supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2008). E64, o2151    [ doi:10.1107/S1600536808031139 ]

1,3,4,6-Tetrachloro-7,7-bis(4-chlorophenyl)bicyclo[4.2.0]oct-3-ene-2,5-dione

H. Hu, L. Li, J.-F. Ji and Z.-G. Shen

Abstract top

The title compound, C20H10Cl6O2, a quinone derivative, was obtained by the irradiation of 2,3,5,6-tetrachlorobenzoquinone and 4,4'-(ethene-1,1-diyl)bis(chlorobenzene). The six- and four-membered rings are fused in a cis configuration. The dihedral angle between them is 53.4 (3)°.

Comment top

The reactions of the high potential 2,3,5,6-tetrachlorobenzoquinone with alkenes display varied reaction sites and regioselectivity, depending on the structure of the alkenes and reaction conditions (Schenk 1960; Miyashi et al. 1985; Eckert & Goez 1994; Xu, Song et al. 1994; Xu, Wang et al. 1994). While irradiation of a benzene solution of 2,3,5,6-tetrachlorobenzoquinone and 4,4'-(ethene-1,1-diyl)bis(chlorobenzene) with light of wavelength longer than 400 nm resulted in formation products of the title compound as a yellow solid (Xue et al. 2000). The yellow crystals were obtained by recrystallization of these solids from petroleum ether-chloroform.

The title compound, C20H10Cl6O2, is a quinone derivative. In the quinone, the distances of the C=O bonds are 1.191 (7) and 1.199 (7) Å, which are considered to to have full double-bond character. Meanwhile, the distances of C1—C2 and C5—C6 are, respectively, 1.478 (9) and 1.475 (8) Å, which are a little longer than that of C1=C6 (1.354 (9) Å), but shorter than those of C—C bonds (1.527 (8)–1.560 (7) Å). This shows that C1—C2 and C5—C6 bonds both have part double-bond character.

Related literature top

For related literature, see: Eckert & Goez (1994); Miyashi et al. (1985); Schenk (1960); Xu, Song et al. (1994); Xu, Wang et al. 1994); Xue et al. (2000). For a related structure, see: Braun et al. (1999)

Experimental top

Irradiation of a benzene solution of 2,3,5,6-tetrachlorobenzoquinone (0.05 mol L-1) and 4,4'-(ethene-1,1-diyl)bis(chlorobenzene) (0.10 mol L-1) with light of wavelength longer than 400 nm for 10 h resulted in complete consumption of 2,3,5,6-tetrachlorobenzoquinone and the formation of products 1,3,4,6-tetrachloro-7,7-bis(4-chlorophenyl)bicyclo[4.2.0]oct-3-ene-2,5-dione. Recrystallization from petroleum ether (bp 60–90 °) and chloroform gave a slightly yellow crystal.

