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ISSN: 2056-9890

2-[2-(2,4-Di­nitro­phen­yl)eth­yl]-1,3,5-tri­nitro­benzene

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 5 October 2011; online 8 October 2011)

In the title compound, C14H9N5O10, the two benzene rings are inclined at a dihedral angle of 14.81 (5)°, and the nitro groups are twisted with respect to the benzene rings to which they are attached, making dihedral angles of 57.89 (7), 14.93 (7), 62.58 (7), 2.80 (12) and 22.38 (12)°. Weak inter­molecular C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

The title compound is an inter­mediate in the synthesis of the high energy density compound 2,2′,4,4′,6,6′-hexa­nitro­stilbene, see: Shipp (1964[Shipp, K. G. (1964). J. Org. Chem. 29, 2620-2623.]). For the synthesis, see: Blatt & Rytina (1950[Blatt, A. H. & Rytina, A. W. (1950). J. Am. Chem. Soc. 72, 403-405.]).

[Scheme 1]

Experimental

Crystal data
  • C14H9N5O10

  • Mr = 407.26

  • Monoclinic, P 21 /n

  • a = 14.099 (7) Å

  • b = 8.227 (4) Å

  • c = 15.356 (8) Å

  • β = 114.758 (7)°

  • V = 1617.6 (14) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.15 mm−1

  • T = 113 K

  • 0.20 × 0.18 × 0.12 mm

Data collection
  • Rigaku Saturn724 CCD diffractometer

  • Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2000[Rigaku/MSC (2000). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.971, Tmax = 0.983

  • 16454 measured reflections

  • 3823 independent reflections

  • 2847 reflections with I > 2σ(I)

  • Rint = 0.043

Refinement
  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 0.107

  • S = 1.03

  • 3823 reflections

  • 262 parameters

  • H-atom parameters constrained

  • Δρmax = 0.35 e Å−3

  • Δρmin = −0.33 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C4—H4⋯O8i 0.95 2.39 3.249 (2) 151
C10—H10⋯O2ii 0.95 2.58 3.508 (3) 167
C11—H11⋯O9ii 0.95 2.40 3.353 (3) 176
Symmetry codes: (i) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]; (ii) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}].

Data collection: CrystalClear (Rigaku/MSC, 2000[Rigaku/MSC (2000). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

2,2',4,4',6,6'-Hexantanitrobibenzyl, which can be prepared from bibenzyl by nitration (Blatt & Rytina, 1950), is a intermediate for synthesizing high energy density compound 2,2',4,4',6,6'-hexanitrostilbene (Shipp, 1964). As a byproduct, 2,2',4,4',6–pentantanitrobibenzyl is separated from the nitrate product. Here we report the crystal structure of the title compound.

In the crystal structure, because the number of nitro group is not identical in two benzene rings, the two benzene rings are inclined at a dihedral angle 14.811 (48)°, For the interaction of nitro groups, the nitro groups is rotated out the benzene plane, making dihedral angles of 57.885 (65)°(N1/O1, O2), 14.934 (68)°(N2/O3, O4), 62.579 (71)° (N3/O5, O6), 2.799 (121)°(N4/O7, O8) and 22.376 (115)° (N5/O9, O10).

Related literature top

The title compound is an intermediate in the synthesis of the high

energy density compound 2,2',4,4',6,6'-hexanitrostilbene, see: Shipp (1964). For the synthesis, see: Blatt & Rytina (1950).

Experimental top

The title compound was prepared according to literature method (Blatt et al., 1950). Single crystals were obtained by evaporation of a solution of the title compound in ethyl acetate at room temperature.

Refinement top

All the Friedel pairs were merged. All H atoms were positioned geometrically and treated as riding, with C—H bond lengths constrained to 0.95 ° for benzene ring H and 0.99 ° for methylene H atoms, and with Uiso(H) = 1.2Ueq(C).

