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Acta Cryst. (2008). E64, o545    [ doi:10.1107/S1600536808003206 ]

3,8-Bis(4-chlorophenyl)-4,7-dimethyltricyclo[4.2.2.02,5]deca-3,7-diene

M. Tomura and Y. Yamashita

Abstract top

The title tricyclic diene, C24H22Cl2, is the product of thermal ring-opening of a corresponding basketane (pentacyclo[4.4.0.02,5.03,8.04,7]decane) derivative. The cyclobutene ring is planar to within 0.0032 (12) Å and its geometry is normal. The two 4-chlorophenyl groups are oriented in an approximately face-to-face conformation with a dihedral angle of 44.14 (6)° between them. The 4-chlorophenyl group bonded to the cyclobutene ring lies almost in the plane of the cyclobutene ring, with a dihedral angle of 8.29 (17)° between the ring planes. The average intramolecular C...C distance between the two C=C bonds is 2.92 Å. In the crystal structure, the molecules are well separated with no close C-H...Cl or C-H...[pi] intermolecular interactions.

Comment top

There is considerable interest in the chemistry of highly strained polycyclic "cage" compounds (Osawa & Yonemitsu, 1992). The title tricyclic diene, (I), Fig 1, 3,8-bis(4-chlorophenyl)-4,7-dimethyltricyclo[4.2.2.02,5] deca-3,7-diene, C24H22Cl2, is the product of thermal ring-opening of a corresponding basketane (pentacyclo[4.4.0.02,5.03,8.04,7]decane) and reverts to the basketane derivative quantitatively upon irradiation (Tezuka et al., 1976). A search for tricyclo[4.2.2.02,5]deca-3,7-diene skeleton in the Cambridge Structural Database (Version 5.29; Allen, 2002) gave only four examples, CTCYDD (Lemley et al., 1976), CNUNDC (Hanson, 1981), KEVGEX (Mehta et al., 1990) and GACFIA (Mehta et al., 2003).

Bond lengths and angles in the molecule are within the normal ranges (Allen et al., 1987) and the geometry of the cyclobutene ring is also similar to that of cyclobutene (Allen, 1984). The cyclobutene ring adopts a planar, rather than a puckered conformation, where the maximum deviation of the fitted atoms from the least-squares plane is 0.0032 (12) Å. The C3—C4 bond distance [1.562 (3) Å] in the cyclobutene ring is 1.8% shorter than the corresponding distance in the 2,3,4,5-tetrachloro derivative (Lemley et al., 1976). The two 4-chlorophenyl groups are oriented in an approximately face-to-face conformation with a dihedral angle of 44.14 (6)° between them. The 4-chlorophenyl group bonded to the cyclobutene ring lies almost in the plane of the cyclobutene ring with a dihedral angle of 8.29 (17)° between the ring planes. Upon irradiation, an intramolecular photocyclization occurs between the C1?C2 and C6?C7 bonds. Intramolecular C1···C6 and C2···C7 distances are 2.918 (3) and 2.921 (3) Å, respectively, and the dihedral angle between the cyclobutene plane (C1–C4) and the C5–C8 plane is 60.89 (12)°. In the crystal structure the molecules are well separated with no close C—H···Cl or C—H···π intermolecular interactions.

Related literature top

For the preparation of the title compound, see: Tezuka et al. (1976); Mukai et al. (1981). For cage compounds, see: Osawa & Yonemitsu (1992). For the crystal structures of compounds with the tricyclo[4.2.2.02,5]deca-3,7-diene skeleton, see: Lemley et al. (1976); Hanson (1981); Mehta et al. (1990, 2003). For other related literature, see: Allen (1984, 2002); Allen et al. (1987).

Experimental top

The compound (I) was synthesized according to a literature method (Tezuka et al., 1976; Mukai et al., 1981). Colorless crystals of (I) suitable for X-ray analysis were grown from a dichloromethane solution.