Refinement top

H atoms were positioned geometrically and refined using a riding model with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2 times Ueq(C).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms, 1993); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with 30% displacement ellipsoids.
1,3,4,6-Tetrachloro-7,7-bis(4-chlorophenyl)bicyclo[4.2.0]oct-3-ene-2,5-dione top
Crystal data top
C20H10Cl6O2Z = 2
Mr = 494.98F(000) = 496
Triclinic, P1Dx = 1.650 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.6710 (17) ÅCell parameters from 25 reflections
b = 9.6850 (19) Åθ = 10–13°
c = 12.864 (3) ŵ = 0.88 mm−1
α = 105.49 (3)°T = 293 K
β = 97.11 (3)°Block, yellow
γ = 102.68 (3)°0.30 × 0.20 × 0.10 mm
V = 996.4 (3) Å3
Data collection top
Enraf–Nonius CAD-4
diffractometer		2787 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.049
graphiteθmax = 25.3°, θmin = 1.7°
ω/2θ scansh = −10→10
Absorption correction: ψ scan
(SHELXTL; Sheldrick, 2008)		k = −11→11
Tmin = 0.779, Tmax = 0.917l = 0→15
3879 measured reflections3 standard reflections every 200 reflections
3619 independent reflections intensity decay: none
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)] = 0.066Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.192H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.06P)2 + 6P]
where P = (Fo2 + 2Fc2)/3
3619 reflections(Δ/σ)max < 0.001
253 parametersΔρmax = 0.66 e Å−3
0 restraintsΔρmin = −0.57 e Å−3
Crystal data top
C20H10Cl6O2γ = 102.68 (3)°
Mr = 494.98V = 996.4 (3) Å3
Triclinic, P1Z = 2
a = 8.6710 (17) ÅMo Kα radiation
b = 9.6850 (19) ŵ = 0.88 mm−1
c = 12.864 (3) ÅT = 293 K
α = 105.49 (3)°0.30 × 0.20 × 0.10 mm
β = 97.11 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		2787 reflections with I > 2σ(I)
Absorption correction: ψ scan
(SHELXTL; Sheldrick, 2008)		Rint = 0.049
Tmin = 0.779, Tmax = 0.917θmax = 25.3°
3879 measured reflections3 standard reflections every 200 reflections
3619 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.066H-atom parameters constrained
wR(F2) = 0.192Δρmax = 0.66 e Å−3
S = 1.00Δρmin = −0.57 e Å−3
3619 reflectionsAbsolute structure: ?
253 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Cl10.3758 (2)0.1746 (2)0.61309 (16)0.0752 (6)
Cl20.0143 (2)−0.07268 (16)0.83090 (14)0.0527 (4)
Cl30.4819 (2)0.4713 (2)0.81185 (19)0.0761 (6)
Cl40.25830 (19)0.20039 (18)1.01117 (12)0.0524 (4)
Cl5−0.2014 (3)0.5682 (2)0.53637 (17)0.0788 (6)
Cl6−0.7475 (2)−0.30216 (19)0.73595 (17)0.0653 (5)
O10.0754 (6)−0.0161 (5)0.6230 (4)0.0625 (12)
