Monitoring structural transformations in crystals. 7. 1-Chloro­anthracene and its photodimer

Crystals of the 1-chloro­anthracene photodimer, viz. trans-bi(1-chloro-9,10-di­hydro-9,10-anthracenediyl), C₂₈H₁₈Cl₂, were obtained from the solid-state [4+4]-photodimerization of the monomer, C₁₄H₉Cl, followed by recrystallization. The symmetry of the product mol­ecules is defined by the orientation of the reactant mol­ecules in the crystal. The mutual orientation parameters calculated for adjacent monomers explain the reactivity of the compound. The mol­ecules in the crystal of the monomer and the recrystallized photodimer pack differently and the photodimer has crystallographically imposed inversion symmetry.

S1. Comment

Crystallographic structural studies of [4 + 4] photodimerization in crystals have in most cases been limited to analyses of the crystal structure of the reactant (Bart & Schmidt, 1971; Heller & Schmidt, 1971; Ihmels et al., 1999, 2000; Wang & Jones, 1987, 1994). The structures of the photodimers are also known, but usually the photodimerization was carried out in solution (Abboud et al., 1990; Becker et al., 1988; Langer & Becker, 1993a,b,c,d; Ojima et al., 2000; Peters et al., 2000; Sinha et al., 1991; Sundell & Becker, 1994) and seldom in crystals (Chandross & Ferguson, 1966; Craig & Sarti-Fantoni, 1966; Dougherty et al., 1986; Ehrenberg, 1966, 1968; Harada et al., 1995, 1996; Wada & Tanaka, 1977). [4 + 4] photodimerization of the single-crystal-to-single-crystal type is very rare (Craig & Sarti-Fantoni, 1966; Dougherty et al., 1986; Ehrenberg, 1966, 1968; Harada et al., 1995; Wada & Tanaka, 1977).

Recently, the crystal structure changes monitored step-by-step during [2 + 2] photodimerization (Turowska-Tyrk, 2001, 2003), [4 + 4] photodimerization (Turowska-Tyrk & Trzop, 2003), thermal isomerization (Bogadi et al., 2002), [4 + 2] dimerization (Kim, Hubig et al., 2001; Kim, Lindeman et al., 2001) and polymerization (Foley et al., 1999) have been described. In this part of our series, we will analyze the structures of the reactant, (I), and product, (II), of the [4 + 4] photodimerization of 1-chloroanthracene in crystals. The possibility of such photodimerization in the solid state was stated by Heller & Schmidt (1971). Unfortunately, the reaction cannot be conducted in the single-crystal-to-single-crystal manner. Although we undertook many trials using different wavelengths, always on the monomer low-energy absorption tail (Enkelmann et al., 1993; Novak et al., 1993a,b), the crystals collapsed into microcrystalline material. \sch

Figs. 1 and 2 show views of the molecules and fragments of the crystal lattices for the reactant, (I), and the product, (II), respectively. The product molecule has a characteristic shape of two united butterflies related by an inversion centre. The adjacent reactant molecules have the same orientation in the crystal. The central bonds formed between the two moieties of the dimer are elongated (Table 1), and this is also observed for photoproducts of other anthracenes. It is worth adding that there are known examples of [4 + 4] photodimerization when, although the monomers were situated head-to-head in the crystal, the dimers obtained by single-crystal-to-single-crystal photoreaction had head-to-tail symmetry (Craig & Sarti-Fantoni, 1966; Ehrenberg, 1968; Kaupp, 1993). A very interesting explanation of this phenomenon was given by Kaupp (1993).