Refinement top

All H atoms were placed in geometrically calculated positions and refined using a riding model, with C—H distances of 0.93, 0.96, 0.97 and 0.98 Å for aromatic, methyl, methylene and methine H atoms, respectively, and with Uiso(H) = 1.2Ueq(C) for aromatic, methylene and methine or 1.5Ueq(C) for methyl H atoms.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1992); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1992); data reduction: TEXSAN (Rigaku/MSC, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 20% probability displacement ellipsoids for non-H atoms. H atoms are shown as small spheres with arbitrary radii.
3,8-Bis(4-chlorophenyl)-4,7-dimethyltricyclo[4.2.2.02,5]deca-3,7-diene top
Crystal data top
C24H22Cl2F000 = 800
Mr = 381.32Dx = 1.269 Mg m−3
Monoclinic, P21/cCu Kα radiation
λ = 1.54178 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 8.3389 (7) Åθ = 22.7–42.6º
b = 21.2224 (12) ŵ = 2.94 mm−1
c = 11.6074 (13) ÅT = 295 (1) K
β = 103.732 (7)ºBlock, colorless
V = 1995.5 (3) Å30.48 × 0.35 × 0.25 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.021
Monochromator: graphiteθmax = 74.2º
T = 295(1) Kθmin = 4.2º
ω–2θ scansh = 0→10
Absorption correction: ψ scan
(North et al., 1968)		k = 0→26
Tmin = 0.328, Tmax = 0.484l = −14→14
4348 measured reflections3 standard reflections
4070 independent reflections every 120 min
2872 reflections with I > 2σ(I) intensity decay: 1.3%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.160  w = 1/[σ2(Fo2) + (0.0822P)2 + 0.357P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.007
4070 reflectionsΔρmax = 0.20 e Å−3
237 parametersΔρmin = −0.32 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C24H22Cl2V = 1995.5 (3) Å3
Mr = 381.32Z = 4
Monoclinic, P21/cCu Kα
a = 8.3389 (7) ŵ = 2.94 mm−1
b = 21.2224 (12) ÅT = 295 (1) K
c = 11.6074 (13) Å0.48 × 0.35 × 0.25 mm
β = 103.732 (7)º
Data collection top
Enraf–Nonius CAD-4
diffractometer		2872 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.021
Tmin = 0.328, Tmax = 0.4843 standard reflections
4348 measured reflections every 120 min
4070 independent reflections intensity decay: 1.3%
Refinement top
R[F2 > 2σ(F2)] = 0.050237 parameters
wR(F2) = 0.160H-atom parameters constrained
S = 1.04Δρmax = 0.20 e Å−3
4070 reflectionsΔρmin = −0.32 e Å−3
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
Cl10.49013 (12)0.19930 (4)1.21790 (6)0.1028 (3)
Cl21.19192 (12)0.35095 (4)0.98762 (11)0.1347 (4)
C10.7177 (3)0.00447 (11)0.7920 (3)0.0761 (7)
C20.6407 (3)0.05850 (10)0.8097 (2)0.0661 (5)
