Cyclopropanation reactions on [alpha]-cis-himachalene and a [beta

CIF access Acta Cryst. (1999). C55, IUC9900055

[ doi:10.1107/S010827019909931X ]

Cyclopropanation reactions on -cis-himachalene and a -himachalene A. Auhmani, E. Kossareva, E. Lassaba, M. Réglier, M. Pierrot and A. Benharref Abstract The crystallographic structures of 2a,3a,7a,15a-tetrabromocarbene-himachalane, C17H24Br4, (3), 2a,3a,7a,15a-tetrachlorocarbene-himachalane, C17H24Cl4, (4), and 6a,7a-dichlorocarbene-himachal-2-ene, C16H24Cl2, (5), resulting from cyclopropanation reactions of the C═C double bonds of α-cis-himachalene and β-himachalene, are reported. Comment α-cis-Himachalene and β-himachalene are the main constituents of Atlas Cedar (cedrus atlantica) essential oils (Plattier & Teisseire, 1974). The reactivity of the α-cis -himachalene (1) (Chiaroni et al., 1992; Lassaba et al., 1997) and of the β-himachalane (2) (Chiaroni et al., 1991; Benharref et al., 1991) has been widely investigated in our laboratory in order to improve their olfactive properties. We present now the cyclopropanation reaction of the double bonds of (1) and the dichloro- or dibromocarbene condensation on (1). The cycloaddition on (1) has been performed according to the phase-transfer process (Doering & Kentaro Hoffman, 1954; Demhlow, 1974), the dibromo- or dichlorocarbene being generated in situ from bromo- or chloroform, using N-benzyltriethylammonium chloride as catalyst. Only one product resulting from the double condensation of the dibromocarbene, product (3), or of the dichlorocarbene, product (4), is obtained in one step. However, the reaction performed on β-himachalane (2) under the same conditions of phase-transfer catalysis allows the condensation on only one double bond, compound (5), a second condensation being necessary for obtaining (6). The stereochemistry of the reaction products has been found by crystallography, and is in agreement with results obtained previously (Lassaba et al., 1997, 1998).

Experimental To a solution of α-cis-himachalene (1) (2 g, 9.8 mmol) in dichloromethane at 273 K, were added CHBr3 (2 ml, 22.0 mmol) N-benzyltriethylammonium chloride (50 mg, 0.21 mmol) and NaOH (1 g, 25 mmol). The mixture was stirred for 4 h at 273 K and then filtered on celite and dried over Na2SO4. The expected product (3) was obtained by pentane elution on a silice column, yield: 10.2%, m.p.: 437–438 K. The same procedure was employed for the preparation of (4), with CHCl3 used as reactive and solvent; yield: 20.4%, m.p.: 408–409 K. β-Himachalene (2) (2 g, 9.8 mmol) was dissolved in 60 ml of hexane at 268 K, then 4 g (35.6 mmol) of potassium tertiobutylate were added. The mixture was stirred for 10 min, then a stiochiometric quantity of CHCl3 was added drop wise and the mixture was stirred for 8 h. After hydrolysis by 20 ml of water the hexanic phase is extracted by (ethyl) ether, washed with water and concentrated under vacuum. Chromatography on alumina column and hexane elution leads to the expected compound (5), yield: 50%, m.p. 357–358 K. Compound (6) was obtained by the same procedure: starting from 334 mg (1.16 mmol) of (5), 1.15 ml of CHBr3 (17.17 mmol), 1 g (25

CIF access mmol) of NaOH and 50 mg of N-benzyltriethylammonium chloride; yield: 8%; m.p. 396–397 K. Compounds (3), (4), (5) and (6) were crystallized by evaporation at room temperature of a pentane solution. Refinement In this series of compounds, molecules (3), (4) and (5) crystallize in space group P212121, but compound (6) belongs to the monoclinic C2 space group with eight molecules per unit cell. The structure can not be solved in the centrosymetric space group C2/m. In space group C2 there is no relationships between the atomic coordinates of the two independent molecules indicating the existence of a higher symmetry. The data/parameter ratio is equal to 5.7 and the refinement of this structure is not satisfactory, particularly for the goodness of fit and for some bond distance lengths. Therefore this crystal structure cannot be published but atom coordinates and complete geometry may be obtained on request to the authors. Computing details Data collection: KappaCCD (Nonius, 1998) for (3); KappaCCD for (5), (4). Data reduction: MAXUS (Mackay et al., 1998) for (3); MAXUS for (5), (4). For all compounds, program(s) used to solve structure: MAXUS; program(s) used to refine structure: MAXUS; molecular graphics: MAXUS; software used to prepare material for publication: MAXUS

(3) Crystal data C17H24Br4

V = 1887.9 (5) Å3

Mr = 548.02

Z=4

Orthorhombic, P212121

Mo Kα

a = 11.046 (1) Å

µ = 8.44 mm−1 T = 298 K 0.25 × 0.20 × 0.20 mm

b = 12.545 (1) Å c = 13.624 (1) Å

Data collection KappaCCD diffractometer Absorption correction: multi-scan SORTAV (Blessing, 1995, 1997) Tmin = 0.150, Tmax = 0.185

2164 independent reflections 1914 reflections with I > σ(I) Rint = 0.06

12413 measured reflections

Refinement R[F2 > 2σ(F2)] = 0.041

H-atom parameters not refined

wR(F ) = 0.071

Δρmax = 0.51 e Å−3

1914 reflections

Δρmin = −0.47 e Å−3

2

191 parameters

(4)

