1,2-Bis(2,4,6-trinitro­phen­yl)ethane

Wang, W.-Y.; Diao, Y.; Wei, Z.-H.; Wang, J.-L.

doi:10.1107/S1600536811042802

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3044

doi:10.1107/S1600536811042802

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1,2-Bis(2,4,6-trinitrophenyl)ethane

Wen-Yan Wang,^a Ying Diao,^a Zhi-Hua Wei ^a and Jian-Long Wang ^a ^*

^aSchool of Chemical Engineering and Environment, North University of China, Taiyuan, People's Republic of China
^*Correspondence e-mail: wangjianlong@nuc.edu.cn

(Received 2 October 2011; accepted 15 October 2011; online 29 October 2011)

The title compound, C₁₄H₈N₆O₁₂, is centrosymmetric, the mid-point of the central C—C bond being located on an inversion centre. Two of the three independent nitro groups are disordered over two sites, with a site-occupancy ratio of 0.513 (3):0.487 (3). Weak intermolecular C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For the synthesis of the title compound, see: Shipp (1964 ); Gilbert & Morristown (1980 ).

Experimental

Crystal data

C₁₄H₈N₆O₁₂
M_r = 452.26
Monoclinic, P 2₁ /c
a = 5.8468 (5) Å
b = 8.1253 (11) Å
c = 17.977 (2) Å
β = 97.154 (8)°
V = 847.38 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 113 K
0.22 × 0.20 × 0.16 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2000 ) T_min = 0.966, T_max = 0.975
7531 measured reflections
2013 independent reflections
1503 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.099
S = 1.04
2013 reflections
186 parameters
70 restraints
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O4ⁱ	0.99	2.43	3.3669 (15)	158
C1—H1B⋯O5ⁱⁱ	0.99	2.37	3.147 (2)	134
Symmetry codes: (i) x, y+1, z; (ii) -x, -y+1, -z.

Data collection: CrystalClear (Rigaku/MSC, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811042802/xu5348sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811042802/xu5348Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811042802/xu5348Isup3.cml

checkCIF report

Comment top

2,2',4,4',6,6'-Hexanitrostilbene is one of the most important heat resistant explosives. It can be prepared by treating the solution of TNT in tetrahydrofuran–methanol mixture with 5% sodium hypochlorite (Shipp, 1964). Later on its synthesis method was improved by Gilbert & Morristown (1980). As an intermediate, 2,2',4,4',6,6'-hexanitrobibenzyl was synthesized by the oxidation of TNT. Here we report the crystal structure of the title compound.

In the crystal structure, there is an inversion center in the molecule. Weak intermolecular C—H···O hydrogen bonding is present in the crystal structure.

Related literature top

For the synthesis of the title compound, see: Shipp (1964); Gilbert & Morristown (1980).

Experimental top

The title compound was prepared according to literature method (Gilbert & Morristown, 1980). Single crystals were obtained by evaporation of a solution of the title compound in acetone at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2000); cell refinement: CrystalClear (Rigaku/MSC, 2000); data reduction: CrystalClear (Rigaku/MSC, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. The crystal packing of the title compound.

1,2-Bis(2,4,6-trinitrophenyl)ethane top

Crystal data top

C₁₄H₈N₆O₁₂	F(000) = 460
M_r = 452.26	D_x = 1.773 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3228 reflections
a = 5.8468 (5) Å	θ = 2.3–27.9°
b = 8.1253 (11) Å	µ = 0.16 mm⁻¹
c = 17.977 (2) Å	T = 113 K
β = 97.154 (8)°	Prism, colourless
V = 847.38 (17) Å³	0.22 × 0.20 × 0.16 mm
Z = 2

Data collection top

Rigaku Saturn724 CCD diffractometer	2013 independent reflections
Radiation source: rotating anode	1503 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.034
Detector resolution: 14.22 pixels mm^-1	θ_max = 27.9°, θ_min = 2.3°
ω and ϕ scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2000)	k = −8→10
T_min = 0.966, T_max = 0.975	l = −23→23
7531 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0569P)² + 0.0176P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2013 reflections	Δρ_max = 0.26 e Å⁻³
186 parameters	Δρ_min = −0.25 e Å⁻³
70 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.025 (5)