O20.2265 (5)0.4901 (4)0.9419 (4)0.0574 (11)
C10.2697 (7)0.2059 (7)0.7168 (5)0.0444 (13)
C20.1230 (7)0.0867 (6)0.7046 (4)0.0409 (13)
C30.0404 (6)0.1008 (6)0.8037 (4)0.0365 (11)
C40.1223 (7)0.2309 (6)0.9110 (4)0.0382 (12)
C50.2210 (6)0.3667 (6)0.8877 (4)0.0384 (12)
C60.3165 (6)0.3339 (6)0.8013 (5)0.0422 (13)
C7−0.0468 (6)0.2385 (6)0.9327 (4)0.0385 (12)
H7A−0.08510.18190.98060.046*
H7B−0.05800.33890.95770.046*
C8−0.1175 (6)0.1593 (6)0.8105 (4)0.0337 (11)
C9−0.1295 (6)0.2656 (6)0.7408 (4)0.0360 (11)
C10−0.1477 (7)0.2165 (6)0.6274 (5)0.0449 (13)
H10A−0.14630.11930.59320.054*
C11−0.1680 (9)0.3087 (7)0.5634 (5)0.0554 (16)
H11A−0.17660.27470.48760.067*
C12−0.1752 (7)0.4491 (6)0.6133 (5)0.0445 (13)
C13−0.1599 (7)0.5022 (6)0.7252 (5)0.0452 (13)
H13A−0.16300.59910.75850.054*
C14−0.1399 (7)0.4087 (6)0.7877 (5)0.0459 (14)
H14A−0.13320.44320.86330.055*
C15−0.2792 (6)0.0423 (6)0.7864 (4)0.0341 (11)
C16−0.3207 (7)−0.0869 (6)0.6989 (5)0.0441 (13)
H16A−0.2506−0.10290.65050.053*
C17−0.4660 (7)−0.1935 (7)0.6820 (5)0.0493 (14)
H17A−0.4930−0.28010.62290.059*
C18−0.5684 (7)−0.1687 (6)0.7538 (5)0.0431 (13)
C19−0.5304 (7)−0.0393 (7)0.8409 (5)0.0487 (14)
H19A−0.6005−0.02320.88930.058*
C20−0.3883 (7)0.0644 (6)0.8548 (4)0.0421 (13)
H20A−0.36420.15270.91220.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0764 (12)0.0926 (14)0.0673 (11)0.0278 (10)0.0554 (10)0.0190 (10)
Cl20.0647 (10)0.0394 (8)0.0665 (10)0.0226 (7)0.0264 (8)0.0234 (7)
Cl30.0535 (10)0.0653 (11)0.1098 (16)0.0045 (8)0.0405 (10)0.0250 (10)
Cl40.0565 (9)0.0623 (9)0.0436 (8)0.0229 (7)0.0147 (6)0.0167 (7)
Cl50.1310 (18)0.0587 (10)0.0781 (12)0.0495 (11)0.0479 (12)0.0402 (10)
Cl60.0518 (9)0.0553 (10)0.0947 (13)0.0112 (7)0.0326 (9)0.0267 (9)
O10.080 (3)0.054 (3)0.049 (3)0.019 (2)0.038 (2)−0.003 (2)
O20.069 (3)0.037 (2)0.064 (3)0.014 (2)0.032 (2)0.003 (2)
C10.050 (3)0.052 (3)0.043 (3)0.025 (3)0.031 (3)0.015 (3)
C20.048 (3)0.049 (3)0.039 (3)0.030 (3)0.026 (2)0.014 (3)
C30.048 (3)0.034 (3)0.036 (3)0.019 (2)0.023 (2)0.011 (2)
C40.047 (3)0.034 (3)0.035 (3)0.013 (2)0.018 (2)0.005 (2)
C50.036 (3)0.038 (3)0.039 (3)0.010 (2)0.014 (2)0.005 (2)
C60.032 (3)0.047 (3)0.052 (3)0.014 (2)0.015 (2)0.017 (3)
C70.047 (3)0.048 (3)0.029 (3)0.023 (2)0.019 (2)0.011 (2)
C80.042 (3)0.038 (3)0.031 (2)0.021 (2)0.021 (2)0.012 (2)
C90.044 (3)0.035 (3)0.040 (3)0.020 (2)0.026 (2)0.014 (2)
C100.067 (4)0.037 (3)0.040 (3)0.028 (3)0.023 (3)0.010 (2)
C110.091 (5)0.045 (3)0.044 (3)0.033 (3)0.034 (3)0.016 (3)
C120.047 (3)0.036 (3)0.058 (4)0.014 (2)0.023 (3)0.018 (3)