The mutual orientation of adjacent monomer molecules in a crystal is one of the factors influencing [4 + 4] photodimerization (Bart & Schmidt, 1971; Heller & Schmidt, 1971; Ihmels et al., 1999, 2000; Wang & Jones, 1987, 1994). This orientation can be described by the following five parameters (Ihmels et al., 2000; Turowska-Tyrk & Trzop, 2003; Wang & Jones, 1994): α, the C9···C10···C9ⁱ and C10···C9···C10ⁱ angles, τ, the C9···C10···C9ⁱ···C10ⁱ and C10···C9···C10ⁱ···C9ⁱ torsion angles, ϕ, the dihedral angle between the cantral rings of adjacent monomers, κ, the angle between the central ring of the parent monomer molecule and the plane formed by the atoms C9, C10, C9ⁱ and C10ⁱ, and d_i, the C9···C10ⁱ and C10···C9ⁱ distances [symmetry code: (i)]. The ideal values for these are 90°, 0°, 0°, 90° and less than 4.2 Å, respectively. The parameters are 98.21 (8), 0, 0 and 67.86 (8)° and 3.760 (3) Å, respectively, for (I), and 108.2, 0, 0 and 74.3° and 3.859 Å for 9-methylanthracene (Turowska-Tyrk & Trzop, 2003). Please make sure the parameters are in the same order as the definitions. These values explain the reactivity of both compounds.

There are also differences between (I) and 9-methylanthracene. The reactant and recrystallized product crystals of the former belong to different space groups, namely P2₁/c and C2/c, respectively. The a cell constant is doubled in the product. Moreover, comparison of Figs. 1 and 2 shows that, although the orientation of the upper molecules (A and B pairs) is similar, the orientation of the bottom ones (C and D pairs) is very different for the reactant and the product. This might be the reason why the photoreaction is accompanied by crystal disintegration, making the monitoring of structural changes by means of X-ray structure analysis impossible. We succeeded in carrying out such monitoring in the case of 9-methylanthracene, although only to about 30% reaction progress (Turowska-Tyrk & Trzop, 2003). In the case of 9-methylanthracene, the space group was the same (P2₁/c) and the cell constants and crystal packing more similar for the reactant and the recrystallized photoproduct crystals.

S2. Experimental

Crystals of 1-chloroathracene monomer, (I), were obtained by crystallization from a mixture of acetone and cyclohexane (Ratio?). Crystals of the photodimer, (II), were obtained by irradiation of the reactant powder with the 430 nm line from a 150 W Xe lamp, followed by recrystallization from a mixture of chloroform and toluene (Ratio?).

S3. Refinement

Low-angle reflections with θ below 5.8° were not measured. H-atom parameters were freely refined.

Computing details

For both compounds, data collection: KM-4 CCD Software (Kuma Diffraction, 2000); cell refinement: KM-4 CCD Software; data reduction: KM-4 CCD Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Johnson et al., 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the reactant molecule, (I) (top) and a fragment of the crystal lattice (bottom). Displacement ellipsoids are drawn at the 25% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the product molecule, (II) (top) and a fragment of the crystal lattice (bottom). Displacement ellipsoids are drawn at the 25% probability level and H atoms are shown as small spheres of arbitrary radii.

(I) 1-chloroanthracene

Crystal data

C14H9Cl	F(000) = 440
Mr = 212.66	Dx = 1.366 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1959 reflections
a = 10.3280 (9) Å	θ = 5–26°
b = 12.0802 (11) Å	µ = 0.33 mm^−1
c = 8.4369 (7) Å	T = 293 K
β = 100.673 (8)°	Prism, yellow
V = 1034.41 (16) Å^3	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection

Kuma KM-4 CCD area-detector diffractometer	1641 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 26.0°, θmin = 5.8°
ω scans	h = −12→12
4935 measured reflections	k = −14→14
1991 independent reflections	l = −5→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.057	Hydrogen site location: difference Fourier map
wR(F^2) = 0.161	All H-atom parameters refined
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0851P)^2 + 0.3292P] where P = (Fo^2 + 2Fc^2)/3
1991 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

Experimental. Intensities of reflections were collected with a CCD camera diffractometer. The general strategy of data collection for area-detector diffractometers was described by Scheidt, W. R. & Turowska-Tyrk, I. (1994). Inorg. Chem. 33, 1314–1318. Low-angle reflections with θ below 5.8° were not measured.

