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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o951.
Published online 2008 May 3. doi:  10.1107/S1600536808011926
PMCID: PMC2961469

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

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 [triangle]); Fischer et al. (2007 [triangle]); Narayanan et al. (2005 [triangle]); Saito & Koizumi (2005 [triangle]); Xiao et al. (2007 [triangle]); Yang et al. (2005 [triangle]).

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Object name is e-64-0o951-scheme1.jpg

Experimental

Crystal data

  • C14H9N5O12
  • M r = 439.26
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o951-efi1.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.21 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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.

Refinement

H atoms were positioned geometrically and treated as riding, with C—H bonding lengths constrained to 0.93 (aromatic H), 0.96 Å (methyl H), and with Uĩso~(H) = 1.2Ueq (aromatic H) or Uĩso~(H) = 1.5Ueq (methyl H).

Figures

Fig. 1.
Atom numbering scheme for the title compound with 30% probability displacement ellipsoids.
Fig. 2.
View of the two-dimensional sheet structure. (C—H···O interactions are represented as broken lines).

Crystal data

C14H9N5O12Z = 2
Mr = 439.26F000 = 448
Triclinic, P1Dx = 1.687 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 10.3765 (13) ÅCell parameters from 2971 reflections
b = 10.4423 (13) Åθ = 2.4–25.5º
c = 10.4429 (13) ŵ = 0.15 mm1
α = 82.5650 (10)ºT = 291 (2) K
β = 62.2850 (10)ºBlock, yellow
γ = 60.5200 (10)º0.41 × 0.34 × 0.29 mm
V = 864.73 (19) Å3

Data collection

Bruker APEXII CCD area-detector diffractometer3194 independent reflections
Radiation source: fine-focus sealed tube2686 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.013
T = 291(2) Kθmax = 25.5º
[var phi] and ω scansθmin = 2.4º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −12→12
Tmin = 0.940, Tmax = 0.958k = −12→12
6598 measured reflectionsl = −12→12

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.117  w = 1/[σ2(Fo2) + (0.059P)2 + 0.3851P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
3194 reflectionsΔρmax = 0.25 e Å3
282 parametersΔρmin = −0.21 e Å3
Primary atom site location: structure-invariant direct methodsExtinction 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 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 (Å2)