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
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The crystal packing of the title compound.
2-[2-(2,4-Dinitrophenyl)ethyl]-1,3,5-trinitrobenzene top
Crystal data top
C14H9N5O10F(000) = 832
Mr = 407.26Dx = 1.672 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5515 reflections
a = 14.099 (7) Åθ = 1.6–27.9°
b = 8.227 (4) ŵ = 0.15 mm1
c = 15.356 (8) ÅT = 113 K
β = 114.758 (7)°Prism, colorless
V = 1617.6 (14) Å30.20 × 0.18 × 0.12 mm
Z = 4
Data collection top
Rigaku Saturn724 CCD
diffractometer
3823 independent reflections
Radiation source: rotating anode2847 reflections with I > 2σ(I)
Multilayer monochromatorRint = 0.043
Detector resolution: 14.22 pixels mm-1θmax = 27.9°, θmin = 1.7°
ω and ϕ scansh = 1812
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2000)
k = 1010
Tmin = 0.971, Tmax = 0.983l = 2019
16454 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0594P)2]
where P = (Fo2 + 2Fc2)/3
3823 reflections(Δ/σ)max = 0.002
262 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
C14H9N5O10V = 1617.6 (14) Å3
Mr = 407.26Z = 4
Monoclinic, P21/nMo Kα radiation
a = 14.099 (7) ŵ = 0.15 mm1
b = 8.227 (4) ÅT = 113 K
c = 15.356 (8) Å0.20 × 0.18 × 0.12 mm
β = 114.758 (7)°
Data collection top
Rigaku Saturn724 CCD
diffractometer
3823 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2000)
2847 reflections with I > 2σ(I)
Tmin = 0.971, Tmax = 0.983Rint = 0.043
16454 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.107H-atom parameters constrained
S = 1.03Δρmax = 0.35 e Å3
3823 reflectionsΔρmin = 0.33 e Å3
262 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
xyzUiso*/Ueq
O10.64474 (9)0.08191 (14)1.03105 (8)0.0325 (3)
O20.68105 (8)0.33883 (14)1.06099 (7)0.0270 (3)
O30.86607 (8)0.48825 (14)0.85862 (7)0.0273 (3)
O40.79057 (8)0.43068 (14)0.70657 (7)0.0283 (3)
O50.39540 (8)0.33811 (14)0.60692 (8)0.0291 (3)
O60.40895 (9)0.07989 (14)0.63732 (8)0.0369 (3)
O70.06620 (8)0.15196 (13)0.84028 (8)0.0264 (3)
O80.02060 (9)0.19441 (17)0.99188 (8)0.0408 (3)
O90.37441 (8)0.36062 (14)1.11500 (7)0.0281 (3)
O100.46932 (9)0.29102 (18)1.04226 (9)0.0450 (4)
N10.65521 (9)0.22023 (16)1.00726 (9)0.0217 (3)
N20.79545 (9)0.42757 (15)0.78811 (8)0.0199 (3)
N30.43956 (9)0.21995 (16)0.65550 (8)0.0204 (3)
N40.01476 (10)0.18383 (16)0.91063 (9)0.0224 (3)
N50.38449 (10)0.31254 (16)1.04428 (9)0.0227 (3)
C10.63893 (11)0.24823 (17)0.90684 (10)0.0171 (3)
C20.72280 (11)0.31584 (17)0.89544 (10)0.0186 (3)
H20.78660.33920.94900.022*
C30.71003 (11)0.34782 (17)0.80322 (10)0.0163 (3)
C40.61836 (11)0.31584 (17)0.72466 (10)0.0174 (3)
H40.61100.33810.66140.021*
C50.53752 (11)0.25001 (17)0.74139 (10)0.0166 (3)
C60.54234 (11)0.21345 (17)0.83201 (10)0.0168 (3)
C70.44685 (11)0.16298 (17)0.84700 (11)0.0193 (3)
H7A0.46870.10850.90990.023*
H7B0.40460.08530.79640.023*
C80.38085 (11)0.31511 (19)0.84336 (11)0.0224 (3)
H8A0.42570.39620.89010.027*
H8B0.35530.36420.77870.027*
C90.28820 (11)0.27651 (17)0.86572 (10)0.0184 (3)
C100.19285 (11)0.24056 (18)0.78975 (10)0.0206 (3)
H100.18920.23830.72660.025*
C110.10317 (11)0.20795 (18)0.80267 (10)0.0207 (3)
H110.03920.18310.74970.025*
C120.10966 (10)0.21278 (17)0.89524 (10)0.0168 (3)
C130.20092 (11)0.24750 (17)0.97324 (10)0.0184 (3)
H130.20370.25121.03610.022*
C140.28871 (11)0.27693 (17)0.95696 (10)0.0174 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0369 (7)0.0277 (7)0.0361 (7)0.0037 (5)0.0186 (5)0.0142 (5)
O20.0267 (6)0.0344 (7)0.0198 (6)0.0049 (5)0.0096 (5)0.0043 (5)
O30.0223 (6)0.0302 (7)0.0264 (6)0.0099 (5)0.0074 (5)0.0005 (5)
O40.0273 (6)0.0392 (7)0.0234 (6)0.0053 (5)0.0156 (5)0.0023 (5)
O50.0249 (6)0.0293 (7)0.0249 (6)0.0011 (5)0.0023 (5)0.0041 (5)
O60.0293 (7)0.0235 (7)0.0455 (7)0.0058 (5)0.0035 (6)0.0108 (5)
O70.0151 (6)0.0305 (6)0.0307 (6)0.0029 (4)0.0069 (5)0.0059 (5)
O80.0273 (7)0.0792 (10)0.0204 (6)0.0048 (6)0.0143 (5)0.0012 (6)
O90.0260 (6)0.0374 (7)0.0180 (5)0.0030 (5)0.0063 (5)0.0062 (5)
O100.0147 (6)0.0825 (11)0.0368 (7)0.0038 (6)0.0097 (5)0.0248 (7)
N10.0182 (7)0.0254 (7)0.0224 (7)0.0017 (5)0.0094 (5)0.0051 (5)
N20.0185 (7)0.0211 (7)0.0211 (7)0.0016 (5)0.0094 (5)0.0018 (5)
N30.0172 (6)0.0243 (7)0.0216 (6)0.0020 (5)0.0100 (5)0.0048 (5)
N40.0180 (7)0.0263 (7)0.0227 (7)0.0004 (5)0.0083 (6)0.0007 (5)
N50.0170 (7)0.0268 (7)0.0228 (7)0.0007 (5)0.0069 (5)0.0055 (5)
C10.0193 (7)0.0166 (7)0.0172 (7)0.0013 (5)0.0094 (6)0.0021 (5)
C20.0168 (7)0.0186 (7)0.0185 (7)0.0007 (6)0.0056 (6)0.0011 (6)
C30.0144 (7)0.0162 (7)0.0213 (7)0.0004 (5)0.0103 (6)0.0005 (5)
C40.0195 (7)0.0178 (7)0.0158 (7)0.0017 (6)0.0083 (6)0.0005 (5)
C50.0127 (7)0.0178 (7)0.0183 (7)0.0007 (5)0.0053 (6)0.0032 (5)
C60.0173 (7)0.0136 (7)0.0203 (7)0.0006 (5)0.0089 (6)0.0012 (5)
C70.0179 (8)0.0194 (8)0.0242 (8)0.0028 (6)0.0122 (6)0.0015 (6)
C80.0221 (8)0.0217 (8)0.0269 (8)0.0003 (6)0.0137 (7)0.0000 (6)
C90.0190 (8)0.0160 (7)0.0223 (8)0.0013 (5)0.0107 (6)0.0001 (6)
C100.0229 (8)0.0247 (8)0.0163 (7)0.0015 (6)0.0101 (6)0.0007 (6)
C110.0181 (8)0.0239 (8)0.0171 (7)0.0005 (6)0.0044 (6)0.0027 (6)
C120.0148 (7)0.0176 (7)0.0199 (7)0.0003 (5)0.0091 (6)0.0000 (6)
C130.0203 (8)0.0194 (7)0.0164 (7)0.0015 (6)0.0084 (6)0.0003 (5)
C140.0138 (7)0.0172 (7)0.0186 (7)0.0004 (5)0.0041 (6)0.0024 (6)
Geometric parameters (Å, º) top
O1—N11.2229 (17)C4—C51.380 (2)
O2—N11.2305 (17)C4—H40.9500
O3—N21.2289 (15)C5—C61.397 (2)
O4—N21.2252 (16)C6—C71.516 (2)
O5—N31.2248 (17)C7—C81.547 (2)
O6—N31.2211 (17)C7—H7A0.9900
O7—N41.2272 (16)C7—H7B0.9900
O8—N41.2187 (18)C8—C91.517 (2)
O9—N51.2187 (16)C8—H8A0.9900
O10—N51.2222 (17)C8—H8B0.9900
N1—C11.4789 (19)C9—C101.394 (2)
N2—C31.4727 (18)C9—C141.398 (2)
N3—C51.4774 (18)C10—C111.386 (2)
N4—C121.472 (2)C10—H100.9500
N5—C141.4801 (19)C11—C121.386 (2)
C1—C21.383 (2)C11—H110.9500
C1—C61.395 (2)C12—C131.372 (2)
C2—C31.376 (2)C13—C141.383 (2)
C2—H20.9500C13—H130.9500
C3—C41.374 (2)
O1—N1—O2125.21 (13)C5—C6—C7122.30 (12)
O1—N1—C1118.10 (13)C6—C7—C8109.39 (12)
O2—N1—C1116.66 (12)C6—C7—H7A109.8
O4—N2—O3124.75 (12)C8—C7—H7A109.8
O4—N2—C3118.08 (12)C6—C7—H7B109.8
O3—N2—C3117.16 (12)C8—C7—H7B109.8
O6—N3—O5124.67 (13)H7A—C7—H7B108.2
O6—N3—C5118.09 (12)C9—C8—C7112.61 (12)
O5—N3—C5117.23 (12)C9—C8—H8A109.1
O8—N4—O7123.76 (13)C7—C8—H8A109.1
O8—N4—C12118.46 (12)C9—C8—H8B109.1
O7—N4—C12117.78 (12)C7—C8—H8B109.1
O9—N5—O10123.38 (13)H8A—C8—H8B107.8
O9—N5—C14117.97 (13)C10—C9—C14115.96 (13)
O10—N5—C14118.65 (13)C10—C9—C8118.37 (13)
C2—C1—C6124.74 (13)C14—C9—C8125.65 (13)
C2—C1—N1115.28 (12)C11—C10—C9122.64 (14)
C6—C1—N1119.91 (13)C11—C10—H10118.7
C3—C2—C1117.19 (13)C9—C10—H10118.7
C3—C2—H2121.4C10—C11—C12117.96 (13)
C1—C2—H2121.4C10—C11—H11121.0
C4—C3—C2122.44 (13)C12—C11—H11121.0
C4—C3—N2118.51 (13)C13—C12—C11122.44 (13)
C2—C3—N2118.96 (12)C13—C12—N4118.48 (13)
C3—C4—C5117.27 (13)C11—C12—N4119.06 (12)
C3—C4—H4121.4C12—C13—C14117.52 (13)
C5—C4—H4121.4C12—C13—H13121.2
C4—C5—C6124.78 (13)C14—C13—H13121.2
C4—C5—N3115.83 (13)C13—C14—C9123.46 (13)
C6—C5—N3119.38 (13)C13—C14—N5114.64 (13)
C1—C6—C5113.57 (13)C9—C14—N5121.89 (13)
C1—C6—C7123.63 (13)
O1—N1—C1—C2122.42 (14)N3—C5—C6—C77.6 (2)
O2—N1—C1—C255.76 (17)C1—C6—C7—C893.28 (16)
O1—N1—C1—C660.38 (18)C5—C6—C7—C878.03 (17)
O2—N1—C1—C6121.44 (15)C6—C7—C8—C9175.40 (12)
C6—C1—C2—C31.3 (2)C7—C8—C9—C1092.16 (15)
N1—C1—C2—C3178.37 (12)C7—C8—C9—C1489.32 (18)
C1—C2—C3—C40.4 (2)C14—C9—C10—C110.4 (2)
C1—C2—C3—N2176.88 (12)C8—C9—C10—C11178.27 (14)
O4—N2—C3—C415.38 (19)C9—C10—C11—C120.4 (2)
O3—N2—C3—C4163.70 (13)C10—C11—C12—C130.3 (2)
O4—N2—C3—C2167.96 (13)C10—C11—C12—N4178.04 (13)
O3—N2—C3—C212.96 (19)O8—N4—C12—C131.2 (2)
C2—C3—C4—C50.3 (2)O7—N4—C12—C13179.59 (13)
N2—C3—C4—C5176.20 (12)O8—N4—C12—C11177.28 (13)
C3—C4—C5—C60.2 (2)O7—N4—C12—C112.0 (2)
C3—C4—C5—N3178.94 (12)C11—C12—C13—C140.6 (2)
O6—N3—C5—C4117.21 (15)N4—C12—C13—C14178.95 (12)
O5—N3—C5—C462.02 (17)C12—C13—C14—C91.5 (2)
O6—N3—C5—C663.64 (18)C12—C13—C14—N5179.64 (13)
O5—N3—C5—C6117.13 (15)C10—C9—C14—C131.4 (2)
C2—C1—C6—C51.4 (2)C8—C9—C14—C13177.18 (14)
N1—C1—C6—C5178.36 (12)C10—C9—C14—N5179.81 (13)
C2—C1—C6—C7170.56 (14)C8—C9—C14—N51.6 (2)
N1—C1—C6—C76.4 (2)O9—N5—C14—C1321.49 (19)
C4—C5—C6—C10.7 (2)O10—N5—C14—C13157.85 (15)
N3—C5—C6—C1179.73 (12)O9—N5—C14—C9157.42 (14)
C4—C5—C6—C7171.45 (13)O10—N5—C14—C923.2 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O8i0.952.393.249 (2)151
C10—H10···O2ii0.952.583.508 (3)167
C11—H11···O9ii0.952.403.353 (3)176
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x1/2, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC14H9N5O10
Mr407.26
Crystal system, space groupMonoclinic, P21/n
Temperature (K)113
a, b, c (Å)14.099 (7), 8.227 (4), 15.356 (8)
β (°) 114.758 (7)
V3)1617.6 (14)
Z4
Radiation typeMo Kα
µ (mm1)0.15
Crystal size (mm)0.20 × 0.18 × 0.12
Data collection
DiffractometerRigaku Saturn724 CCD
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku/MSC, 2000)
Tmin, Tmax0.971, 0.983
No. of measured, independent and
observed [I > 2σ(I)] reflections
16454, 3823, 2847
Rint0.043
(sin θ/λ)max1)0.658
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.107, 1.03
No. of reflections3823
No. of parameters262
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.35, 0.33

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

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O8i0.952.393.249 (2)151
C10—H10···O2ii0.952.583.508 (3)167
C11—H11···O9ii0.952.403.353 (3)176
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x1/2, y+1/2, z1/2.
 

Acknowledgements

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

References

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