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2065 (2)	0.13424 (18)	−0.0230 (2)	0.0522 (5)
C2	0.3087 (2)	0.0755 (2)	−0.0574 (3)	0.0599 (6)
C3	0.2842 (3)	−0.0103 (2)	−0.1778 (3)	0.0682 (7)
C4	0.1625 (3)	−0.0308 (2)	−0.2546 (3)	0.0637 (6)
C5	−0.3146 (3)	0.0461 (3)	−0.3448 (3)	0.0770 (8)
C6	−0.4159 (3)	0.1058 (3)	−0.3083 (4)	0.0867 (10)
C7	−0.3948 (3)	0.1884 (3)	−0.1911 (4)	0.0791 (8)
C8	−0.2728 (2)	0.2102 (2)	−0.1097 (3)	0.0636 (6)
C9	−0.0341 (2)	0.17319 (17)	−0.0639 (3)	0.0481 (5)
C10	−0.0757 (2)	0.00846 (19)	−0.2980 (3)	0.0573 (6)
C11	0.07394 (19)	0.11499 (16)	−0.1001 (2)	0.0446 (5)
C12	0.0512 (2)	0.02983 (16)	−0.2200 (2)	0.0495 (5)
C13	−0.1823 (2)	0.06662 (18)	−0.2634 (2)	0.0539 (5)
C14	−0.16198 (19)	0.15141 (17)	−0.1440 (2)	0.0487 (5)
Cl1	0.23845 (7)	0.23691 (6)	0.12162 (9)	0.0804 (3)
H2	0.396 (3)	0.087 (3)	−0.006 (4)	0.089 (9)*
H3	0.359 (4)	−0.053 (3)	−0.194 (4)	0.107 (10)*
H4	0.145 (3)	−0.089 (3)	−0.339 (4)	0.105 (10)*
H5	−0.330 (3)	−0.011 (2)	−0.421 (4)	0.077 (8)*
H6	−0.494 (4)	0.094 (3)	−0.360 (5)	0.128 (13)*
H7	−0.470 (4)	0.232 (3)	−0.173 (5)	0.102 (11)*
H8	−0.258 (3)	0.269 (3)	−0.017 (4)	0.091 (10)*
H9	−0.028 (3)	0.224 (2)	0.010 (3)	0.059 (7)*
H10	−0.096 (3)	−0.051 (2)	−0.379 (4)	0.084 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0505 (11)	0.0549 (11)	0.0510 (11)	−0.0048 (9)	0.0089 (8)	0.0031 (9)
C2	0.0477 (12)	0.0697 (14)	0.0634 (13)	0.0026 (11)	0.0129 (10)	0.0150 (11)
C3	0.0642 (15)	0.0703 (15)	0.0767 (16)	0.0169 (13)	0.0304 (13)	0.0176 (13)
C4	0.0830 (17)	0.0546 (13)	0.0580 (13)	0.0012 (12)	0.0251 (12)	0.0016 (10)
C5	0.0719 (18)	0.092 (2)	0.0611 (14)	−0.0291 (16)	−0.0040 (12)	0.0069 (14)
C6	0.0458 (14)	0.120 (3)	0.088 (2)	−0.0210 (16)	−0.0063 (13)	0.0263 (19)
C7	0.0478 (14)	0.093 (2)	0.097 (2)	0.0008 (14)	0.0148 (13)	0.0290 (17)
C8	0.0539 (13)	0.0654 (14)	0.0735 (16)	−0.0005 (11)	0.0173 (11)	0.0129 (12)
C9	0.0518 (11)	0.0457 (10)	0.0466 (10)	−0.0068 (9)	0.0089 (8)	−0.0023 (8)
C10	0.0716 (15)	0.0537 (12)	0.0463 (11)	−0.0126 (11)	0.0100 (10)	−0.0039 (9)
C11	0.0436 (10)	0.0473 (10)	0.0437 (10)	−0.0061 (8)	0.0098 (7)	0.0085 (8)
C12	0.0627 (12)	0.0444 (10)	0.0437 (10)	−0.0044 (9)	0.0156 (9)	0.0038 (8)
C13	0.0538 (12)	0.0588 (12)	0.0473 (11)	−0.0133 (10)	0.0051 (9)	0.0080 (9)
C14	0.0441 (10)	0.0515 (11)	0.0514 (11)	−0.0048 (8)	0.0115 (8)	0.0104 (9)
Cl1	0.0630 (5)	0.0885 (5)	0.0848 (5)	−0.0153 (3)	0.0015 (3)	−0.0278 (3)

Geometric parameters (Å, º)

C1—C2	1.347 (3)	C6—H6	0.85 (4)
C1—C11	1.422 (3)	C7—C8	1.345 (4)
C1—Cl1	1.728 (2)	C7—H7	0.97 (4)
C2—C3	1.440 (4)	C8—C14	1.421 (3)
C2—H2	0.93 (3)	C8—H8	1.04 (3)
C3—C4	1.327 (4)	C9—C14	1.393 (3)
C3—H3	0.96 (4)	C9—C11	1.399 (3)
C4—C12	1.438 (3)	C9—H9	0.87 (3)
C4—H4	1.00 (3)	C10—C12	1.378 (3)
C5—C6	1.353 (5)	C10—C13	1.382 (3)
C5—C13	1.432 (3)	C10—H10	0.99 (3)
C5—H5	0.94 (3)	C11—C12	1.431 (3)
C6—C7	1.393 (5)	C13—C14	1.425 (3)
C2—C1—C11	122.8 (2)	C7—C8—C14	120.8 (3)
C2—C1—Cl1	118.37 (18)	C7—C8—H8	120.4 (19)
C11—C1—Cl1	118.85 (16)	C14—C8—H8	118.7 (18)
C1—C2—C3	119.3 (2)	C14—C9—C11	121.5 (2)
C1—C2—H2	123.3 (19)	C14—C9—H9	114.8 (17)
C3—C2—H2	117.4 (19)	C11—C9—H9	123.7 (17)
C4—C3—C2	120.3 (2)	C12—C10—C13	121.9 (2)
C4—C3—H3	123 (2)	C12—C10—H10	121.6 (17)
C2—C3—H3	117 (2)	C13—C10—H10	116.4 (17)
C3—C4—C12	121.8 (2)	C9—C11—C1	123.82 (19)
C3—C4—H4	121 (2)	C9—C11—C12	118.82 (18)
C12—C4—H4	118 (2)	C1—C11—C12	117.35 (19)
C6—C5—C13	120.5 (3)	C10—C12—C11	119.3 (2)
C6—C5—H5	120.8 (18)	C10—C12—C4	122.2 (2)
C13—C5—H5	118.7 (19)	C11—C12—C4	118.5 (2)
C5—C6—C7	121.2 (3)	C10—C13—C14	119.72 (19)
C5—C6—H6	119 (3)	C10—C13—C5	122.5 (2)
C7—C6—H6	119 (3)	C14—C13—C5	117.8 (2)
C8—C7—C6	120.7 (3)	C9—C14—C8	122.3 (2)
C8—C7—H7	121 (2)	C9—C14—C13	118.77 (19)
C6—C7—H7	118 (2)	C8—C14—C13	119.0 (2)

(II) trans-bi(1-chloro-9,10-dihydro-9,10-anthracenediyl)

Crystal data

C28H18Cl2	F(000) = 880
Mr = 425.32	Dx = 1.416 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1164 reflections
a = 20.232 (2) Å	θ = 5–22°
b = 11.0746 (13) Å	µ = 0.34 mm^−1
c = 9.0872 (11) Å	T = 293 K
β = 101.475 (10)°	Plate, colourless
V = 1995.4 (4) Å^3	0.30 × 0.20 × 0.08 mm
Z = 4

Data collection

Kuma KM-4 CCD area-detector diffractometer	1545 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Graphite monochromator	θmax = 26.0°, θmin = 5.9°
ω scans	h = −21→24
4922 measured reflections	k = −13→13
1945 independent reflections	l = −11→8

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: difference Fourier map
wR(F^2) = 0.119	All H-atom parameters refined
S = 1.08	w = 1/[σ^2(Fo^2) + (0.06P)^2 + 0.9967P] where P = (Fo^2 + 2Fc^2)/3
1945 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

Experimental. Intensities of reflections were collected with a CCD camera diffractometer. The general strategy of data collection for area-detector diffractometers was described by Scheidt, W. R. & Turowska-Tyrk, I. (1994). Inorg. Chem. 33, 1314–1318. Low-angle reflections with θ below 5.8° were not measured.

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.05591 (3)	0.79196 (6)	0.11803 (7)	0.0544 (2)
C1	0.09676 (10)	0.6850 (2)	0.0283 (2)	0.0360 (5)
C2	0.05764 (12)	0.5988 (2)	−0.0591 (3)	0.0445 (6)
C3	0.08870 (12)	0.5126 (2)	−0.1304 (3)	0.0462 (6)
C4	0.15778 (12)	0.5135 (2)	−0.1175 (2)	0.0394 (5)
C5	0.36415 (11)	0.5823 (2)	0.2106 (3)	0.0417 (5)
C6	0.39430 (13)	0.6158 (2)	0.3550 (3)	0.0501 (6)
C7	0.36493 (13)	0.7020 (2)	0.4295 (3)	0.0486 (6)
C8	0.30482 (11)	0.7551 (2)	0.3610 (2)	0.0404 (5)
C9	0.21126 (10)	0.78342 (18)	0.1312 (2)	0.0318 (5)
C10	0.27151 (10)	0.61173 (19)	−0.0212 (2)	0.0321 (5)
C11	0.16630 (10)	0.68827 (18)	0.0444 (2)	0.0319 (5)
C12	0.19651 (10)	0.60097 (18)	−0.0316 (2)	0.0324 (5)
C13	0.30484 (10)	0.63614 (18)	0.1398 (2)	0.0331 (5)
C14	0.27477 (10)	0.72307 (18)	0.2160 (2)	0.0330 (5)
H2	0.0091 (14)	0.600 (2)	−0.070 (3)	0.056 (7)*
H3	0.0605 (15)	0.451 (3)	−0.186 (3)	0.066 (8)*
H4	0.1779 (10)	0.455 (2)	−0.169 (2)	0.031 (5)*
H5	0.3863 (12)	0.525 (2)	0.157 (3)	0.043 (6)*
H6	0.4353 (14)	0.580 (2)	0.399 (3)	0.057 (7)*
H7	0.3871 (14)	0.723 (2)	0.532 (3)	0.061 (8)*
H8	0.2850 (13)	0.814 (2)	0.414 (3)	0.048 (7)*
H9	0.1903 (11)	0.822 (2)	0.200 (3)	0.035 (6)*
H10	0.2890 (11)	0.538 (2)	−0.054 (3)	0.042 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0368 (3)	0.0685 (5)	0.0597 (4)	0.0046 (3)	0.0139 (3)	−0.0094 (3)
C1	0.0321 (10)	0.0424 (12)	0.0341 (11)	−0.0033 (9)	0.0080 (8)	0.0046 (9)
C2	0.0330 (12)	0.0498 (14)	0.0486 (13)	−0.0105 (11)	0.0031 (10)	0.0051 (11)
C3	0.0411 (13)	0.0453 (13)	0.0485 (14)	−0.0151 (11)	0.0002 (10)	−0.0015 (11)
C4	0.0441 (12)	0.0346 (11)	0.0380 (12)	−0.0065 (10)	0.0047 (10)	−0.0014 (9)
C5	0.0392 (12)	0.0403 (12)	0.0436 (13)	0.0018 (10)	0.0037 (10)	0.0037 (10)
C6	0.0402 (13)	0.0530 (15)	0.0493 (14)	0.0005 (12)	−0.0097 (11)	0.0110 (12)
C7	0.0519 (14)	0.0523 (15)	0.0354 (13)	−0.0098 (12)	−0.0060 (11)	0.0040 (11)
C8	0.0435 (13)	0.0440 (12)	0.0327 (11)	−0.0080 (10)	0.0052 (10)	−0.0013 (10)
C9	0.0302 (10)	0.0379 (11)	0.0286 (10)	−0.0011 (9)	0.0089 (8)	−0.0041 (8)
C10	0.0335 (11)	0.0303 (11)	0.0320 (10)	0.0004 (9)	0.0055 (8)	−0.0022 (9)
C11	0.0312 (10)	0.0357 (11)	0.0287 (10)	−0.0060 (9)	0.0060 (8)	0.0035 (8)
C12	0.0338 (11)	0.0333 (11)	0.0291 (10)	−0.0044 (9)	0.0042 (8)	0.0034 (8)
C13	0.0319 (10)	0.0335 (10)	0.0329 (10)	−0.0049 (9)	0.0039 (8)	0.0032 (8)
C14	0.0334 (10)	0.0370 (11)	0.0281 (10)	−0.0070 (9)	0.0050 (8)	0.0021 (8)