xyzUiso*/Ueq
O10.36354 (18)0.70656 (16)0.19497 (14)0.0448 (3)
O20.69388 (15)0.72440 (14)0.24022 (14)0.0382 (3)
O30.4217 (2)0.40331 (19)0.2500 (2)0.0678 (5)
O40.1905 (2)0.4489 (2)0.4428 (3)0.0852 (6)
O50.2186 (3)0.6187 (2)0.84423 (19)0.0803 (6)
O60.2172 (2)0.8273 (2)0.83302 (16)0.0648 (5)
O70.5003 (2)0.8533 (2)0.57692 (17)0.0582 (4)
O80.2549 (2)1.03379 (17)0.61824 (19)0.0640 (5)
O90.2989 (2)1.33902 (17)0.06894 (18)0.0571 (4)
O100.0962 (2)1.3106 (2)0.2303 (2)0.0846 (7)
O110.0882 (2)1.0384 (2)0.2635 (2)0.0761 (6)
O120.04620 (19)1.1239 (2)0.46358 (18)0.0702 (5)
N10.3036 (2)0.4748 (2)0.3675 (2)0.0507 (5)
N20.2378 (2)0.7181 (2)0.77767 (18)0.0484 (4)
N30.3645 (2)0.90493 (19)0.58132 (16)0.0404 (4)
N40.2444 (2)1.26902 (17)0.15879 (17)0.0391 (4)
N50.1327 (2)1.06936 (18)0.3386 (2)0.0433 (4)
C10.3442 (2)0.69672 (19)0.33107 (19)0.0316 (4)
C20.3056 (2)0.59612 (19)0.4225 (2)0.0351 (4)
C30.2736 (2)0.6019 (2)0.5661 (2)0.0371 (4)
H30.24410.53620.62490.045*
C40.2859 (2)0.7060 (2)0.62141 (19)0.0351 (4)
C50.3359 (2)0.80022 (19)0.52985 (19)0.0314 (4)
C60.3661 (2)0.79704 (18)0.38642 (18)0.0283 (4)
C70.4211 (2)0.89880 (18)0.28967 (17)0.0280 (4)
C80.5928 (2)0.85656 (18)0.21610 (18)0.0287 (4)
C90.6454 (2)0.9505 (2)0.12600 (18)0.0330 (4)
H90.75840.92240.07690.040*
C100.5303 (2)1.08464 (19)0.10979 (18)0.0331 (4)
H100.56601.14710.05070.040*
C110.3623 (2)1.12714 (18)0.18047 (18)0.0308 (4)
C120.3096 (2)1.03275 (19)0.26904 (18)0.0302 (4)
C130.2548 (4)0.6888 (3)0.1570 (3)0.0651 (7)
H13A0.31240.59080.10700.098*
H13B0.22430.76090.09460.098*
H13C0.15590.70280.24420.098*
C140.8715 (2)0.6715 (2)0.1654 (3)0.0536 (6)
H14A0.91020.66450.06190.080*
H14B0.92850.57550.19100.080*
H14C0.89390.73940.19340.080*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0591 (9)0.0572 (9)0.0359 (7)−0.0397 (8)−0.0238 (7)0.0089 (6)
O20.0289 (6)0.0334 (7)0.0451 (7)−0.0130 (5)−0.0157 (6)0.0099 (5)
O30.0824 (13)0.0479 (9)0.0718 (12)−0.0313 (9)−0.0322 (10)−0.0061 (8)
O40.0745 (13)0.0756 (13)0.1234 (17)−0.0582 (11)−0.0347 (12)0.0068 (12)
O50.1272 (17)0.1048 (15)0.0559 (10)−0.0899 (15)−0.0508 (11)0.0482 (10)
O60.0882 (13)0.0741 (12)0.0384 (8)−0.0475 (10)−0.0264 (8)0.0091 (8)
O70.0600 (10)0.0829 (12)0.0526 (9)−0.0446 (9)−0.0309 (8)0.0070 (8)
O80.0900 (13)0.0396 (9)0.0696 (11)−0.0276 (9)−0.0460 (10)0.0029 (7)
O90.0681 (10)0.0444 (8)0.0624 (10)−0.0317 (8)−0.0342 (8)0.0286 (7)
O100.0399 (9)0.0592 (11)0.1113 (16)−0.0129 (8)−0.0246 (10)0.0458 (11)
O110.0482 (10)0.0769 (12)0.1132 (16)−0.0263 (9)−0.0453 (10)−0.0055 (11)
O120.0383 (8)0.0812 (12)0.0476 (10)−0.0124 (8)−0.0077 (7)0.0123 (9)
N10.0541 (11)0.0396 (9)0.0703 (13)−0.0277 (9)−0.0332 (10)0.0094 (9)
N20.0543 (11)0.0646 (12)0.0385 (9)−0.0381 (10)−0.0243 (8)0.0213 (9)
N30.0540 (10)0.0481 (10)0.0313 (8)−0.0321 (9)−0.0224 (7)0.0098 (7)
N40.0467 (10)0.0305 (8)0.0402 (9)−0.0181 (7)−0.0226 (8)0.0103 (7)
N50.0327 (8)0.0344 (9)0.0536 (11)−0.0137 (7)−0.0189 (8)0.0149 (7)
C10.0280 (8)0.0314 (9)0.0333 (9)−0.0139 (7)−0.0132 (7)0.0033 (7)
C20.0309 (9)0.0296 (9)0.0464 (10)−0.0163 (7)−0.0173 (8)0.0042 (8)
C30.0335 (9)0.0347 (10)0.0450 (11)−0.0203 (8)−0.0185 (8)0.0158 (8)
C40.0338 (9)0.0400 (10)0.0328 (9)−0.0198 (8)−0.0162 (8)0.0116 (8)
C50.0305 (9)0.0312 (9)0.0340 (9)−0.0153 (7)−0.0166 (7)0.0064 (7)
C60.0247 (8)0.0257 (8)0.0322 (9)−0.0112 (7)−0.0132 (7)0.0055 (7)
C70.0317 (9)0.0279 (8)0.0263 (8)−0.0158 (7)−0.0136 (7)0.0036 (6)
C80.0308 (9)0.0288 (8)0.0281 (8)−0.0143 (7)−0.0147 (7)0.0022 (7)
C90.0314 (9)0.0375 (9)0.0306 (9)−0.0202 (8)−0.0109 (7)0.0026 (7)
C100.0427 (10)0.0336 (9)0.0288 (9)−0.0250 (8)−0.0146 (8)0.0060 (7)
C110.0383 (9)0.0271 (8)0.0288 (8)−0.0156 (7)−0.0177 (7)0.0048 (7)
C120.0303 (9)0.0311 (9)0.0281 (8)−0.0153 (7)−0.0127 (7)0.0037 (7)
C130.098 (2)0.0792 (18)0.0680 (15)−0.0620 (16)−0.0593 (15)0.0260 (13)
C140.0295 (10)0.0445 (12)0.0705 (15)−0.0120 (9)−0.0182 (10)0.0085 (10)

Geometric parameters (Å, °)

O1—C11.337 (2)C2—C31.380 (3)
O1—C131.451 (3)C3—C41.379 (3)
O2—C81.341 (2)C3—H30.9300
O2—C141.443 (2)C4—C51.396 (2)
O3—N11.225 (3)C5—C61.382 (2)
O4—N11.211 (2)C6—C71.503 (2)
O5—N21.220 (2)C7—C121.379 (2)
O6—N21.223 (2)C7—C81.414 (2)
O7—N31.215 (2)C8—C91.399 (2)
O8—N31.214 (2)C9—C101.377 (3)
O9—N41.212 (2)C9—H90.9300
O10—N41.212 (2)C10—C111.381 (3)
O11—N51.218 (2)C10—H100.9300
O12—N51.197 (2)C11—C121.396 (2)
N1—C21.470 (2)C13—H13A0.9600
N2—C41.470 (2)C13—H13B0.9600
N3—C51.481 (2)C13—H13C0.9600
N4—C111.459 (2)C14—H14A0.9600
N5—C121.478 (2)C14—H14B0.9600
C1—C21.405 (2)C14—H14C0.9600
C1—C61.413 (2)
C1—O1—C13120.36 (16)C5—C6—C7120.87 (15)
C8—O2—C14118.30 (14)C1—C6—C7119.98 (15)
O4—N1—O3124.87 (19)C12—C7—C8118.36 (15)
O4—N1—C2118.4 (2)C12—C7—C6122.25 (15)
O3—N1—C2116.66 (17)C8—C7—C6119.39 (14)
O5—N2—O6124.23 (18)O2—C8—C9125.08 (15)
O5—N2—C4117.39 (18)O2—C8—C7115.04 (14)
O6—N2—C4118.38 (16)C9—C8—C7119.88 (15)
O8—N3—O7126.09 (18)C10—C9—C8120.20 (16)
O8—N3—C5117.95 (16)C10—C9—H9119.9
O7—N3—C5115.89 (17)C8—C9—H9119.9
O9—N4—O10122.95 (17)C9—C10—C11120.58 (16)
O9—N4—C11118.70 (16)C9—C10—H10119.7
O10—N4—C11118.34 (15)C11—C10—H10119.7
O12—N5—O11125.41 (19)C10—C11—C12119.36 (16)
O12—N5—C12118.04 (18)C10—C11—N4118.98 (15)
O11—N5—C12116.54 (17)C12—C11—N4121.66 (16)
O1—C1—C2126.17 (16)C7—C12—C11121.61 (16)
O1—C1—C6116.23 (15)C7—C12—N5117.27 (15)
C2—C1—C6117.61 (16)C11—C12—N5121.06 (15)
C3—C2—C1122.38 (16)O1—C13—H13A109.5
C3—C2—N1116.34 (16)O1—C13—H13B109.5
C1—C2—N1121.24 (17)H13A—C13—H13B109.5
C2—C3—C4119.28 (16)O1—C13—H13C109.5
C2—C3—H3120.4H13A—C13—H13C109.5
C4—C3—H3120.4H13B—C13—H13C109.5
C3—C4—C5119.40 (16)O2—C14—H14A109.5
C3—C4—N2118.23 (16)O2—C14—H14B109.5
C5—C4—N2122.31 (17)H14A—C14—H14B109.5
C6—C5—C4121.87 (16)O2—C14—H14C109.5
C6—C5—N3116.95 (15)H14A—C14—H14C109.5
C4—C5—N3121.15 (15)H14B—C14—H14C109.5
C5—C6—C1119.15 (15)
C13—O1—C1—C239.2 (3)C2—C1—C6—C7175.07 (15)
C13—O1—C1—C6−141.22 (19)C5—C6—C7—C12−95.4 (2)
O1—C1—C2—C3−174.24 (17)C1—C6—C7—C1284.4 (2)
C6—C1—C2—C36.2 (3)C5—C6—C7—C884.9 (2)
O1—C1—C2—N18.1 (3)C1—C6—C7—C8−95.26 (19)
C6—C1—C2—N1−171.47 (16)C14—O2—C8—C9−1.7 (3)
O4—N1—C2—C345.1 (3)C14—O2—C8—C7178.11 (16)
O3—N1—C2—C3−132.0 (2)C12—C7—C8—O2−179.37 (14)
O4—N1—C2—C1−137.1 (2)C6—C7—C8—O20.3 (2)
O3—N1—C2—C145.8 (3)C12—C7—C8—C90.4 (2)
C1—C2—C3—C4−2.5 (3)C6—C7—C8—C9−179.88 (15)
N1—C2—C3—C4175.21 (16)O2—C8—C9—C10−179.60 (15)
C2—C3—C4—C5−2.2 (3)C7—C8—C9—C100.6 (2)
C2—C3—C4—N2175.03 (16)C8—C9—C10—C11−0.9 (3)
O5—N2—C4—C312.9 (3)C9—C10—C11—C120.0 (2)
O6—N2—C4—C3−166.04 (19)C9—C10—C11—N4−179.06 (15)
O5—N2—C4—C5−170.01 (19)O9—N4—C11—C106.8 (2)
O6—N2—C4—C511.1 (3)O10—N4—C11—C10−174.16 (19)
C3—C4—C5—C63.1 (3)O9—N4—C11—C12−172.27 (17)
N2—C4—C5—C6−173.96 (16)O10—N4—C11—C126.8 (3)
C3—C4—C5—N3−174.78 (16)C8—C7—C12—C11−1.3 (2)
N2—C4—C5—N38.2 (3)C6—C7—C12—C11179.06 (15)
O8—N3—C5—C681.7 (2)C8—C7—C12—N5175.72 (15)
O7—N3—C5—C6−95.50 (19)C6—C7—C12—N5−3.9 (2)
O8—N3—C5—C4−100.3 (2)C10—C11—C12—C71.0 (2)
O7—N3—C5—C482.5 (2)N4—C11—C12—C7−179.88 (15)
C4—C5—C6—C10.6 (3)C10—C11—C12—N5−175.84 (16)
N3—C5—C6—C1178.61 (15)N4—C11—C12—N53.2 (2)
C4—C5—C6—C7−179.53 (15)O12—N5—C12—C784.0 (2)
N3—C5—C6—C7−1.6 (2)O11—N5—C12—C7−94.7 (2)
O1—C1—C6—C5175.27 (15)O12—N5—C12—C11−99.0 (2)
C2—C1—C6—C5−5.1 (2)O11—N5—C12—C1182.3 (2)
O1—C1—C6—C7−4.6 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C13—H13A···O30.962.452.926 (3)111
C14—H14B···O10i0.962.553.502 (3)174
C14—H14C···O8ii0.962.583.371 (3)140

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2086).

References

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