C130.055 (3)0.025 (3)0.055 (3)0.013 (2)0.023 (3)0.005 (2)
C140.060 (4)0.039 (3)0.046 (3)0.021 (3)0.031 (3)0.010 (2)
C150.041 (3)0.035 (3)0.031 (3)0.012 (2)0.015 (2)0.013 (2)
C160.048 (3)0.043 (3)0.044 (3)0.015 (2)0.029 (3)0.006 (2)
C170.046 (3)0.042 (3)0.054 (4)0.011 (3)0.019 (3)0.003 (3)
C180.038 (3)0.047 (3)0.051 (3)0.014 (2)0.013 (2)0.022 (3)
C190.049 (3)0.057 (4)0.054 (3)0.024 (3)0.035 (3)0.021 (3)
C200.050 (3)0.043 (3)0.039 (3)0.020 (3)0.021 (2)0.011 (2)
Geometric parameters (Å, °) top
Cl1—C11.712 (5)C9—C141.384 (7)
Cl2—C31.779 (5)C9—C101.385 (7)
Cl3—C61.693 (6)C10—C111.390 (8)
Cl4—C41.766 (6)C10—H10A0.9300
Cl5—C121.740 (6)C11—C121.359 (8)
Cl6—C181.734 (6)C11—H11A0.9300
O1—C21.190 (7)C12—C131.372 (8)
O2—C51.200 (6)C13—C141.385 (8)
C1—C61.354 (8)C13—H13A0.9300
C1—C21.478 (8)C14—H14A0.9300
C2—C31.528 (7)C15—C201.382 (7)
C3—C41.560 (7)C15—C161.383 (7)
C3—C81.596 (7)C16—C171.393 (8)
C4—C51.526 (7)C16—H16A0.9300
C4—C71.540 (7)C17—C181.370 (8)
C5—C61.474 (7)C17—H17A0.9300
C7—C81.532 (7)C18—C191.383 (8)
C7—H7A0.9700C19—C201.365 (8)
C7—H7B0.9700C19—H19A0.9300
C8—C151.534 (7)C20—H20A0.9300
C8—C91.545 (7)
C6—C1—C2123.4 (5)C14—C9—C10117.1 (5)
C6—C1—Cl1121.3 (5)C14—C9—C8121.3 (5)
C2—C1—Cl1115.2 (4)C10—C9—C8121.2 (5)
O1—C2—C1121.5 (5)C9—C10—C11121.7 (5)
O1—C2—C3122.3 (5)C9—C10—H10A119.1
C1—C2—C3116.1 (5)C11—C10—H10A119.1
C2—C3—C4118.3 (5)C12—C11—C10119.0 (6)
C2—C3—C8123.0 (4)C12—C11—H11A120.5
C4—C3—C886.8 (4)C10—C11—H11A120.5
C2—C3—Cl2106.0 (3)C11—C12—C13121.4 (5)
C4—C3—Cl2110.3 (4)C11—C12—Cl5120.6 (5)
C8—C3—Cl2111.5 (3)C13—C12—Cl5118.0 (4)
C5—C4—C7115.4 (4)C12—C13—C14118.8 (5)
C5—C4—C3112.4 (4)C12—C13—H13A120.6
C7—C4—C388.4 (4)C14—C13—H13A120.6
C5—C4—Cl4103.3 (4)C9—C14—C13121.9 (5)
C7—C4—Cl4118.9 (4)C9—C14—H14A119.0
C3—C4—Cl4118.7 (4)C13—C14—H14A119.0
O2—C5—C6123.6 (5)C20—C15—C16117.9 (5)
O2—C5—C4121.0 (5)C20—C15—C8119.4 (5)
C6—C5—C4115.2 (5)C16—C15—C8122.6 (4)
C1—C6—C5122.0 (5)C15—C16—C17121.0 (5)
C1—C6—Cl3122.7 (4)C15—C16—H16A119.5
C5—C6—Cl3115.2 (4)C17—C16—H16A119.5
C8—C7—C489.8 (4)C18—C17—C16119.0 (5)
C8—C7—H7A113.7C18—C17—H17A120.5
C4—C7—H7A113.7C16—C17—H17A120.5
C8—C7—H7B113.7C17—C18—C19120.9 (5)
C4—C7—H7B113.7C17—C18—Cl6119.6 (5)
H7A—C7—H7B110.9C19—C18—Cl6119.5 (4)
C7—C8—C15114.9 (4)C20—C19—C18119.0 (5)
C7—C8—C9114.1 (4)C20—C19—H19A120.5
C15—C8—C9109.7 (4)C18—C19—H19A120.5
C7—C8—C387.4 (4)C19—C20—C15122.0 (5)
C15—C8—C3117.2 (4)C19—C20—H20A119.0
C9—C8—C3112.1 (4)C15—C20—H20A119.0
C6—C1—C2—O1171.0 (6)C4—C3—C8—C7−20.4 (4)
Cl1—C1—C2—O1−6.9 (8)Cl2—C3—C8—C790.1 (4)
C6—C1—C2—C3−11.0 (8)C2—C3—C8—C15100.7 (6)
