PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o1052–o1053.
Published online 2009 April 18. doi:  10.1107/S1600536809011088
PMCID: PMC2977734

3,3′,5,5′-Tetra­nitro­biphen­yl

Abstract

The title compound, C12H6N4O8, is a biphenyl system that was synthesized as a building block for a new series of anti­malarial compounds. The aromatic rings are oriented at a dihedral angle of 45.5 (2)°, and inter­molecular short O(...)O contacts form a chain along the b axis. The strength of the inter­actions involved in this chain cause one of the rings to be slightly distorted, with the torsion angle between the nitro groups being 23.4 (2)°, whereas, in the other ring, both nitro systems are parallel, forming an angle of 9.6 (2)° with the plane of the aromatic ring to which they are bound. Furthermore, the three ring C atoms around the ring–ring linkage belong to a plane inclined by 4.5 (1)° in relation to the plane containing the other three C atoms, i.e. (NO2–)C—C—C(NO2). This distortion of the ring causes uncommonly short intermolecular O(...)O [3.038 (2) Å] and O(...)C [3.000 (4) and 3.214 (1) Å] contacts.

Related literature

For the previous synthesis of the title compound and its stability studies, see Case (1942 [triangle]) and Hoffsommer & McCullough (1968 [triangle]). For the use of polynitro­aromatic compounds as explosives, see Davis (1941 [triangle]) and Keshavarz & Pouretedal (2005 [triangle]). For their mutagenic and carcinogenic properties, see Debnath et al. (1991 [triangle]). For previous studies showing distortions induced in aromatic rings, see Murray-Rust (1982 [triangle]), Allen et al. (1998 [triangle]), and Khrustalev et al. (2005 [triangle]). For the preparation, see: Goossen et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1052-scheme1.jpg

Experimental

Crystal data

  • C12H6N4O8
  • M r = 334.21
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1052-efi1.jpg
  • a = 10.0683 (1) Å
  • b = 15.4640 (2) Å
  • c = 16.3436 (2) Å
  • V = 2544.64 (5) Å3
  • Z = 8
  • Cu Kα radiation
  • μ = 1.32 mm−1
  • T = 100 K
  • 0.18 × 0.15 × 0.11 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: none
  • 30954 measured reflections
  • 2315 independent reflections
  • 2294 reflections with I > 2σ(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.081
  • S = 1.09
  • 2315 reflections
  • 225 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2005 [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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809011088/im2105sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011088/im2105Isup2.hkl

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

Acknowledgments

The authors thank the Center for Disease Control and Prevention, USA, for providing financial assistance (CDC cooperative agreements 1UO1 CI000211-03 and 1UO1 CI000362-01). This investigation was conducted in a facility constructed with support from Research Facilities Improvement Program grant No. C06Rr-14503-01 from the National Center for Research Resources, National Institutes of Health.

supplementary crystallographic information

Comment

Synthesis of the 3,3',5,5'-tetranitrobiphenyl has previously been reported by Case (1942), from the reaction of 3,5-dinitroiodobenzene and copper at 270°C. This paper reports the crystal structure of the title compound, obtained by reaction of 1-bromo-3,5-dinitrobenzene and 3,5-dinitrobenzoic acid in a sealed microwave tube in 1,2-dimethoxyethane. It was found to have activity against Plasmodium falciparum with an IC50 of 5.7 µM against the chloroquine resistant D6 clone and 3.9µM against the W2 clone.

Experimental

The title compound was prepared by decarboxylative coupling as previously published (Goossen et al., 2007). Briefly, 1-bromo-3,5-dinitrobenzene (247 mg, 1 mmol), 3,5-dinitrobenzoic acid (211 mg, 1 mmol), copper(II) bromide (180 mg, 0.8 mmol), 1,2-dimethoxyethane (3 ml), [tetrakis(triphenylphosphine)palladium(0)] (100 mg, 0.086 mmol), [dichlorobis(triphenylphospine)palladium (II)] (60 mg, 0.86 mmol), potassium carbonate (495 mg, 3 mmol) and water (1 ml) were added together in a microwave vial and microwaved at 160°C for 30 minutes while stirring, in a Biotage InitiatorTM Sixty, with variable microwave output. To keep the programmed temperature, the initial output was 100 W for 5 minutes, then varying between 0 and 30 W for the next 25 minutes. The reaction mixture was shaken 3 times with water, then brine and dried over magnesium sulfate and concentrated. The resulting residue was purified by column chromatography on silica gel, eluting with ethyl acetate/hexanes (90:10) to afford 62 mg (20% yield) of the title compound. 3,3',5,5'-Tetranitrobiphenyl was recrystallized from MeOH:CHCl3 (5:95) by slow evaporation of the solvent at room temperature.