C30.5989 (3)0.07597 (11)0.6796 (2)0.0652 (5)
H30.48020.07500.64320.078*
C40.6896 (3)0.01375 (11)0.6609 (2)0.0749 (7)
H40.6163−0.01790.61440.090*
C50.8386 (3)0.03011 (12)0.6096 (2)0.0753 (7)
H50.9014−0.00790.60110.090*
C60.9467 (3)0.07722 (11)0.6897 (2)0.0656 (5)
C70.8686 (2)0.13047 (10)0.70463 (19)0.0600 (5)
C80.6880 (2)0.13196 (11)0.63804 (19)0.0618 (5)
H80.63640.17190.65150.074*
C90.6785 (3)0.12218 (14)0.5049 (2)0.0793 (7)
H9A0.56390.11960.46140.095*
H9B0.72900.15760.47430.095*
C100.7692 (3)0.06101 (14)0.4880 (2)0.0858 (8)
H10A0.85850.07040.45030.103*
H10B0.69340.03230.43720.103*
C110.8109 (4)−0.04637 (13)0.8691 (3)0.1037 (10)
H11A0.9228−0.04720.86090.156*
H11B0.7596−0.08630.84550.156*
H11C0.8102−0.03820.95030.156*
C121.1250 (3)0.06200 (12)0.7406 (3)0.0787 (7)
H12A1.18030.09850.78010.118*
H12B1.17560.04970.67790.118*
H12C1.13330.02810.79640.118*
C130.6085 (3)0.09224 (10)0.9117 (2)0.0617 (5)
C140.5426 (3)0.15260 (11)0.8976 (2)0.0721 (6)
H140.51940.17090.82270.086*
C150.5102 (3)0.18636 (12)0.9912 (2)0.0759 (6)
H150.46830.22710.97980.091*
C160.5404 (3)0.15904 (12)1.1008 (2)0.0710 (6)
C170.6047 (4)0.09927 (14)1.1188 (2)0.0875 (8)
H170.62480.08091.19360.105*
C180.6390 (4)0.06678 (12)1.0248 (2)0.0838 (7)
H180.68400.02661.03750.101*
C190.9420 (3)0.18508 (10)0.77687 (19)0.0574 (5)
C200.9320 (3)0.24474 (12)0.7278 (2)0.0772 (7)
H200.87390.25050.64960.093*
C211.0060 (4)0.29581 (13)0.7920 (3)0.0924 (9)
H210.99860.33550.75730.111*
C221.0901 (3)0.28762 (13)0.9069 (3)0.0810 (7)
C231.0954 (3)0.23022 (14)0.9607 (2)0.0826 (7)
H231.14860.22561.04030.099*
C241.0210 (3)0.17907 (12)0.8956 (2)0.0736 (6)
H241.02390.14000.93210.088*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.1386 (7)0.1011 (5)0.0714 (4)−0.0031 (5)0.0303 (4)−0.0133 (3)
Cl20.1042 (6)0.0980 (6)0.1974 (11)−0.0306 (5)0.0271 (6)−0.0685 (6)
C10.0663 (14)0.0549 (12)0.1071 (19)0.0000 (10)0.0209 (13)−0.0022 (12)
C20.0562 (12)0.0574 (12)0.0851 (15)0.0019 (9)0.0176 (11)0.0013 (11)
C30.0487 (10)0.0662 (12)0.0783 (14)0.0005 (9)0.0103 (10)−0.0110 (11)
C40.0571 (12)0.0666 (14)0.1002 (18)−0.0060 (10)0.0171 (12)−0.0246 (13)
C50.0591 (12)0.0737 (14)0.0931 (17)0.0031 (11)0.0181 (12)−0.0285 (13)
C60.0520 (11)0.0691 (13)0.0746 (14)0.0025 (10)0.0127 (10)−0.0114 (11)
C70.0524 (11)0.0636 (12)0.0625 (12)0.0005 (9)0.0110 (9)−0.0040 (9)
C80.0530 (11)0.0680 (12)0.0626 (12)0.0069 (9)0.0104 (9)−0.0029 (10)
C90.0639 (13)0.108 (2)0.0635 (13)0.0046 (13)0.0109 (11)−0.0095 (13)
C100.0675 (14)0.113 (2)0.0764 (16)−0.0002 (14)0.0156 (12)−0.0309 (15)
C110.101 (2)0.0642 (15)0.150 (3)0.0211 (14)0.039 (2)0.0158 (17)