CIF access Crystal data C17H24Cl4

V = 1799.1 (4) Å3

Mr = 370.19

Z=4


Mo Kα

a = 11.018 (1) Å

µ = 0.65 mm−1 T = 298 K 0.45 × 0.25 × 0.20 mm

b = 12.278 (1) Å c = 13.299 (1) Å

Data collection KappaCCD diffractometer Absorption correction: none 10704 measured reflections




wR(F ) = 0.131

Δρmax = 0.29 e Å−3

1905 reflections

Δρmin = −0.24 e Å−3

2

190 parameters

(5) Crystal data C16H24Cl2

V = 1546.9 (4) Å3

Mr = 287.28

Z=4


Mo Kα

a = 9.599 (1) Å

µ = 0.40 mm−1 T = 298 K 0.55 × 0.35 × 0.35 mm

b = 11.922 (1) Å c = 13.517 (1) Å

Data collection KappaCCD diffractometer Absorption correction: none 7887 measured reflections




wR(F ) = 0.134

Δρmax = 0.29 e Å−3

1626 reflections

Δρmin = −0.27 e Å−3

2

163 parameters

CIF access References Benharref, A., Checkroun, A. & Lavergne, J. P. (1991). Bull. Soc. Chim. Fr. 128, 738–741. Blessing, R. H. (1995). Acta Cryst. A51, 33–37. Blessing, R. H. (1997). J. Appl. Cryst. 30, 421–426. Chiaroni, A., Pais, M., Riche, C., Benharref, A., Checkroun, A. & Lavergne, J. P. (1991). Acta Cryst. C47, 1991–1948. Chiaroni, A., Riche, C., Benharref, A., Checkroun, A. & Lavergne, J. P. (1992). Acta Cryst. C48, 1720–1722. Chiaroni, A., Riche, C., Benharref, A., Lassaba, E. & Baouib, A. (1996). Acta Cryst. C52, 2504–2507. Dehmlow, E. V. (1974). Angew. Chem. Int. Ed. Engl. 13, 170–199. Doering, W. V. & Kentaro Hoffman, A. (1954). J. Am. Chem. Soc. 76, 6162 -6165. Lassaba, E., Checkroun, A., Benharref, A., Chiaroni, A. M., Riche, C. & Lavergne, J. P. (1997). Bull. Soc. Chim. Belg. 106, 281–288. Lassaba, E., El Jamili, H., Checkroun, A., Benharref, A., Chiaroni, A. M., Riche, C. & Lavergne, J. P. (1998). Synth. Commun. 28, 2641–2651. Mackay, S., Gilmore, C. J., Edwards, C., Tremayne, M., Stuart, N. & Shankland, K. (1998). MAXUS. A Computer Program for the Solution and Refinement of Crystal Structures from Diffraction Data. University of Glasgow, Scotland, Nonius BV, Delft, The Netherlands, and MacScience Co. Ltd, Yokohama, Japan. Nonius (1998). Kappa CCD Reference Manual. Nonius BV, Delft, The Netherlands. Plattier, M. & Teisseire, P. (1974). Recherches, 19, 131-144. Waasmaier, D. & Kirfel, A. (1995). Acta Cryst. A51, 416–431.

CIF access Scheme 1

supplementary materials

supplementary materials (3) Crystal data C17H24Br4

Dx = 1.928 Mg m−3

Mr = 548.02

Mo Kα radiation λ = 0.71073 Å


Cell parameters from 12413 reflections

a = 11.046 (1) Å

θ = 1–25º

b = 12.545 (1) Å

µ = 8.44 mm−1 T = 298 K

c = 13.624 (1) Å V = 1887.9 (5) Å3 Z=4

Prismatic, colourless 0.25 × 0.20 × 0.20 mm

Data collection 1914 reflections with I > σ(I) Rint = 0.06

KappaCCD diffractometer ψ scan Absorption correction: multi-scan SORTAV (Blessing, 1995, 1997) Tmin = 0.150, Tmax = 0.185

θmax = 25.4º h = 0→13 k = −15→15 l = −16→16

12413 measured reflections 2164 independent reflections

Refinement Refinement on F

Weighting scheme based on measured s.u.'s w = 1/ [σ2(Fo) + 0.03Fo2]

R[F2 > 2σ(F2)] = 0.041

(Δ/σ)max = 0.003

wR(F2) = 0.071

Δρmax = 0.51 e Å−3

1914 reflections

Δρmin = −0.47 e Å−3

191 parameters H-atom parameters not refined

Extinction correction: none

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) Br3 Br2 Br1 Br4 C2 C6 C5 C1 C4

x

y

z

Uiso*/Ueq

−0.16182 (9) 0.27352 (9) 0.36273 (7) −0.38367 (7) −0.1690 (7) 0.0994 (6) 0.0863 (6) −0.1377 (7) 0.0551 (7)

−0.64313 (8) −0.39778 (8) −0.53974 (9) −0.5315 (1) −0.5972 (6) −0.4950 (6) −0.5283 (6) −0.4916 (6) −0.6460 (7)

0.16894 (7) −0.28399 (7) −0.10902 (8) 0.06984 (9) −0.0465 (5) −0.1403 (5) −0.0304 (5) 0.0005 (5) −0.0165 (6)

0.0639 (5) 0.0654 (5) 0.0670 (5) 0.0735 (6) 0.042 (4) 0.037 (3) 0.035 (4) 0.038 (4) 0.046 (4)

sup-1

supplementary materials C3 C11 C9 C16 C15 C17 C13 C7 C10 C12 C18 C8 H5 H1 H4A H4B H3A H3B H11 H9A H9B H16A H16B H15A H15B H15C H13A H13B H13C H7A H7B H12A H12B H12C H8A H8B

−0.0691 (8) −0.0069 (6) −0.0221 (8) 0.1361 (8) −0.2575 (9) 0.2244 (7) 0.1447 (8) 0.0179 (7) 0.0130 (7) −0.066 (1) −0.2139 (7) 0.0438 (8) 0.16164 −0.16333 0.05752 0.11722 −0.06780 −0.05910 −0.00412 −0.00480 −0.10685 0.12125 0.16735 −0.21644 −0.29234 −0.32044 0.19735 0.16425 0.15525 −0.06324 0.02556 −0.14929 −0.05319 −0.04429 0.12889 0.02069

−0.6786 (6) −0.4654 (6) −0.2726 (7) −0.5804 (7) −0.5975 (8) −0.4984 (6) −0.3227 (7) −0.4078 (8) −0.3428 (7) −0.3090 (9) −0.5691 (6) −0.2971 (7) −0.51742 −0.43459 −0.66002 −0.68642 −0.74483 −0.69328 −0.48920 −0.20324 −0.27813 −0.57673 −0.64953 −0.61674 −0.52784 −0.64834 −0.34333 −0.36343 −0.24823 −0.42773 −0.40693 −0.32114 −0.23464 −0.34994 −0.29129 −0.24409

−0.0572 (7) 0.0300 (5) −0.0418 (8) −0.2137 (6) −0.1310 (6) −0.1864 (6) 0.0760 (8) −0.1789 (6) 0.0465 (6) 0.1326 (8) 0.0549 (6) −0.1373 (7) 0.00323 −0.04167 0.05266 −0.04884 −0.02330 −0.12452 0.09691 −0.01886 −0.03570 −0.28311 −0.19731 −0.19052 −0.13812 −0.11792 0.02321 0.13351 0.08961 −0.16141 −0.24911 0.11692 0.14572 0.18962 −0.12415 −0.18455

0.049 (4) 0.036 (4) 0.056 (5) 0.054 (5) 0.060 (5) 0.047 (4) 0.065 (5) 0.052 (5) 0.046 (4) 0.076 (7) 0.046 (4) 0.057 (5) 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000*

Atomic displacement parameters (Å2) Br3 Br2 Br1 Br4 C2 C6 C5 C1

sup-2

U11 0.0804 (6) 0.0704 (6) 0.0372 (4) 0.0444 (4) 0.037 (3) 0.032 (3) 0.030 (3) 0.040 (4)

U22 0.0645 (6) 0.0717 (6) 0.0731 (6) 0.0864 (7) 0.050 (4) 0.048 (5) 0.046 (4) 0.039 (4)

U33 0.0468 (5) 0.0542 (5) 0.0907 (7) 0.0897 (7) 0.038 (4) 0.032 (4) 0.030 (3) 0.035 (4)

U12 −0.0100 (5) −0.0136 (5) 0.0102 (4) −0.0040 (5) −0.002 (3) −0.005 (3) 0.002 (3) 0.002 (3)

U13 0.0046 (5) 0.0221 (5) 0.0005 (5) 0.0210 (5) 0.000 (3) −0.001 (3) −0.002 (3) 0.003 (3)

U23 0.0134 (4) −0.0023 (5) −0.0024 (5) 0.0030 (6) −0.003 (3) −0.005 (3) −0.003 (3) 0.005 (3)

supplementary materials C4 C3 C11 C9 C16 C15 C17 C13 C7 C10 C12 C18 C8

0.052 (4) 0.059 (5) 0.032 (3) 0.054 (4) 0.059 (5) 0.066 (5) 0.040 (4) 0.050 (5) 0.044 (4) 0.041 (4) 0.086 (7) 0.046 (4) 0.055 (5)

0.034 (4) 0.034 (4) 0.042 (4) 0.043 (5) 0.058 (5) 0.067 (6) 0.049 (4) 0.054 (5) 0.068 (6) 0.047 (5) 0.064 (6) 0.039 (4) 0.048 (5)

0.052 (5) 0.054 (5) 0.033 (4) 0.072 (6) 0.045 (4) 0.048 (5) 0.053 (5) 0.091 (7) 0.043 (5) 0.052 (5) 0.078 (7) 0.052 (5) 0.069 (6)

0.010 (4) −0.008 (3) 0.001 (3) 0.017 (4) −0.001 (4) −0.014 (5) −0.002 (3) −0.007 (4) 0.004 (4) −0.006 (3) 0.009 (5) −0.010 (3) 0.013 (4)

0.002 (4) 0.005 (5) 0.003 (3) 0.010 (5) 0.008 (4) −0.012 (4) 0.006 (4) −0.012 (5) −0.002 (4) 0.000 (4) 0.008 (6) −0.002 (4) 0.004 (4)

0.000 (4) −0.007 (4) −0.001 (3) 0.012 (4) −0.018 (4) 0.002 (4) −0.002 (4) −0.009 (5) 0.007 (4) −0.006 (4) −0.027 (6) 0.001 (3) 0.026 (4)

Geometric parameters (Å, °) Br3—C18 Br2—C17 Br1—C17 Br4—C18 C2—C1 C2—C3 C2—C15 C2—C18 C6—C5 C6—C16 C6—C17 C6—C7

1.899 (9) 1.912 (9) 1.927 (8) 1.945 (8) 1.51 (2) 1.51 (2) 1.51 (2) 1.51 (2) 1.56 (1) 1.52 (2) 1.52 (2) 1.51 (2)

C5—C4 C5—C11 C1—C11 C1—C18 C4—C3 C11—C10 C9—C10 C9—C8 C16—C17 C13—C10 C7—C8 C10—C12

1.53 (2) 1.54 (1) 1.54 (1) 1.48 (2) 1.54 (2) 1.57 (2) 1.54 (2) 1.52 (2) 1.47 (2) 1.53 (2) 1.53 (2) 1.52 (2)

C1—C2—C3 C1—C2—C15 C1—C2—C18 C3—C2—C15 C3—C2—C18 C15—C2—C18 C5—C6—C16 C5—C6—C17 C5—C6—C7 C16—C6—C17 C16—C6—C7 C17—C6—C7 C6—C5—C4 C6—C5—C11 C4—C5—C11 C2—C1—C11 C2—C1—C18 C11—C1—C18

117.8 (7) 118.2 (7) 58.8 (5) 113.4 (7) 119.1 (7) 119.0 (7) 117.8 (7) 118.3 (6) 118.2 (7) 57.7 (6) 116.1 (7) 114.8 (7) 113.4 (7) 116.0 (6) 106.2 (6) 120.9 (7) 60.5 (6) 122.9 (7)

C5—C4—C3 C2—C3—C4 C5—C11—C1 C5—C11—C10 C1—C11—C10 C10—C9—C8 C6—C16—C17 C6—C17—C16 C6—C7—C8 C11—C10—C9 C11—C10—C13 C11—C10—C12 C9—C10—C13 C9—C10—C12 C13—C10—C12 C2—C18—C1 C9—C8—C7

114.5 (7) 116.0 (7) 112.4 (6) 119.1 (6) 112.3 (6) 115.6 (8) 61.0 (6) 61.2 (6) 114.7 (7) 114.3 (7) 109.4 (7) 107.6 (7) 110.5 (8) 107.4 (8) 107.2 (8) 60.7 (6) 114.2 (8)

C1—C2—C3—C4 C3—C2—C1—C11 C3—C2—C1—C18

1.3 (7) 4.0 (7) −108.9 (8)

C17—C6—C7—C8 C6—C5—C4—C3 C6—C5—C11—C1

−78.3 (9) −64.7 (8) 70.8 (7)

sup-3

supplementary materials C15—C2—C1—C11 C15—C2—C1—C18 C1—C2—C18—C1 C18—C2—C1—C11 C18—C2—C1—C18 C15—C2—C3—C4 C3—C2—C18—C1 C18—C2—C3—C4 C15—C2—C18—C1 C16—C6—C5—C4 C16—C6—C5—C11 C5—C6—C16—C17 C17—C6—C5—C4 C17—C6—C5—C11 C5—C6—C17—C16 C7—C6—C5—C4 C7—C6—C5—C11 C5—C6—C7—C8 C16—C6—C17—C16 C17—C6—C16—C17 C7—C6—C16—C17 C16—C6—C7—C8 C7—C6—C17—C16

−138.5 (10) 108.6 (9) 0.0 (5) 112.9 (8) 0.0 (5) 145.5 (10) 106.7 (8) −66.6 (9) −107.2 (9) −26.6 (7) −149.9 (10) −107.5 (8) −92.9 (8) 143.7 (9) 106.7 (8) 121.3 (9) −2.1 (7) 68.6 (8) 0.0 (6) 0.0 (5) 104.0 (8) −143.0 (10) −106.4 (8)

C6—C5—C11—C10 C4—C5—C11—C1 C11—C5—C4—C3 C4—C5—C11—C10 C2—C1—C11—C5 C2—C1—C11—C10 C2—C1—C18—C2 C11—C1—C18—C2 C18—C1—C11—C5 C18—C1—C11—C10 C5—C4—C3—C2 C5—C11—C10—C9 C5—C11—C10—C13 C5—C11—C10—C12 C1—C11—C10—C9 C1—C11—C10—C13 C1—C11—C10—C12 C8—C9—C10—C11 C8—C9—C10—C13 C10—C9—C8—C7 C8—C9—C10—C12 C6—C16—C17—C6 C6—C7—C8—C9


Dx = 1.367 Mg m−3

Mr = 370.19




a = 11.018 (1) Å

θ = 1–25º

b = 12.278 (1) Å

µ = 0.65 mm−1 T = 298 K

c = 13.299 (1) Å V = 1799.1 (4) Å3 Z=4

Prism, colourless 0.45 × 0.25 × 0.20 mm

Data collection KappaCCD diffractometer

Rint = 0.07

ψ scan

θmax = 25.5º

Absorption correction: none 10704 measured reflections 2066 independent reflections 1905 reflections with I > σ(I)

h = 0→13 k = −11→15 l = −16→16

sup-4

−63.5 (8) −56.2 (7) 63.9 (8) 169.5 (9) 24.9 (7) 162.4 (10) 0.0 (5) −109.6 (8) 97.7 (9) −124.9 (10) −36.4 (8) 78.7 (9) −45.9 (8) −162.0 (10) −55.7 (8) 179.8 (9) 63.6 (8) −58.4 (9) 65.6 (9) 64.0 (9) −177.7 (11) 0.0 (5) −87.4 (10)

supplementary materials Refinement Refinement on F

H-atom parameters not refined Weighting scheme based on measured s.u.'s w = 1/ [σ2(Fo) + 0.03Fo2]

R[F2 > 2σ(F2)] = 0.048 wR(F2) = 0.131

Δρmax = 0.29 e Å−3

1905 reflections

Δρmin = −0.24 e Å−3

190 parameters

Extinction correction: None

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) Cl1 Cl2 Cl3 Cl4 C17 C16 C6 C7 C8 C9 C13 C10 C12 C11 C5 C4 C3 C2 C15 C18 C1 H16A H16B H7A H7B H8A H8B H9A H9B H13A H13B H13C H12A H12B H12C

x

y

z

Uiso*/Ueq

0.14550 (5) 0.21990 (6) 0.66470 (6) 0.86980 (5) 0.2686 (2) 0.3565 (2) 0.3964 (2) 0.4750 (2) 0.4504 (2) 0.5149 (2) 0.3522 (2) 0.4848 (2) 0.5652 (3) 0.5068 (1) 0.4131 (1) 0.4459 (2) 0.5669 (2) 0.6694 (2) 0.7596 (2) 0.7143 (2) 0.6358 (2) 0.32790 0.36680 0.46310 0.55740 0.36470 0.47310 0.59960 0.54340 0.29940 0.33980 0.33450 0.54540 0.55050 0.64920

0.54280 (5) 0.40960 (5) 0.63700 (5) 0.53350 (6) 0.5052 (2) 0.5888 (2) 0.4998 (2) 0.4113 (2) 0.2964 (2) 0.2696 (2) 0.3199 (2) 0.3384 (1) 0.3016 (2) 0.4638 (1) 0.5308 (2) 0.6509 (2) 0.6836 (2) 0.5994 (2) 0.6023 (2) 0.5682 (2) 0.4906 (1) 0.65960 0.58640 0.41230 0.43070 0.29120 0.24480 0.28130 0.20950 0.34180 0.24410 0.36220 0.34420 0.22600 0.31180

0.10750 (6) 0.27390 (4) −0.16480 (4) −0.07220 (6) 0.1833 (1) 0.2133 (2) 0.1398 (1) 0.1840 (1) 0.1415 (2) 0.0445 (2) −0.0760 (2) −0.0458 (1) −0.1342 (2) −0.0327 (1) 0.0273 (1) 0.0112 (2) 0.0544 (1) 0.0453 (1) 0.1319 (2) −0.0573 (1) −0.0020 (1) 0.19390 0.28490 0.25550 0.16890 0.12920 0.19240 0.05200 0.08280 −0.02220 −0.09040 −0.13490 −0.19250 −0.14800 −0.11760

0.0857 (3) 0.0788 (3) 0.0792 (3) 0.0905 (4) 0.062 (1) 0.072 (1) 0.0511 (8) 0.065 (1) 0.066 (1) 0.063 (1) 0.068 (1) 0.0534 (9) 0.078 (1) 0.0444 (8) 0.0470 (8) 0.061 (1) 0.063 (1) 0.0557 (9) 0.076 (1) 0.061 (1) 0.0490 (8) 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000*

sup-5

supplementary materials H11 H5 H4A H4B H3A H3B H15A H15B H15C H1

0.50630 0.33390 0.38300 0.44710 0.55470 0.58560 0.81960 0.71920 0.79830 0.68610

0.48690 0.51790 0.69380 0.66390 0.68790 0.75040 0.54700 0.58840 0.67230 0.43460

−0.10170 −0.00040 0.04160 −0.06000 0.12500 0.02190 0.12020 0.19460 0.13450 0.02420

0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000*

Atomic displacement parameters (Å2) Cl1 Cl2 Cl3 Cl4 C17 C16 C6 C7 C8 C9 C13 C10 C12 C11 C5 C4 C3 C2 C15 C18 C1

U11 0.0497 (2) 0.0808 (3) 0.1118 (5) 0.0642 (3) 0.0542 (9) 0.073 (1) 0.0499 (8) 0.056 (1) 0.060 (1) 0.058 (1) 0.063 (1) 0.0533 (9) 0.091 (2) 0.0479 (8) 0.0455 (8) 0.076 (1) 0.079 (1) 0.063 (1) 0.076 (1) 0.065 (1) 0.0463 (8)

U22 0.0851 (4) 0.0869 (4) 0.0742 (3) 0.0944 (4) 0.065 (1) 0.076 (1) 0.060 (1) 0.096 (1) 0.065 (1) 0.049 (1) 0.060 (1) 0.0482 (9) 0.064 (1) 0.0438 (8) 0.0510 (9) 0.051 (1) 0.0511 (9) 0.0551 (9) 0.085 (1) 0.061 (1) 0.0474 (9)

U33 0.1223 (5) 0.0687 (3) 0.0516 (3) 0.1129 (5) 0.066 (1) 0.065 (1) 0.0435 (8) 0.0433 (9) 0.072 (1) 0.083 (1) 0.081 (1) 0.059 (1) 0.079 (1) 0.0415 (8) 0.0444 (8) 0.057 (1) 0.058 (1) 0.0495 (9) 0.066 (1) 0.057 (1) 0.0533 (9)

U12 0.0120 (3) −0.0217 (3) −0.0177 (3) −0.0137 (3) −0.0053 (9) −0.013 (1) −0.0042 (8) −0.001 (1) 0.007 (1) 0.0123 (9) −0.009 (1) 0.0002 (8) −0.005 (1) 0.0002 (7) 0.0065 (8) 0.0101 (9) −0.009 (1) −0.0109 (9) −0.022 (1) −0.0076 (9) −0.0017 (7)

U13 0.0018 (3) 0.0266 (3) 0.0112 (3) 0.0307 (3) 0.0121 (9) 0.019 (1) −0.0013 (6) −0.0050 (7) 0.0010 (9) 0.0042 (9) −0.005 (1) 0.0061 (8) 0.026 (1) 0.0023 (6) −0.0033 (6) −0.0003 (9) 0.009 (1) 0.0031 (8) −0.014 (1) 0.0100 (9) 0.0035 (7)

U23 −0.0059 (3) −0.0131 (3) 0.0101 (2) −0.0022 (3) −0.0158 (9) −0.028 (1) −0.0055 (7) 0.0117 (9) 0.028 (1) 0.0138 (9) −0.010 (1) −0.0065 (7) −0.019 (1) 0.0021 (6) −0.0033 (7) −0.0013 (8) −0.0057 (8) −0.0012 (8) 0.002 (1) 0.0011 (8) 0.0032 (7)

Geometric parameters (Å, °) Cl1—C17 Cl2—C17 Cl3—C18 Cl4—C18 C17—C16 C17—C6 C16—C6 C6—C7 C6—C5 C7—C8 C8—C9

sup-6

1.752 (2) 1.766 (3) 1.748 (2) 1.777 (3) 1.467 (3) 1.524 (3) 1.531 (3) 1.509 (3) 1.555 (3) 1.544 (4) 1.509 (4)

C13—C10 C10—C12 C10—C11 C11—C5 C11—C1 C5—C4 C4—C3 C3—C2 C2—C15 C2—C18 C2—C1

1.532 (3) 1.540 (4) 1.568 (3) 1.542 (3) 1.515 (3) 1.533 (3) 1.506 (4) 1.536 (3) 1.522 (3) 1.501 (3) 1.522 (3)

supplementary materials C9—C10

1.505 (3)