Geometric parameters (Å, º)

Cl1—C1	1.737 (2)	C7—C8	1.382 (3)
C1—C2	1.385 (3)	C7—H7	0.98 (3)
C1—C11	1.386 (3)	C8—C14	1.383 (3)
C2—C3	1.374 (4)	C8—H8	0.95 (3)
C2—H2	0.97 (3)	C9—C11	1.508 (3)
C3—C4	1.379 (3)	C9—C14	1.516 (3)
C3—H3	0.96 (3)	C9—C10^i	1.615 (3)
C4—C12	1.385 (3)	C9—H9	0.92 (2)
C4—H4	0.94 (2)	C10—C12	1.506 (3)
C5—C13	1.379 (3)	C10—C13	1.508 (3)
C5—C6	1.383 (3)	C10—C9^i	1.615 (3)
C5—H5	0.96 (2)	C10—H10	0.96 (2)
C6—C7	1.372 (4)	C11—C12	1.398 (3)
C6—H6	0.94 (3)	C13—C14	1.394 (3)
C2—C1—C11	122.0 (2)	C11—C9—C14	108.66 (17)
C2—C1—Cl1	117.93 (17)	C11—C9—C10^i	111.13 (16)
C11—C1—Cl1	120.03 (16)	C14—C9—C10^i	111.49 (16)
C3—C2—C1	119.1 (2)	C11—C9—H9	111.4 (14)
C3—C2—H2	120.6 (16)	C14—C9—H9	108.3 (14)
C1—C2—H2	120.2 (16)	C10^i—C9—H9	105.8 (14)
C2—C3—C4	120.4 (2)	C12—C10—C13	109.02 (16)
C2—C3—H3	117.3 (17)	C12—C10—C9^i	110.89 (16)
C4—C3—H3	122.3 (17)	C13—C10—C9^i	111.20 (16)
C3—C4—C12	120.2 (2)	C12—C10—H10	110.0 (14)
C3—C4—H4	119.0 (13)	C13—C10—H10	109.5 (14)
C12—C4—H4	120.7 (13)	C9^i—C10—H10	106.1 (14)
C13—C5—C6	120.3 (2)	C1—C11—C12	117.68 (18)
C13—C5—H5	119.8 (14)	C1—C11—C9	124.56 (19)
C6—C5—H5	119.7 (14)	C12—C11—C9	117.66 (17)
C7—C6—C5	120.2 (2)	C4—C12—C11	120.54 (19)
C7—C6—H6	121.3 (16)	C4—C12—C10	122.76 (19)
C5—C6—H6	118.5 (16)	C11—C12—C10	116.63 (17)
C6—C7—C8	120.1 (2)	C5—C13—C14	119.48 (19)
C6—C7—H7	118.4 (16)	C5—C13—C10	123.67 (19)
C8—C7—H7	121.4 (16)	C14—C13—C10	116.76 (18)
C7—C8—C14	120.0 (2)	C8—C14—C13	119.8 (2)
C7—C8—H8	119.2 (15)	C8—C14—C9	122.6 (2)
C14—C8—H8	120.7 (15)	C13—C14—C9	117.48 (17)

Symmetry code: (i) −x+1/2, −y+3/2, −z.