Crystal data top

C₁₄H₈N₆O₁₂	V = 847.38 (17) Å³
M_r = 452.26	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.8468 (5) Å	µ = 0.16 mm⁻¹
b = 8.1253 (11) Å	T = 113 K
c = 17.977 (2) Å	0.22 × 0.20 × 0.16 mm
β = 97.154 (8)°

Data collection top

Rigaku Saturn724 CCD diffractometer	2013 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2000)	1503 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.975	R_int = 0.034
7531 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	70 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.04	Δρ_max = 0.26 e Å⁻³
2013 reflections	Δρ_min = −0.25 e Å⁻³
186 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
N1	0.788 (2)	0.4687 (13)	0.1645 (5)	0.0296 (16)	0.513 (3)
O1	0.8771 (5)	0.5628 (3)	0.12216 (13)	0.0302 (6)	0.513 (3)
O2	0.815 (3)	0.489 (2)	0.2328 (6)	0.0260 (15)	0.513 (3)
N1'	0.824 (2)	0.4472 (14)	0.1631 (5)	0.0296 (16)	0.487 (3)
O1'	0.9430 (5)	0.4872 (4)	0.11433 (14)	0.0355 (7)	0.487 (3)
O2'	0.822 (3)	0.503 (2)	0.2263 (7)	0.035 (3)	0.487 (3)
O3	0.72410 (17)	−0.11091 (14)	0.26187 (5)	0.0387 (3)
O4	0.48405 (19)	−0.23368 (11)	0.17726 (5)	0.0344 (3)
N3	0.15225 (18)	0.19328 (12)	0.00293 (5)	0.0229 (3)
O5	−0.0105 (3)	0.2748 (3)	0.01446 (10)	0.0295 (6)	0.513 (3)
O6	0.1555 (3)	0.0949 (3)	−0.04988 (9)	0.0301 (7)	0.513 (3)
O5'	−0.0438 (3)	0.1733 (4)	0.01768 (11)	0.0328 (6)	0.487 (3)
O6'	0.2022 (4)	0.2111 (3)	−0.06168 (10)	0.0345 (7)	0.487 (3)
N2	0.59258 (19)	−0.11271 (15)	0.20272 (6)	0.0299 (3)
C1	0.4345 (2)	0.49440 (15)	0.03484 (6)	0.0222 (3)
H1A	0.4797	0.5885	0.0685	0.027*
H1B	0.2668	0.5029	0.0185	0.027*
C2	0.4834 (2)	0.33521 (15)	0.07792 (6)	0.0226 (3)
C3	0.6575 (2)	0.31668 (17)	0.13844 (6)	0.0267 (3)
C4	0.6978 (2)	0.17462 (17)	0.18056 (6)	0.0271 (3)
H4	0.8168	0.1692	0.2216	0.033*
C5	0.5584 (2)	0.04194 (16)	0.16040 (7)	0.0263 (3)
C6	0.3810 (2)	0.04812 (17)	0.10198 (7)	0.0268 (3)
H6	0.2850	−0.0445	0.0892	0.032*
C7	0.3490 (2)	0.19428 (16)	0.06306 (6)	0.0229 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.011 (3)	0.047 (2)	0.0282 (8)	−0.005 (2)	−0.0062 (11)	0.0187 (11)
O1	0.0339 (14)	0.0303 (14)	0.0260 (10)	−0.0121 (10)	0.0020 (9)	0.0048 (10)
O2	0.027 (3)	0.024 (3)	0.026 (2)	−0.0047 (19)	0.001 (2)	−0.002 (3)
N1'	0.011 (3)	0.047 (2)	0.0282 (8)	−0.005 (2)	−0.0062 (11)	0.0187 (11)
O1'	0.0315 (16)	0.0473 (18)	0.0260 (12)	−0.0210 (12)	−0.0031 (10)	0.0114 (12)
O2'	0.028 (3)	0.031 (4)	0.048 (5)	−0.004 (2)	0.010 (3)	0.008 (2)
O3	0.0289 (6)	0.0549 (7)	0.0298 (5)	−0.0031 (5)	−0.0069 (4)	0.0208 (5)
O4	0.0452 (7)	0.0309 (5)	0.0262 (5)	0.0059 (4)	0.0002 (4)	0.0024 (4)
N3	0.0192 (6)	0.0277 (6)	0.0213 (5)	−0.0009 (4)	0.0011 (4)	0.0056 (4)
O5	0.0182 (10)	0.0352 (14)	0.0345 (10)	0.0056 (9)	0.0009 (8)	0.0059 (9)
O6	0.0282 (11)	0.0410 (15)	0.0203 (9)	−0.0031 (9)	0.0001 (7)	−0.0006 (8)
O5'	0.0170 (11)	0.0421 (16)	0.0390 (12)	0.0004 (10)	0.0016 (9)	0.0030 (11)
O6'	0.0379 (13)	0.0474 (16)	0.0169 (9)	−0.0111 (10)	−0.0022 (8)	0.0054 (9)
N2	0.0254 (6)	0.0418 (7)	0.0225 (5)	0.0051 (5)	0.0030 (4)	0.0104 (5)
C1	0.0214 (7)	0.0296 (6)	0.0155 (5)	−0.0056 (5)	0.0013 (5)	0.0023 (5)
C2	0.0172 (6)	0.0361 (7)	0.0151 (5)	−0.0018 (5)	0.0039 (4)	0.0053 (5)
C3	0.0194 (7)	0.0426 (8)	0.0182 (6)	−0.0075 (5)	0.0026 (5)	0.0063 (5)
C4	0.0170 (7)	0.0473 (8)	0.0166 (6)	−0.0013 (5)	0.0003 (5)	0.0089 (5)
C5	0.0235 (7)	0.0370 (7)	0.0186 (6)	0.0023 (6)	0.0033 (5)	0.0108 (5)
C6	0.0235 (7)	0.0347 (7)	0.0220 (6)	−0.0040 (5)	0.0016 (5)	0.0066 (5)
C7	0.0162 (6)	0.0371 (7)	0.0149 (5)	−0.0006 (5)	0.0004 (4)	0.0052 (5)