C120.0565 (12)0.0775 (15)0.0983 (18)0.0090 (11)0.0107 (12)−0.0098 (13)
C130.0554 (11)0.0564 (11)0.0729 (13)0.0017 (9)0.0141 (10)0.0067 (10)
C140.0868 (16)0.0643 (13)0.0687 (13)0.0126 (11)0.0255 (12)0.0139 (11)
C150.0925 (17)0.0610 (13)0.0795 (15)0.0102 (12)0.0308 (13)0.0075 (11)
C160.0742 (14)0.0717 (14)0.0666 (13)−0.0071 (11)0.0157 (11)−0.0029 (11)
C170.105 (2)0.0858 (17)0.0691 (15)0.0102 (16)0.0156 (14)0.0184 (13)
C180.0937 (18)0.0691 (15)0.0869 (17)0.0185 (13)0.0180 (14)0.0162 (13)
C190.0526 (10)0.0575 (11)0.0636 (12)0.0002 (8)0.0163 (9)−0.0031 (9)
C200.0820 (16)0.0708 (15)0.0762 (15)−0.0063 (12)0.0137 (12)0.0103 (12)
C210.095 (2)0.0620 (14)0.121 (2)−0.0147 (13)0.0270 (18)0.0067 (15)
C220.0630 (14)0.0708 (15)0.112 (2)−0.0092 (11)0.0267 (14)−0.0259 (15)
C230.0796 (17)0.0903 (18)0.0723 (15)−0.0016 (13)0.0067 (12)−0.0191 (14)
C240.0837 (16)0.0633 (13)0.0685 (14)−0.0029 (11)0.0075 (12)0.0006 (11)
Geometric parameters (Å, °) top
Cl1—C161.739 (3)C11—H11A0.9600
Cl2—C221.740 (3)C11—H11B0.9600
C1—C21.353 (3)C11—H11C0.9600
C1—C111.496 (4)C12—H12A0.9600
C1—C41.496 (4)C12—H12B0.9600
C2—C131.462 (3)C12—H12C0.9600
C2—C31.513 (3)C13—C181.386 (3)
C3—C81.538 (3)C13—C141.388 (3)
C3—C41.562 (3)C14—C151.381 (3)
C3—H30.9800C14—H140.9300
C4—C51.540 (3)C15—C161.366 (3)
C4—H40.9800C15—H150.9300
C5—C61.510 (3)C16—C171.374 (4)
C5—C101.539 (4)C17—C181.377 (4)
C5—H50.9800C17—H170.9300
C6—C71.336 (3)C18—H180.9300
C6—C121.499 (3)C19—C201.383 (3)
C7—C191.476 (3)C19—C241.385 (3)
C7—C81.521 (3)C20—C211.376 (4)
C8—C91.543 (3)C20—H200.9300
C8—H80.9800C21—C221.363 (4)
C9—C101.538 (4)C21—H210.9300
C9—H9A0.9700C22—C231.365 (4)
C9—H9B0.9700C23—C241.383 (3)
C10—H10A0.9700C23—H230.9300
C10—H10B0.9700C24—H240.9300
C2—C1—C11135.9 (3)C1—C11—H11A109.5
C2—C1—C494.5 (2)C1—C11—H11B109.5
C11—C1—C4129.5 (2)H11A—C11—H11B109.5
C1—C2—C13136.3 (2)C1—C11—H11C109.5
C1—C2—C393.5 (2)H11A—C11—H11C109.5
C13—C2—C3130.17 (19)H11B—C11—H11C109.5
C2—C3—C8119.23 (18)C6—C12—H12A109.5
C2—C3—C485.80 (18)C6—C12—H12B109.5
C8—C3—C4108.89 (17)H12A—C12—H12B109.5
C2—C3—H3113.3C6—C12—H12C109.5
C8—C3—H3113.3H12A—C12—H12C109.5
C4—C3—H3113.3H12B—C12—H12C109.5
C1—C4—C5118.5 (2)C18—C13—C14116.7 (2)
C1—C4—C386.23 (18)C18—C13—C2123.2 (2)
C5—C4—C3109.0 (2)C14—C13—C2120.0 (2)
C1—C4—H4113.4C15—C14—C13122.2 (2)
C5—C4—H4113.4C15—C14—H14118.9
C3—C4—H4113.4C13—C14—H14118.9
C6—C5—C10108.8 (2)C16—C15—C14119.0 (2)
C6—C5—C4109.20 (19)C16—C15—H15120.5
C10—C5—C4106.8 (2)C14—C15—H15120.5
C6—C5—H5110.6C15—C16—C17120.9 (2)
C10—C5—H5110.6C15—C16—Cl1119.6 (2)
C4—C5—H5110.6C17—C16—Cl1119.5 (2)
