2 N (2) C11 C (2) C2 C (2) C11 C (2) C21 H21A C12 C (2) C21 H21B C12 H C21 H21C C13 C (2) N3 C (2) C13 H C4 C (2) C14 C (2) C4 N (2) C14 N (2) N4 O (19) N14 O (19) N4 O (19) N14 O (19) C5 H C15 C (2) C5 N1 C (15) C15 C16 H C5 N1 C (15) C11 C16 H C2 N1 C (15) N3 C2 N (15) C12 C11 C (16) N3 C2 C (16) C12 C11 N (15) N1 C2 C (16) C16 C11 N (15) C2 C21 H21A C11 C12 C (17) C2 C21 H21B C11 C12 H H21A C21 H21B C13 C12 H C2 C21 H21C C14 C13 C (16) H21A C21 H21C C14 C13 H H21B C21 H21C C12 C13 H C2 N3 C (15) C15 C14 C (16) C5 C4 N (16) C15 C14 N (16) C5 C4 N (16) C13 C14 N (16) N3 C4 N (15) O141 N14 O (16) O41 N4 O (16) O141 N14 C (15) O41 N4 C (15) O142 N14 C (16) O42 N4 C (15) C14 C15 C (17) C4 C5 N (15) C14 C15 H C4 C5 H C16 C15 H N1 C5 H C15 C16 C (16) C5 N1 C11 C (19) N1 C11 C16 C (15) C2 N1 C11 C (2) C5 N1 C2 N3 0.3 (2) C5 N1 C11 C (2) C11 N1 C2 N (15) C2 N1 C11 C (19) C5 N1 C2 C (16) C16 C11 C12 C (3) C11 N1 C2 C (3) N1 C11 C12 C (15) N1 C2 N3 C (19) sup-4

9 C11 C12 C13 C (2) C21 C2 N3 C (17) C12 C13 C14 C (3) C2 N3 C4 C5 1.0 (2) C12 C13 C14 N (15) C2 N3 C4 N (15) C15 C14 N14 O (2) C5 C4 N4 O (17) C13 C14 N14 O (15) N3 C4 N4 O (2) C15 C14 N14 O (15) C5 C4 N4 O (3) C13 C14 N14 O (2) N3 C4 N4 O (15) C13 C14 C15 C (3) N3 C4 C5 N1 1.2 (2) N14 C14 C15 C (15) N4 C4 C5 N (15) C14 C15 C16 C (2) C2 N1 C5 C (18) C12 C11 C16 C (3) C11 N1 C5 C (15) Hydrogen-bond geometry (Å, ) D H A D H H A D A D H A C12 H12 N3 i (2) 177 C15 H15 O42 ii (2) 145 C21 H21A O141 iii (2) 156 C5 H5 O141 iv (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. sup-5

10 Fig. 1 sup-6

11 Fig. 2 sup-7