Geometric parameters (Å, º) top

N1—O2	1.231 (8)	N2—C5	1.4697 (16)
N1—O1	1.238 (7)	C1—C2	1.5164 (16)
N1—C3	1.496 (7)	C1—C1ⁱ	1.550 (2)
N1'—O2'	1.226 (8)	C1—H1A	0.9900
N1'—O1'	1.228 (8)	C1—H1B	0.9900
N1'—C3	1.471 (7)	C2—C7	1.3957 (17)
O3—N2	1.2323 (13)	C2—C3	1.4024 (16)
O4—N2	1.2271 (15)	C3—C4	1.3846 (18)
N3—O5	1.199 (2)	C4—C5	1.3728 (19)
N3—O5'	1.219 (2)	C4—H4	0.9500
N3—O6'	1.241 (2)	C5—C6	1.3820 (17)
N3—O6	1.243 (2)	C6—C7	1.3792 (18)
N3—C7	1.4772 (14)	C6—H6	0.9500

O2—N1—O1	121.2 (11)	C1ⁱ—C1—H1B	109.1
O2—N1—C3	114.9 (9)	H1A—C1—H1B	107.8
O1—N1—C3	123.7 (6)	C7—C2—C3	113.41 (11)
O2'—N1'—O1'	129.5 (12)	C7—C2—C1	122.43 (10)
O2'—N1'—C3	117.6 (10)	C3—C2—C1	124.07 (11)
O1'—N1'—C3	112.9 (6)	C4—C3—C2	124.86 (12)
O5—N3—O5'	41.21 (12)	C4—C3—N1'	112.0 (6)
O5—N3—O6'	112.46 (16)	C2—C3—N1'	123.1 (6)
O5'—N3—O6'	123.81 (15)	C4—C3—N1	118.2 (5)
O5—N3—O6	125.15 (16)	C2—C3—N1	116.5 (5)
O5'—N3—O6	100.65 (16)	N1'—C3—N1	10.7 (11)
O6'—N3—O6	48.11 (12)	C5—C4—C3	117.07 (11)
O5—N3—C7	115.66 (13)	C5—C4—H4	121.5
O5'—N3—C7	120.60 (13)	C3—C4—H4	121.5
O6'—N3—C7	115.58 (13)	C4—C5—C6	122.48 (11)
O6—N3—C7	118.54 (12)	C4—C5—N2	119.78 (11)
O4—N2—O3	124.71 (11)	C6—C5—N2	117.73 (12)
O4—N2—C5	117.46 (10)	C7—C6—C5	117.28 (12)
O3—N2—C5	117.81 (11)	C7—C6—H6	121.4
C2—C1—C1ⁱ	112.47 (13)	C5—C6—H6	121.4
C2—C1—H1A	109.1	C6—C7—C2	124.88 (11)
C1ⁱ—C1—H1A	109.1	C6—C7—N3	114.24 (11)
C2—C1—H1B	109.1	C2—C7—N3	120.87 (10)