Cl1—C1—C2—C3171.1 (4)C4—C3—C8—C15−137.3 (4)
O1—C2—C3—C4173.7 (5)Cl2—C3—C8—C15−26.7 (5)
C1—C2—C3—C4−4.3 (7)C2—C3—C8—C9−27.4 (7)
O1—C2—C3—C8−80.5 (7)C4—C3—C8—C994.6 (4)
C1—C2—C3—C8101.6 (6)Cl2—C3—C8—C9−154.9 (4)
O1—C2—C3—Cl249.4 (7)C7—C8—C9—C14−25.0 (7)
C1—C2—C3—Cl2−128.6 (4)C15—C8—C9—C14105.5 (6)
C2—C3—C4—C529.4 (6)C3—C8—C9—C14−122.4 (5)
C8—C3—C4—C5−96.7 (4)C7—C8—C9—C10162.0 (5)
Cl2—C3—C4—C5151.6 (4)C15—C8—C9—C10−67.4 (6)
C2—C3—C4—C7146.4 (5)C3—C8—C9—C1064.7 (7)
C8—C3—C4—C720.3 (4)C14—C9—C10—C112.9 (9)
Cl2—C3—C4—C7−91.5 (4)C8—C9—C10—C11176.2 (6)
C2—C3—C4—Cl4−91.2 (5)C9—C10—C11—C12−2.1 (10)
C8—C3—C4—Cl4142.7 (4)C10—C11—C12—C131.2 (10)
Cl2—C3—C4—Cl430.9 (5)C10—C11—C12—Cl5−179.7 (5)
C7—C4—C5—O244.0 (7)C11—C12—C13—C14−1.2 (9)
C3—C4—C5—O2143.4 (5)Cl5—C12—C13—C14179.7 (5)
Cl4—C4—C5—O2−87.4 (6)C10—C9—C14—C13−3.0 (9)
C7—C4—C5—C6−140.6 (5)C8—C9—C14—C13−176.2 (5)
C3—C4—C5—C6−41.2 (6)C12—C13—C14—C92.2 (9)
Cl4—C4—C5—C688.0 (5)C7—C8—C15—C2034.1 (7)
C2—C1—C6—C5−1.7 (9)C9—C8—C15—C20−96.0 (5)
Cl1—C1—C6—C5176.1 (4)C3—C8—C15—C20134.7 (5)
C2—C1—C6—Cl3−178.1 (4)C7—C8—C15—C16−145.2 (5)
Cl1—C1—C6—Cl3−0.3 (8)C9—C8—C15—C1684.8 (6)
O2—C5—C6—C1−155.5 (6)C3—C8—C15—C16−44.6 (7)
C4—C5—C6—C129.3 (8)C20—C15—C16—C17−1.8 (9)
O2—C5—C6—Cl321.2 (8)C8—C15—C16—C17177.4 (5)
C4—C5—C6—Cl3−154.1 (4)C15—C16—C17—C180.0 (9)
C5—C4—C7—C893.0 (5)C16—C17—C18—C191.0 (9)
C3—C4—C7—C8−21.1 (4)C16—C17—C18—Cl6−178.5 (5)
Cl4—C4—C7—C8−143.4 (4)C17—C18—C19—C20−0.1 (9)
C4—C7—C8—C15139.6 (4)Cl6—C18—C19—C20179.4 (5)
C4—C7—C8—C9−92.5 (5)C18—C19—C20—C15−1.8 (9)
C4—C7—C8—C320.7 (4)C16—C15—C20—C192.8 (8)
C2—C3—C8—C7−142.4 (5)C8—C15—C20—C19−176.5 (5)
Acknowledgements top

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

references
References top

Braun, M., Christl, M., Peters, E.-M. & Peters, K. (1999). J. Chem. Soc. Perkin Trans. 1, pp. 2813–2820.

Eckert, G. & Goez, M. (1994). J. Am. Chem. Soc. 116, 11999–12009.

Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.

Harms, K. (1993). XCAD4. University of Marburg, Germany.

Miyashi, T., Takahashi, Y., Mukai, T., Roth, H. D. & Schilling, M. L. M. (1985). J. Am. Chem. Soc. 107, 1079–1080.

Schenk, G. O. Z. (1960). Electrochemistry, 64, 997–1011.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Xu, J. H., Song, Y. L., Zhang, Z. G., Wang, L. C. & Xu, J. W. (1994). Tetrahedron, 50, 1199–1210.

Xu, J. H., Wang, L. C., Xu, J. W., Yan, B. Z. & Yuan, H. C. (1994). J. Chem. Soc. Perkin Trans. 1, pp.571–577.

Xue, J., Xu, J.-W., Yang, L. & Xu, J.-H. (2000). J. Org. Chem. 65, 30–40.