Refinement

All H atoms were located in difference maps, and treated as riding atoms, except H2' (C—H = 0.95 Å) and H4' (C—H = 0.94 Å), with the following distance restraints: C—H = 0.93 Å, Uiso=1.2Ueq (C) for Csp2.

Figures

Fig. 1.
Molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
Partial view of the crystal packing of the title compound viewed along the b axis, showing molecules linked into chains by short intermolecular O1'···O4' interactions.

Crystal data

C12H6N4O8Dx = 1.745 Mg m3
Mr = 334.21Melting point: not measured K
Orthorhombic, PbcaCu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2abCell parameters from 9828 reflections
a = 10.0683 (1) Åθ = 3.9–67.6°
b = 15.4640 (2) ŵ = 1.32 mm1
c = 16.3436 (2) ÅT = 100 K
V = 2544.64 (5) Å3Block, yellow
Z = 80.18 × 0.15 × 0.11 mm
F(000) = 1360

Data collection

Bruker APEXII CCD diffractometer2294 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.021
graphiteθmax = 68.0°, θmin = 5.4°
[var phi] and ω scansh = −12→12
30954 measured reflectionsk = −18→18
2315 independent reflectionsl = −19→19

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H atoms treated by a mixture of independent and constrained refinement
S = 1.09w = 1/[σ2(Fo2) + (0.0431P)2 + 1.2464P] where P = (Fo2 + 2Fc2)/3
2315 reflections(Δ/σ)max < 0.001
225 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = −0.31 e Å3
0 constraints

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
C10.34665 (12)0.30780 (8)0.43269 (7)0.0157 (3)
C20.33233 (12)0.30138 (8)0.51737 (7)0.0156 (3)
H20.28940.34480.54660.019*
C30.38272 (12)0.22966 (8)0.55741 (7)0.0162 (3)
C40.44841 (12)0.16333 (8)0.51778 (8)0.0168 (3)
H40.48280.11600.54580.020*
C50.45990 (12)0.17162 (8)0.43369 (8)0.0165 (3)
C60.41093 (12)0.24155 (8)0.39006 (7)0.0162 (3)
H60.42060.24430.33350.019*
N10.37026 (10)0.22503 (7)0.64699 (6)0.0182 (2)
N20.52978 (10)0.10245 (7)0.38839 (7)0.0189 (2)
O10.30268 (11)0.28031 (6)0.68111 (5)0.0259 (2)
O20.42893 (10)0.16675 (6)0.68273 (5)0.0236 (2)
O30.58781 (10)0.04674 (6)0.42849 (6)0.0276 (2)
O40.52572 (10)0.10442 (6)0.31365 (6)0.0253 (2)
C1'0.30389 (12)0.38719 (8)0.38844 (7)0.0155 (3)
C2'0.33837 (12)0.46789 (8)0.42007 (7)0.0162 (3)