C1ⁱ—C1—C2—C7	−90.86 (16)	C3—C4—C5—C6	−1.5 (2)
C1ⁱ—C1—C2—C3	92.64 (16)	C3—C4—C5—N2	179.85 (11)
C7—C2—C3—C4	0.13 (18)	O4—N2—C5—C4	−171.13 (12)
C1—C2—C3—C4	176.91 (12)	O3—N2—C5—C4	10.35 (18)
C7—C2—C3—N1'	178.3 (5)	O4—N2—C5—C6	10.15 (18)
C1—C2—C3—N1'	−4.9 (5)	O3—N2—C5—C6	−168.36 (12)
C7—C2—C3—N1	−172.0 (4)	C4—C5—C6—C7	0.7 (2)
C1—C2—C3—N1	4.8 (5)	N2—C5—C6—C7	179.42 (11)
O2'—N1'—C3—C4	−64.8 (15)	C5—C6—C7—C2	0.6 (2)
O1'—N1'—C3—C4	117.4 (9)	C5—C6—C7—N3	−178.30 (11)
O2'—N1'—C3—C2	116.8 (13)	C3—C2—C7—C6	−0.98 (18)
O1'—N1'—C3—C2	−61.0 (13)	C1—C2—C7—C6	−177.82 (12)
O2'—N1'—C3—N1	62 (4)	C3—C2—C7—N3	177.83 (10)
O1'—N1'—C3—N1	−116 (5)	C1—C2—C7—N3	0.99 (18)
O2—N1—C3—C4	−38.7 (14)	O5—N3—C7—C6	109.24 (19)
O1—N1—C3—C4	136.6 (10)	O5'—N3—C7—C6	62.5 (2)
O2—N1—C3—C2	134.0 (11)	O6'—N3—C7—C6	−116.35 (17)
O1—N1—C3—C2	−50.7 (13)	O6—N3—C7—C6	−61.96 (18)
O2—N1—C3—N1'	−96 (4)	O5—N3—C7—C2	−69.7 (2)
O1—N1—C3—N1'	79 (3)	O5'—N3—C7—C2	−116.4 (2)
C2—C3—C4—C5	1.1 (2)	O6'—N3—C7—C2	64.72 (19)
N1'—C3—C4—C5	−177.3 (5)	O6—N3—C7—C2	119.11 (17)
N1—C3—C4—C5	173.0 (5)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O4ⁱⁱ	0.99	2.43	3.3669 (15)	158
C1—H1B···O5ⁱⁱⁱ	0.99	2.37	3.147 (2)	134

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

Experimental details

Crystal data
Chemical formula	C₁₄H₈N₆O₁₂
M_r	452.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	5.8468 (5), 8.1253 (11), 17.977 (2)
β (°)	97.154 (8)
V (Å³)	847.38 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.22 × 0.20 × 0.16

Data collection
Diffractometer	Rigaku Saturn724 CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2000)
T_min, T_max	0.966, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	7531, 2013, 1503
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.099, 1.04
No. of reflections	2013
No. of parameters	186
No. of restraints	70
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.25

Computer programs: CrystalClear (Rigaku/MSC, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O4ⁱ	0.99	2.43	3.3669 (15)	158
C1—H1B···O5ⁱⁱ	0.99	2.37	3.147 (2)	134

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

Acknowledgements

The authors thank China North Industries Group Corporation for financial support.

References

Gilbert, E. E. & Morristown, N. J. (1980). US Patent 4221745. Google Scholar
Rigaku/MSC (2000). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shipp, K. G. (1964). J. Org. Chem. 29, 2620–2623. CrossRef CAS Web of Science Google Scholar