C18—C1

1.482 (3)

Cl1—C17—Cl2 Cl1—C17—C16 Cl1—C17—C6 Cl2—C17—C16 Cl2—C17—C6 C16—C17—C6 C17—C16—C6 C17—C6—C16 C17—C6—C7 C17—C6—C5 C16—C6—C7 C16—C6—C5 C7—C6—C5 C6—C7—C8 C7—C8—C9 C8—C9—C10 C9—C10—C13 C9—C10—C12 C9—C10—C11 C13—C10—C12 C13—C10—C11 C12—C10—C11 C10—C11—C5

109.4 (2) 118.9 (2) 120.6 (2) 118.7 (2) 120.7 (2) 61.5 (2) 61.1 (2) 57.4 (2) 114.4 (2) 117.7 (2) 115.5 (2) 118.3 (2) 118.9 (2) 114.5 (2) 115.4 (2) 117.1 (2) 109.6 (2) 108.5 (2) 115.4 (2) 107.8 (2) 108.8 (2) 106.5 (2) 118.5 (2)

C10—C11—C1 C5—C11—C1 C6—C5—C11 C6—C5—C4 C11—C5—C4 C5—C4—C3 C4—C3—C2 C3—C2—C15 C3—C2—C18 C3—C2—C1 C15—C2—C18 C15—C2—C1 C18—C2—C1 Cl3—C18—Cl4 Cl3—C18—C2 Cl3—C18—C1 Cl4—C18—C2 Cl4—C18—C1 C2—C18—C1 C11—C1—C2 C11—C1—C18 C2—C1—C18

112.8 (2) 111.9 (2) 116.5 (2) 113.4 (2) 106.4 (2) 114.3 (2) 116.2 (2) 113.9 (2) 119.1 (2) 116.4 (2) 118.6 (2) 119.5 (2) 58.7 (2) 109.0 (2) 121.1 (2) 122.3 (2) 118.7 (2) 117.6 (2) 61.4 (2) 122.0 (2) 123.6 (2) 59.9 (2)

Cl1—C17—C16—C6 Cl1—C17—C6—C16 Cl1—C17—C6—C7 Cl1—C17—C6—C5 Cl2—C17—C16—C6 Cl2—C17—C6—C16 Cl2—C17—C6—C7 Cl2—C17—C6—C5 C16—C17—C6—C16 C6—C17—C16—C6 C16—C17—C6—C7 C16—C17—C6—C5 C17—C16—C6—C17 C17—C16—C6—C7 C17—C16—C6—C5 C17—C6—C7—C8 C17—C6—C5—C11 C17—C6—C5—C4 C16—C6—C7—C8 C16—C6—C5—C11 C16—C6—C5—C4 C5—C6—C7—C8 C7—C6—C5—C11 C7—C6—C5—C4

−111.2 (2) 108.6 (2) −145.8 (3) 1.1 (2) 111.5 (2) −108.3 (2) −2.6 (2) 144.3 (3) 0.0 (2) 0.0 (2) 105.7 (2) −107.4 (2) 0.0 (2) −103.8 (2) 106.3 (2) 79.2 (2) −142.7 (3) 93.1 (2) 143.2 (3) 151.4 (3) 27.3 (2) −67.2 (2) 2.6 (2) −121.5 (3)

C10—C11—C5—C4 C10—C11—C1—C2 C10—C11—C1—C18 C1—C11—C5—C6 C1—C11—C5—C4 C5—C11—C1—C2 C5—C11—C1—C18 C6—C5—C4—C3 C11—C5—C4—C3 C5—C4—C3—C2 C4—C3—C2—C15 C4—C3—C2—C18 C4—C3—C2—C1 C3—C2—C18—Cl3 C3—C2—C18—Cl4 C3—C2—C18—C1 C3—C2—C1—C11 C3—C2—C1—C18 C15—C2—C18—Cl3 C15—C2—C18—Cl4 C15—C2—C18—C1 C15—C2—C1—C11 C15—C2—C1—C18 C1—C2—C18—Cl3

−170.0 (2) −161.1 (3) 126.0 (3) −71.6 (2) 56.0 (2) −24.4 (2) −97.3 (2) 64.4 (2) −65.0 (2) 38.0 (2) −147.8 (3) 64.5 (2) −2.7 (2) 7.5 (2) 147.4 (3) −104.9 (2) −3.6 (2) 109.4 (2) −138.7 (3) 1.3 (2) 108.9 (2) 139.5 (3) −107.5 (2) 112.4 (2)

sup-7

supplementary materials C6—C7—C8—C9 C7—C8—C9—C10 C8—C9—C10—C13 C8—C9—C10—C12 C8—C9—C10—C11 C9—C10—C11—C5 C9—C10—C11—C1 C13—C10—C11—C5 C13—C10—C11—C1 C12—C10—C11—C5 C12—C10—C11—C1 C10—C11—C5—C6

84.1 (3) −62.0 (2) −65.6 (2) 176.9 (3) 57.6 (2) −77.6 (2) 56.0 (2) 46.0 (2) 179.6 (2) 161.9 (3) −64.5 (2) 62.3 (2)

C1—C2—C18—Cl4 C18—C2—C1—C11 C18—C2—C1—C18 C1—C2—C18—C1 Cl3—C18—C1—C11 Cl3—C18—C1—C2 Cl4—C18—C1—C11 Cl4—C18—C1—C2 C2—C18—C1—C11 C2—C18—C1—C2 C6—C7—C8—H9B H9B—C8—C9—C10


Dx = 1.233 Mg m−3

Mr = 287.28




a = 9.599 (1) Å

θ = 1–25º

b = 11.922 (1) Å

µ = 0.40 mm−1 T = 298 K

c = 13.517 (1) Å V = 1546.9 (4) Å3 Z=4

Prism, colourless 0.55 × 0.35 × 0.35 mm

Data collection KappaCCD diffractometer

Rint = 0.06

ψ scan

θmax = 25.4º

Absorption correction: none 7887 measured reflections 1800 independent reflections 1626 reflections with I > σ(I)

h = −11→11 k = −14→14 l = 0→16

Refinement Refinement on F

Weighting scheme based on measured s.u.'s w = 1/ [σ2(Fo) + 0.03Fo2]

R[F2 > 2σ(F2)] = 0.063

(Δ/σ)max = 0.002

wR(F2) = 0.134

Δρmax = 0.29 e Å−3

1626 reflections

Δρmin = −0.27 e Å−3

163 parameters H-atom parameters not refined

Extinction correction: None

sup-8

−107.7 (2) −113.1 (2) 0.0 (2) 0.0 (2) −0.1 (2) −110.6 (2) −140.1 (3) 109.4 (2) 110.5 (2) 0.0 (2) 121.3 (3) 173.1 (3)

supplementary materials Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) Cl1 Cl2 C9 C10 C13 C12 C1 C2 C15 C11 C4 C5 C19 C6 C7 C8 C14 C3 H9A H9B H13A H13B H13C H12A H12B H12C H11 H1 H15A H15B H15C H3A H3B H4A H4B H7A H7B H8A H8B H14A H14B H14C

x

y

z

Uiso*/Ueq

0.15570 (8) −0.09320 (7) 0.3395 (3) 0.4107 (2) 0.5476 (3) 0.4366 (3) 0.3396 (2) 0.2476 (2) 0.2757 (3) 0.3160 (2) 0.0931 (2) 0.1605 (2) 0.0784 (2) 0.1076 (3) 0.2168 (3) 0.3052 (3) −0.0107 (3) 0.1096 (3) 0.38970 0.25200 0.53010 0.59440 0.60510 0.34890 0.49360 0.48290 0.34210 0.42820 0.36790 0.20870 0.26770 0.09270 0.04160 −0.00310 0.14140 0.17220 0.27830 0.25010 0.38910 −0.07630 −0.05600 0.02440

0.60200 (5) 0.69180 (6) 0.9845 (2) 0.8951 (2) 0.8611 (3) 0.9593 (3) 0.7277 (2) 0.7165 (2) 0.6472 (3) 0.7885 (2) 0.8555 (2) 0.8091 (2) 0.7250 (2) 0.8384 (2) 0.8462 (2) 0.9513 (3) 0.9198 (2) 0.7728 (2) 1.05290 1.01100 0.82250 0.81160 0.92540 0.98240 1.02410 0.91030 0.74100 0.69300 0.61610 0.58750 0.69360 0.80910 0.71490 0.87260 0.92270 0.84380 0.78310 1.00990 0.94150 0.91110 0.90460 0.99520

0.62100 (5) 0.70240 (5) 0.6593 (2) 0.7256 (2) 0.6833 (3) 0.8238 (2) 0.8361 (2) 0.9078 (2) 0.9976 (2) 0.7404 (2) 0.8194 (2) 0.7264 (2) 0.6681 (2) 0.6228 (2) 0.5431 (2) 0.5542 (2) 0.6080 (2) 0.9033 (2) 0.66470 0.68230 0.62230 0.72840 0.67080 0.85110 0.81200 0.86960 0.68610 0.84810 0.99440 1.00110 1.05540 0.96550 0.89320 0.80710 0.83820 0.47960 0.54960 0.52520 0.51650 0.66110 0.54610 0.60780

0.0752 (4) 0.0725 (4) 0.071 (2) 0.059 (1) 0.095 (2) 0.083 (2) 0.056 (1) 0.058 (1) 0.083 (2) 0.049 (1) 0.049 (1) 0.045 (1) 0.054 (1) 0.056 (1) 0.068 (1) 0.077 (2) 0.077 (2) 0.056 (1) 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000* 0.05000*

sup-9

supplementary materials Atomic displacement parameters (Å2) Cl1 Cl2 C9 C10 C13 C12 C1 C2 C15 C11 C4 C5 C19 C6 C7 C8 C14 C3

U11 0.0880 (5) 0.0547 (3) 0.076 (2) 0.047 (1) 0.062 (2) 0.080 (2) 0.042 (1) 0.053 (1) 0.072 (2) 0.047 (1) 0.044 (1) 0.044 (1) 0.054 (1) 0.061 (1) 0.084 (2) 0.088 (2) 0.075 (2) 0.054 (1)

U22 0.0561 (3) 0.0814 (4) 0.065 (1) 0.072 (1) 0.118 (3) 0.094 (2) 0.058 (1) 0.063 (1) 0.095 (2) 0.051 (1) 0.049 (1) 0.0462 (9) 0.052 (1) 0.056 (1) 0.076 (2) 0.090 (2) 0.071 (2) 0.064 (1)

U33 0.0814 (4) 0.0815 (4) 0.074 (2) 0.058 (1) 0.105 (3) 0.075 (2) 0.067 (1) 0.059 (1) 0.082 (2) 0.048 (1) 0.052 (1) 0.046 (1) 0.055 (1) 0.049 (1) 0.044 (1) 0.054 (1) 0.084 (2) 0.049 (1)

U12 −0.0057 (3) −0.0180 (3) −0.020 (1) −0.012 (1) −0.010 (2) −0.029 (2) 0.007 (1) −0.008 (1) −0.014 (2) 0.0045 (9) 0.0047 (9) 0.0003 (9) −0.006 (1) −0.004 (1) −0.011 (1) −0.024 (2) 0.004 (1) −0.001 (1)

U13 0.0048 (3) −0.0078 (3) 0.009 (1) 0.004 (1) 0.023 (2) 0.000 (1) −0.007 (1) −0.007 (1) −0.014 (1) 0.0071 (8) 0.0077 (9) 0.0007 (8) 0.002 (1) −0.009 (1) −0.002 (1) 0.007 (1) −0.022 (1) 0.0075 (9)

