3,3',5,5'-Tetra-nitro-biphen-yl.

The title compound, C(12)H(6)N(4)O(8), is a biphenyl system that was synthesized as a building block for a new series of anti-malarial compounds. The aromatic rings are oriented at a dihedral angle of 45.5 (2)°, and inter-molecular short O⋯O contacts form a chain along the b axis. The strength of the inter-actions 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. (NO(2)-)C-C-C(NO(2)). 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 ▶) and Hoffsommer & McCullough (1968 ▶). For the use of polynitro­aromatic compounds as explosives, see Davis (1941 ▶) and Keshavarz & Pouretedal (2005 ▶). For their mutagenic and carcinogenic properties, see Debnath et al. (1991 ▶). For previous studies showing distortions induced in aromatic rings, see Murray-Rust (1982 ▶), Allen et al. (1998 ▶), and Khrustalev et al. (2005 ▶). For the preparation, see: Goossen et al. (2007 ▶).

Experimental

Crystal data

C12H6N4O8

M = 334.21

Orthorhombic,

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 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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.

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

C12H6N4O8	Dx = 1.745 Mg m−3
Mr = 334.21	Melting point: not measured K
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9828 reflections
a = 10.0683 (1) Å	θ = 3.9–67.6°
b = 15.4640 (2) Å	µ = 1.32 mm−1
c = 16.3436 (2) Å	T = 100 K
V = 2544.64 (5) Å3	Block, yellow
Z = 8	0.18 × 0.15 × 0.11 mm
F(000) = 1360

Bruker APEXII CCD diffractometer	2294 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
graphite	θmax = 68.0°, θmin = 5.4°
φ and ω scans	h = −12→12
30954 measured reflections	k = −18→18
2315 independent reflections	l = −19→19

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

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.

	x	y	z	Uiso*/Ueq
C1	0.34665 (12)	0.30780 (8)	0.43269 (7)	0.0157 (3)
C2	0.33233 (12)	0.30138 (8)	0.51737 (7)	0.0156 (3)
H2	0.2894	0.3448	0.5466	0.019*
C3	0.38272 (12)	0.22966 (8)	0.55741 (7)	0.0162 (3)
C4	0.44841 (12)	0.16333 (8)	0.51778 (8)	0.0168 (3)
H4	0.4828	0.1160	0.5458	0.020*
C5	0.45990 (12)	0.17162 (8)	0.43369 (8)	0.0165 (3)
C6	0.41093 (12)	0.24155 (8)	0.39006 (7)	0.0162 (3)
H6	0.4206	0.2443	0.3335	0.019*
N1	0.37026 (10)	0.22503 (7)	0.64699 (6)	0.0182 (2)
N2	0.52978 (10)	0.10245 (7)	0.38839 (7)	0.0189 (2)
O1	0.30268 (11)	0.28031 (6)	0.68111 (5)	0.0259 (2)
O2	0.42893 (10)	0.16675 (6)	0.68273 (5)	0.0236 (2)
O3	0.58781 (10)	0.04674 (6)	0.42849 (6)	0.0276 (2)
O4	0.52572 (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'	0.2127	0.3292	0.2918	0.019*
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)

	U11	U22	U33	U12	U13	U23
C1	0.0138 (6)	0.0161 (6)	0.0173 (6)	−0.0029 (5)	−0.0013 (4)	0.0007 (5)
C2	0.0155 (6)	0.0143 (6)	0.0171 (6)	−0.0015 (5)	0.0002 (5)	−0.0013 (5)
C3	0.0170 (6)	0.0179 (6)	0.0137 (6)	−0.0044 (5)	−0.0009 (4)	0.0009 (5)
C4	0.0162 (6)	0.0149 (6)	0.0193 (6)	−0.0018 (5)	−0.0024 (5)	0.0028 (5)
C5	0.0148 (6)	0.0154 (6)	0.0192 (6)	−0.0021 (5)	0.0010 (5)	−0.0025 (5)
C6	0.0163 (6)	0.0183 (6)	0.0140 (6)	−0.0035 (5)	−0.0005 (4)	−0.0003 (5)
N1	0.0214 (5)	0.0174 (5)	0.0158 (5)	−0.0039 (4)	0.0003 (4)	0.0015 (4)
N2	0.0167 (5)	0.0169 (5)	0.0230 (6)	−0.0012 (4)	0.0017 (4)	−0.0019 (4)
O1	0.0409 (6)	0.0193 (5)	0.0175 (5)	0.0015 (4)	0.0061 (4)	−0.0017 (4)
O2	0.0248 (5)	0.0269 (5)	0.0191 (5)	0.0004 (4)	−0.0015 (4)	0.0084 (4)
O3	0.0309 (5)	0.0200 (5)	0.0320 (5)	0.0079 (4)	0.0017 (4)	0.0022 (4)
O4	0.0263 (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)