C7—C6—C12126.8 (2)C16—C17—C18119.3 (2)
C7—C6—C5113.71 (19)C16—C17—H17120.4
C12—C6—C5119.4 (2)C18—C17—H17120.4
C6—C7—C19126.06 (19)C17—C18—C13122.0 (2)
C6—C7—C8113.95 (19)C17—C18—H18119.0
C19—C7—C8119.98 (18)C13—C18—H18119.0
C7—C8—C3108.55 (18)C20—C19—C24117.5 (2)
C7—C8—C9108.40 (18)C20—C19—C7120.6 (2)
C3—C8—C9107.24 (19)C24—C19—C7121.9 (2)
C7—C8—H8110.8C21—C20—C19121.5 (2)
C3—C8—H8110.8C21—C20—H20119.2
C9—C8—H8110.8C19—C20—H20119.2
C10—C9—C8109.4 (2)C22—C21—C20119.3 (3)
C10—C9—H9A109.8C22—C21—H21120.3
C8—C9—H9A109.8C20—C21—H21120.3
C10—C9—H9B109.8C21—C22—C23121.0 (2)
C8—C9—H9B109.8C21—C22—Cl2120.0 (2)
H9A—C9—H9B108.3C23—C22—Cl2119.0 (2)
C9—C10—C5109.39 (19)C22—C23—C24119.2 (2)
C9—C10—H10A109.8C22—C23—H23120.4
C5—C10—H10A109.8C24—C23—H23120.4
C9—C10—H10B109.8C23—C24—C19121.2 (2)
C5—C10—H10B109.8C23—C24—H24119.4
H10A—C10—H10B108.2C19—C24—H24119.4
C11—C1—C2—C13−1.7 (5)C4—C3—C8—C961.1 (2)
C4—C1—C2—C13−177.6 (3)C7—C8—C9—C1054.9 (3)
C11—C1—C2—C3176.4 (3)C3—C8—C9—C10−62.1 (2)
C4—C1—C2—C30.50 (19)C8—C9—C10—C50.1 (3)
C1—C2—C3—C8−109.8 (2)C6—C5—C10—C9−55.6 (3)
C13—C2—C3—C868.5 (3)C4—C5—C10—C962.2 (3)
C1—C2—C3—C4−0.48 (18)C1—C2—C13—C18−9.6 (4)
C13—C2—C3—C4177.8 (2)C3—C2—C13—C18172.8 (2)
C2—C1—C4—C5109.1 (2)C1—C2—C13—C14171.1 (3)
C11—C1—C4—C5−67.2 (3)C3—C2—C13—C14−6.5 (4)
C2—C1—C4—C3−0.48 (18)C18—C13—C14—C150.7 (4)
C11—C1—C4—C3−176.8 (3)C2—C13—C14—C15−179.9 (2)
C2—C3—C4—C10.43 (16)C13—C14—C15—C16−1.5 (4)
C8—C3—C4—C1119.93 (19)C14—C15—C16—C171.1 (4)
C2—C3—C4—C5−118.5 (2)C14—C15—C16—Cl1−176.6 (2)
C8—C3—C4—C51.0 (3)C15—C16—C17—C180.1 (4)
C1—C4—C5—C6−41.3 (3)Cl1—C16—C17—C18177.8 (2)
C3—C4—C5—C654.8 (3)C16—C17—C18—C13−0.9 (5)
C1—C4—C5—C10−158.8 (2)C14—C13—C18—C170.5 (4)
C3—C4—C5—C10−62.6 (2)C2—C13—C18—C17−178.8 (3)
C10—C5—C6—C757.9 (3)C6—C7—C19—C20125.7 (3)
C4—C5—C6—C7−58.3 (3)C8—C7—C19—C20−54.0 (3)
C10—C5—C6—C12−120.4 (2)C6—C7—C19—C24−55.3 (3)
C4—C5—C6—C12123.4 (2)C8—C7—C19—C24125.1 (2)
C12—C6—C7—C19−1.3 (4)C24—C19—C20—C213.9 (4)
C5—C6—C7—C19−179.5 (2)C7—C19—C20—C21−177.0 (2)
C12—C6—C7—C8178.3 (2)C19—C20—C21—C22−0.5 (4)
C5—C6—C7—C80.2 (3)C20—C21—C22—C23−3.1 (4)
C6—C7—C8—C358.3 (3)C20—C21—C22—Cl2177.3 (2)
C19—C7—C8—C3−122.0 (2)C21—C22—C23—C243.2 (4)
C6—C7—C8—C9−57.9 (3)Cl2—C22—C23—C24−177.2 (2)
C19—C7—C8—C9121.8 (2)C22—C23—C24—C190.3 (4)
C2—C3—C8—C740.1 (3)C20—C19—C24—C23−3.7 (4)
C4—C3—C8—C7−55.8 (2)C7—C19—C24—C23177.2 (2)
C2—C3—C8—C9156.98 (19)
Acknowledgements top

We thank the Instrument Center of the Institute for Molecular Science for the X-ray structure analysis.

references
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