6,6′-Dimeth­oxy-2,2′,3,3′,5-penta­nitro-1,1′-biphen­yl

Yuan-Yuan Jiang; Shao-Bin Miao; Dong-Sheng Deng; Bao-Ming Ji

doi:10.1107/S1600536808011926

. 2008 May 3;64(Pt 6):o951. doi: 10.1107/S1600536808011926

6,6′-Dimethoxy-2,2′,3,3′,5-pentanitro-1,1′-biphenyl

Yuan-Yuan Jiang ^a, Shao-Bin Miao ^b, Dong-Sheng Deng ^b, Bao-Ming Ji ^b,^*

PMCID: PMC2961469 PMID: 21202685

Abstract

In the axially chiral title compound, C₁₄H₉N₅O₁₂, the dihedral angle between the two benzene rings is 86.0 (8)°. In the crystal structure, the molecules display a two-dimensional framework formed by weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For related literature, see: Chen et al. (2001 ▶); Fischer et al. (2007 ▶); Narayanan et al. (2005 ▶); Saito & Koizumi (2005 ▶); Xiao et al. (2007 ▶); Yang et al. (2005 ▶).

Experimental

Crystal data

C₁₄H₉N₅O₁₂
M _r = 439.26
Triclinic,
a = 10.3765 (13) Å
b = 10.4423 (13) Å
c = 10.4429 (13) Å
α = 82.5650 (10)°
β = 62.2850 (10)°
γ = 60.5200 (10)°
V = 864.73 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 291 (2) K
0.41 × 0.34 × 0.29 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.940, T _max = 0.958
6598 measured reflections
3194 independent reflections
2686 reflections with I > 2σ(I)
R _int = 0.013

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.117
S = 1.02
3194 reflections
282 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808011926/si2086sup1.cif

e-64-0o951-sup1.cif^{(20.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808011926/si2086Isup2.hkl

e-64-0o951-Isup2.hkl^{(156.7KB, hkl)}

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
C13—H13A⋯O3	0.96	2.45	2.926 (3)	111
C14—H14B⋯O10ⁱ	0.96	2.55	3.502 (3)	174
C14—H14C⋯O8ⁱⁱ	0.96	2.58	3.371 (3)	140

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work was supported by the Henan Innovation Project for University Prominent Research Talents (No. 2005 KYCX021), and the Natural Science Foundation of Henan Province.

supplementary crystallographic information

Comment

Nitro compounds, specially aromatic nitro compounds have been widely studied owing to their potential application in, for example, pathology (Narayanan, et al., 2005), materials science (Saito & Koizumi, 2005). On the other hand, in our search for chiral compounds, the title related chiral 6,6'-dimethoxy-2,3,2',5'-tetranitro-1,1'-biphenyl compound was synthesized by Xiao et al., (2007). Herein, as an extension to our previous investigation, we report the synthesis and structural characterization of the title compound.

In contrast to our highly substituted biphenyl compounds, the unsubstituted biphenyl groups in compounds synthesized by Fischer et al., (2007) were found to be approximately planar. The molecular geometry in the title compound displays special behavior, the dihedral angle between the benzene rings is 94.0 (8)°, and all the nitro groups at positions 2,3,5,2',3' are twisted out of the corresponding rings which is 45.5 (3)°, 13.5 (5)°, 98.4 (3)°, 6.6 (4)° and 83.5 (5)°, respectively, as depicted in Fig.1. Bond lengths and angles are in good agreement with the dinitrophenyl group in the structure of 1-(2,4-dinitrophenyl)azo-1-nitrocyclohexane, reported by Yang et al., (2005). One intramolecular C—H···O hydrogen bond is observed in the title molecule, and the two intermolecular C—H···O hydrogen bonding contacts (Table 1) form closed two-dimensional grid motifs (Fig. 2).

Experimental

All chemicals and solvents purchased were of reagent grade and used without further purification. The precursor 6,6'-Dimethoxy-2,2'-dinitro-1,1'-biphenyl was prepared according to the reported procedure (Chen et al., 2001). However, the title compound was obtained by chance when we tried to prepare the 6,6'-Dimethoxy-2,3,5,2',3',5'-hexanitro-1,1'-biphenyl compound. That is, the title compound was synthesized by the nitration reaction of the precursor (0.5 mmol) in 10 ml of concentrated nitric acid at room temperature for 24 h. The resulting solution was poured into 30 ml of ice water and the resulting precipitate was collected by filtration and recrystallized from ethyl acetate to obtain the title crystals, which were suitable for X-ray diffraction analysis. Cautious, the title compound has potential explosive property.