C1—C1'	1.4885 (17)	C5'—N2'	1.4783 (16)
C1'—C2'	1.3947 (17)	C5—N2	1.4790 (16)
C1'—C6'	1.3971 (18)	C6—C1	1.3978 (17)
C2—C1	1.3950 (17)	C6—C5	1.3860 (17)
C2—C3	1.3842 (17)	C6—H6	0.9300
C2—H2	0.9300	C6'—H6'	0.9300
C2'—H2'	0.953 (15)	N1'—C3'	1.4702 (15)
C3'—C2'	1.3828 (17)	N1—O1	1.2266 (14)
C3—C4	1.3816 (18)	N1'—O1'	1.2278 (14)
C3—N1	1.4712 (15)	N1—O2	1.2257 (14)
C4'—C3'	1.3843 (17)	N1'—O2'	1.2268 (14)
C4—H4	0.9300	N2'—O3'	1.2263 (14)
C4'—H4'	0.942 (15)	N2—O3	1.2301 (14)
C5'—C4'	1.3828 (17)	N2—O4	1.2226 (15)
C5—C4	1.3851 (18)	N2'—O4'	1.2252 (14)
C5'—C6'	1.3876 (17)
C1—C2—H2	120.4	C4—C5—N2	118.00 (11)
C1'—C2'—H2'	122.1 (9)	C5'—C4'—C3'	115.76 (11)
C1'—C6'—H6'	120.6	C5—C4—H4	122.1
C1—C6—H6	120.7	C5'—C4'—H4'	122.1 (9)
C2'—C1'—C1	119.08 (11)	C5—C6—C1	118.69 (11)
C2—C1—C1'	120.71 (11)	C5'—C6'—C1'	118.79 (11)
C2—C1—C6	119.36 (11)	C5'—C6'—H6'	120.6
C2'—C1'—C6'	119.44 (11)	C5—C6—H6	120.7
C2'—C3'—C4'	123.55 (11)	C6—C1—C1'	119.75 (11)
C2'—C3'—N1'	118.27 (11)	C6'—C1'—C1	121.31 (11)
C2—C3—N1	118.57 (11)	C6—C5—N2	118.42 (11)
C3'—C2'—C1'	118.90 (11)	C6'—C5'—N2'	118.84 (11)
C3—C2—C1	119.21 (11)	O1'—N1'—C3'	117.71 (10)
C3'—C2'—H2'	118.9 (9)	O1—N1—C3	117.76 (10)
C3—C2—H2	120.4	O2'—N1'—C3'	117.81 (10)
C3—C4—C5	115.88 (11)	O2—N1—C3	117.96 (10)
C3—C4—H4	122.1	O2—N1—O1	124.27 (10)
C3'—C4'—H4'	122.2 (9)	O2'—N1'—O1'	124.48 (11)
C4—C3—C2	123.28 (11)	O3—N2—C5	117.76 (10)
C4'—C3'—N1'	118.09 (10)	O3'—N2'—C5'	117.84 (10)
C4—C3—N1	118.11 (11)	O4'—N2'—C5'	117.72 (10)
C4'—C5'—C6'	123.42 (11)	O4—N2—C5	117.79 (10)
C4—C5—C6	123.57 (11)	O4'—N2'—O3'	124.44 (10)
C4'—C5'—N2'	117.70 (10)	O4—N2—O3	124.45 (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—C4	0.57 (18)	C5—C6—C1—C1'	174.55 (11)
C1—C2—C3—N1	178.25 (11)	C5—C6—C1—C2	−0.67 (17)
C1—C6—C5—C4	0.20 (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—C3	0.62 (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—O3	170.62 (11)
C2—C3—N1—O1	7.99 (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—C6	0.31 (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—O2	6.44 (16)	N2—C5—C4—C3	179.81 (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—O4	171.23 (11)	O2'—N1'—C3'—C2'	158.99 (11)
C4'—C5'—N2'—O4'	175.71 (11)	O2'—N1'—C3'—C4'	−17.83 (16)