H2'0.3828 (15)0.4741 (10)0.4712 (9)0.018 (4)*
C3'0.31428 (12)0.54092 (8)0.37355 (7)0.0156 (3)
C4'0.25353 (12)0.53897 (8)0.29759 (7)0.0159 (3)
H4'0.2391 (15)0.5895 (9)0.2666 (9)0.018 (4)*
C5'0.21448 (12)0.45823 (8)0.27031 (7)0.0160 (3)
C6'0.23899 (12)0.38234 (8)0.31302 (7)0.0161 (3)
H6'0.21270.32920.29180.019*
N1'0.36202 (10)0.62466 (7)0.40437 (6)0.0169 (2)
N2'0.14792 (10)0.45304 (7)0.18984 (6)0.0177 (2)
O1'0.38516 (9)0.63076 (6)0.47790 (5)0.0231 (2)
O2'0.37639 (9)0.68355 (6)0.35486 (6)0.0212 (2)
O3'0.12418 (9)0.52096 (6)0.15399 (5)0.0233 (2)
O4'0.12047 (10)0.38108 (6)0.16341 (6)0.0246 (2)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0138 (6)0.0161 (6)0.0173 (6)−0.0029 (5)−0.0013 (4)0.0007 (5)
C20.0155 (6)0.0143 (6)0.0171 (6)−0.0015 (5)0.0002 (5)−0.0013 (5)
C30.0170 (6)0.0179 (6)0.0137 (6)−0.0044 (5)−0.0009 (4)0.0009 (5)
C40.0162 (6)0.0149 (6)0.0193 (6)−0.0018 (5)−0.0024 (5)0.0028 (5)
C50.0148 (6)0.0154 (6)0.0192 (6)−0.0021 (5)0.0010 (5)−0.0025 (5)
C60.0163 (6)0.0183 (6)0.0140 (6)−0.0035 (5)−0.0005 (4)−0.0003 (5)
N10.0214 (5)0.0174 (5)0.0158 (5)−0.0039 (4)0.0003 (4)0.0015 (4)
N20.0167 (5)0.0169 (5)0.0230 (6)−0.0012 (4)0.0017 (4)−0.0019 (4)
O10.0409 (6)0.0193 (5)0.0175 (5)0.0015 (4)0.0061 (4)−0.0017 (4)
O20.0248 (5)0.0269 (5)0.0191 (5)0.0004 (4)−0.0015 (4)0.0084 (4)
O30.0309 (5)0.0200 (5)0.0320 (5)0.0079 (4)0.0017 (4)0.0022 (4)
O40.0263 (5)0.0304 (5)0.0193 (5)0.0025 (4)0.0033 (4)−0.0057 (4)
C1'0.0137 (6)0.0173 (6)0.0155 (6)0.0000 (4)0.0026 (4)0.0011 (5)
C2'0.0146 (6)0.0194 (6)0.0147 (6)0.0005 (5)0.0003 (5)0.0008 (5)
C3'0.0138 (6)0.0154 (6)0.0177 (6)−0.0008 (4)0.0017 (5)−0.0011 (5)
C4'0.0138 (5)0.0173 (6)0.0166 (6)0.0018 (5)0.0024 (5)0.0030 (5)
C5'0.0133 (6)0.0206 (6)0.0141 (6)0.0006 (5)0.0001 (4)0.0007 (5)
C6'0.0154 (6)0.0164 (6)0.0165 (6)−0.0005 (5)0.0021 (5)−0.0004 (5)
N1'0.0144 (5)0.0172 (5)0.0192 (5)0.0008 (4)−0.0004 (4)0.0003 (4)
N2'0.0165 (5)0.0211 (5)0.0155 (5)0.0003 (4)−0.0004 (4)0.0013 (4)
O1'0.0283 (5)0.0236 (5)0.0175 (5)−0.0042 (4)−0.0031 (4)−0.0022 (4)
O2'0.0246 (5)0.0154 (4)0.0236 (5)−0.0015 (4)−0.0009 (4)0.0042 (4)
O3'0.0274 (5)0.0222 (5)0.0205 (5)0.0013 (4)−0.0059 (4)0.0063 (4)
O4'0.0314 (5)0.0213 (5)0.0210 (5)−0.0028 (4)−0.0074 (4)−0.0024 (4)