U23 −0.0200 (3) 0.0031 (3) 0.004 (1) 0.002 (1) −0.001 (2) −0.012 (2) 0.006 (1) 0.010 (1) 0.034 (2) −0.0036 (9) −0.0016 (9) 0.0020 (9) −0.002 (1) 0.003 (1) 0.002 (1) 0.016 (1) 0.017 (2) 0.003 (1)

Geometric parameters (Å, °) Cl1—C19 Cl2—C19 C9—C10 C9—C8 C10—C13 C10—C12 C10—C11 C1—C2 C1—C11 C2—C15

1.762 (3) 1.756 (3) 1.551 (4) 1.511 (4) 1.489 (5) 1.552 (4) 1.575 (4) 1.318 (4) 1.500 (4) 1.493 (5)

Cl1···C15i

3.470 (3)

C10—C9—C8 C9—C10—C13 C9—C10—C12 C9—C10—C11 C13—C10—C12 C13—C10—C11 C12—C10—C11 C2—C1—C11 C1—C2—C15 C1—C2—C3 C15—C2—C3 C10—C11—C1

117.3 (3) 110.7 (3) 103.0 (3) 111.9 (2) 108.7 (3) 109.8 (3) 112.4 (3) 125.6 (3) 122.2 (3) 121.4 (3) 116.4 (3) 114.3 (2)

sup-10

C2—C3 C11—C5 C4—C5 C4—C3 C5—C19 C5—C6 C19—C6 C6—C7 C6—C14 C7—C8

1.486 (4) 1.525 (3) 1.518 (3) 1.511 (4) 1.499 (4) 1.530 (4) 1.510 (4) 1.506 (4) 1.507 (4) 1.521 (5)

C4—C5—C19 C4—C5—C6 C19—C5—C6 Cl1—C19—Cl2 Cl1—C19—C5 Cl1—C19—C6 Cl2—C19—C5 Cl2—C19—C6 C5—C19—C6 C5—C6—C19 C5—C6—C7 C5—C6—C14

117.1 (2) 122.2 (2) 59.8 (2) 107.6 (2) 121.7 (2) 121.3 (2) 120.3 (2) 118.9 (2) 61.1 (2) 59.1 (2) 116.0 (3) 121.2 (3)

supplementary materials C10—C11—C5 C1—C11—C5 C5—C4—C3 C11—C5—C4 C11—C5—C19 C11—C5—C6

114.8 (2) 109.4 (2) 109.8 (2) 111.9 (2) 118.2 (2) 118.4 (2)

C8—C9—C10—C13 61.0 (3) C8—C9—C10—C12 177.1 (4) C8—C9—C10—C11 −61.8 (3) C10—C9—C8—C7 54.9 (3) C9—C10—C11—C1 −151.5 (3) C9—C10—C11—C5 −23.8 (2) C13—C10—C11—C1 85.1 (3) C13—C10—C11—C5 −147.2 (3) C12—C10—C11—C1 −36.1 (3) C12—C10—C11—C5 91.6 (3) C2—C1—C11—C10 115.8 (3) C11—C1—C2—C15 175.2 (4) C2—C1—C11—C5 −14.6 (3) C11—C1—C2—C3 −4.8 (3) C1—C2—C3—C4 −8.6 (3) C15—C2—C3—C4 171.3 (4) C10—C11—C5—C4 −83.2 (3) C10—C11—C5—C19 136.3 (3) C10—C11—C5—C6 67.3 (3) C1—C11—C5—C4 46.9 (2) C1—C11—C5—C19 −93.6 (3) C1—C11—C5—C6 −162.6 (3) C5—C4—C3—C2 40.2 (2) C3—C4—C5—C11 −60.7 (2) C3—C4—C5—C19 80.3 (3) C3—C4—C5—C6 150.1 (3) C11—C5—C19—Cl1 2.8 (2) C11—C5—C19—Cl2 143.4 (3) C11—C5—C19—C6 −108.2 (3) Symmetry codes: (i) −x+1/2, −y+1, z−1/2.

C19—C6—C7 C19—C6—C14 C7—C6—C14 C6—C7—C8 C9—C8—C7 C2—C3—C4

118.3 (3) 119.4 (3) 112.9 (3) 111.6 (3) 115.5 (3) 114.8 (2)

C11—C5—C6—C19 C11—C5—C6—C7 C11—C5—C6—C14 C4—C5—C19—Cl1 C4—C5—C19—Cl2 C4—C5—C19—C6 C4—C5—C6—C19 C4—C5—C6—C7 C4—C5—C6—C14 C6—C5—C19—Cl1 C6—C5—C19—Cl2 C19—C5—C6—C19 C6—C5—C19—C6 C19—C5—C6—C7 C19—C5—C6—C14 Cl1—C19—C6—C5 Cl1—C19—C6—C7 Cl1—C19—C6—C14 Cl2—C19—C6—C5 Cl2—C19—C6—C7 Cl2—C19—C6—C14 C5—C19—C6—C5 C5—C19—C6—C7 C5—C19—C6—C14 C5—C6—C7—C8 C19—C6—C7—C8 C14—C6—C7—C8 C6—C7—C8—C9

107.9 (3) −1.0 (2) −144.4 (4) −135.7 (3) 4.9 (2) 113.3 (3) −104.8 (3) 146.3 (3) 3.0 (3) 111.0 (3) −108.4 (3) 0.0 (2) 0.0 (2) −108.9 (3) 107.8 (3) −111.5 (3) −6.6 (2) 137.6 (3) 110.8 (3) −144.4 (3) −0.1 (2) 0.0 (2) 104.9 (3) −110.9 (3) −72.7 (3) −139.9 (4) 73.7 (3) 37.8 (3)

sup-11