Geometric parameters (Å, °)

C1—C1'1.4885 (17)C5'—N2'1.4783 (16)
C1'—C2'1.3947 (17)C5—N21.4790 (16)
C1'—C6'1.3971 (18)C6—C11.3978 (17)
C2—C11.3950 (17)C6—C51.3860 (17)
C2—C31.3842 (17)C6—H60.9300
C2—H20.9300C6'—H6'0.9300
C2'—H2'0.953 (15)N1'—C3'1.4702 (15)
C3'—C2'1.3828 (17)N1—O11.2266 (14)
C3—C41.3816 (18)N1'—O1'1.2278 (14)
C3—N11.4712 (15)N1—O21.2257 (14)
C4'—C3'1.3843 (17)N1'—O2'1.2268 (14)
C4—H40.9300N2'—O3'1.2263 (14)
C4'—H4'0.942 (15)N2—O31.2301 (14)
C5'—C4'1.3828 (17)N2—O41.2226 (15)
C5—C41.3851 (18)N2'—O4'1.2252 (14)
C5'—C6'1.3876 (17)
C1—C2—H2120.4C4—C5—N2118.00 (11)
C1'—C2'—H2'122.1 (9)C5'—C4'—C3'115.76 (11)
C1'—C6'—H6'120.6C5—C4—H4122.1
C1—C6—H6120.7C5'—C4'—H4'122.1 (9)
C2'—C1'—C1119.08 (11)C5—C6—C1118.69 (11)
C2—C1—C1'120.71 (11)C5'—C6'—C1'118.79 (11)
C2—C1—C6119.36 (11)C5'—C6'—H6'120.6
C2'—C1'—C6'119.44 (11)C5—C6—H6120.7
C2'—C3'—C4'123.55 (11)C6—C1—C1'119.75 (11)
C2'—C3'—N1'118.27 (11)C6'—C1'—C1121.31 (11)
C2—C3—N1118.57 (11)C6—C5—N2118.42 (11)
C3'—C2'—C1'118.90 (11)C6'—C5'—N2'118.84 (11)
C3—C2—C1119.21 (11)O1'—N1'—C3'117.71 (10)
C3'—C2'—H2'118.9 (9)O1—N1—C3117.76 (10)
C3—C2—H2120.4O2'—N1'—C3'117.81 (10)
C3—C4—C5115.88 (11)O2—N1—C3117.96 (10)
C3—C4—H4122.1O2—N1—O1124.27 (10)
C3'—C4'—H4'122.2 (9)O2'—N1'—O1'124.48 (11)
C4—C3—C2123.28 (11)O3—N2—C5117.76 (10)
C4'—C3'—N1'118.09 (10)O3'—N2'—C5'117.84 (10)
C4—C3—N1118.11 (11)O4'—N2'—C5'117.72 (10)
C4'—C5'—C6'123.42 (11)O4—N2—C5117.79 (10)
C4—C5—C6123.57 (11)O4'—N2'—O3'124.44 (10)
C4'—C5'—N2'117.70 (10)O4—N2—O3124.45 (11)
C1—C1'—C2'—C3'171.43 (11)C5'—C4'—C3'—C2'1.28 (18)
C1—C1'—C6'—C5'−172.98 (11)C5'—C4'—C3'—N1'177.92 (10)
C1—C2—C3—C40.57 (18)C5—C6—C1—C1'174.55 (11)
C1—C2—C3—N1178.25 (11)C5—C6—C1—C2−0.67 (17)
C1—C6—C5—C40.20 (18)C6—C1—C1'—C2'−129.65 (12)
C1—C6—C5—N2−178.99 (10)C6—C1—C1'—C6'45.44 (17)
C2—C1—C1'—C2'45.51 (17)C6'—C1'—C2'—C3'−3.76 (18)
C2—C1—C1'—C6'−139.40 (12)C6—C5—C4—C30.62 (18)
C2'—C1'—C6'—C5'2.09 (18)C6'—C5'—C4'—C3'−3.07 (18)
C2—C3—C4—C5−1.01 (18)C6—C5—N2—O3170.62 (11)
C2—C3—N1—O17.99 (17)C6'—C5'—N2'—O3'178.23 (11)
C2—C3—N1—O2−171.36 (11)C6'—C5'—N2'—O4'−1.94 (17)
C3—C2—C1—C1'−174.87 (11)C6—C5—N2—O4−9.53 (16)
C3—C2—C1—C60.31 (18)N1'—C3'—C2'—C1'−174.56 (11)
C4'—C3'—C2'—C1'2.08 (19)N1—C3—C4—C5−178.70 (10)
C4—C3—N1—O1−174.20 (11)N2'—C5'—C4'—C3'179.39 (10)
C4—C3—N1—O26.44 (16)N2—C5—C4—C3179.81 (10)
C4'—C5'—C6'—C1'1.44 (19)N2'—C5'—C6'—C1'178.95 (10)
C4'—C5'—N2'—O3'−4.12 (16)O1'—N1'—C3'—C2'−20.79 (16)
C4—C5—N2—O3−8.62 (16)O1'—N1'—C3'—C4'162.39 (11)
C4—C5—N2—O4171.23 (11)O2'—N1'—C3'—C2'158.99 (11)
C4'—C5'—N2'—O4'175.71 (11)O2'—N1'—C3'—C4'−17.83 (16)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IM2105).

References

  • Allen, F. H., Baalham, C. A., Lommerse, J. P. M. & Raithby, P. R. (1998). Acta Cryst. B54, 320–329.
  • Bruker (2005). SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2008). APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  • Case, F. H. (1942). J. Am. Chem. Soc.64, 1848–1852.
  • Davis, T. L. (1941). Chemistry of Powder and Explosives Hollywood, CA: Angriff Press.
  • Debnath, A. K., Lopez de Compadre, R. L., Debnath, G., Shusterman, A. J. & Hansch, C. (1991). J. Med. Chem.34, 786–797. [PubMed]
  • Goossen, L. J., Rodriguez, N., Melzer, B., Linder, C., Deng, G. & Levy, L. M. (2007). J. Am. Chem. Soc.129, 4824–4833. [PubMed]
  • Hoffsommer, J. C. & McCullough, J. F. (1968). J. Chromatogr.38, 508–514.
  • Keshavarz, M. H. & Pouretedal, H. R. (2005). J. Hazard. Mater 124, 27–33. [PubMed]
  • Khrustalev, V. N., Vasil’kov, A. Y. & Antipin, M. Y. (2005). Acta Cryst. B61, 304–311. [PubMed]
  • Murray-Rust, P. (1982). Acta Cryst. B38, 2818–2825.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography