1-[(1R,2S,4R,7S)-3,3-Dichloro-4,11,11-trimethyl­tricyclo[5.4.0.02,4]undecan-7-yl]ethanone

Benharref, A.; El Ammari, L.; Saadi, M.; Ait Elhad, M.; Oukhrib, A.; Berraho, M.

doi:10.1107/S2414314617001985

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 2| February 2017| x170198

https://doi.org/10.1107/S2414314617001985

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access

1-[(1R,2S,4R,7S)-3,3-Dichloro-4,11,11-trimethyltricyclo[5.4.0.0^2,4]undecan-7-yl]ethanone

Ahmed Benharref,^a ^* Lahcen El Ammari,^b Mohamed Saadi,^b Mustapha Ait Elhad,^a Abdelouahd Oukhrib ^a and Moha Berraho ^a

^aLaboratoire de Chimie des Substances Naturelles, `Unité Associé au CNRST (URAC16)', Faculté des Sciences Semlalia, BP 2390 Bd My Abdellah, Université Cadi Ayyad, 40000 Marrakech, Morocco, and ^bLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Mohammed V University in Rabat, Avenue Ibn Battouta, BP 1014 Rabat, Morocco
^*Correspondence e-mail: benharref@uca.ac.ma

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 23 January 2017; accepted 7 February 2017; online 14 February 2017)

The title compound, C₁₆H₂₄Cl₂O, crystallizes with two independent molecules in the asymmetric unit. Each molecule is built up from two fused six-membered rings, one of which is fused to a three-membered ring. The two molecules differ essentially in the orientation of two of the methyl groups. The dihedral angles between the mean planes through the two six-membered rings are 57.98 (13) and 55.29 (13)°. The molecular conformation is stabilized by intramolecular C—H⋯Cl hydrogen bonds.

Keywords: crystal structure; β-himachalene; Atlas cedar; Cedrus atlantica.

CCDC reference: 1531481

Structure description

The bicyclic sesquiterpene β-himachalene is the main constituent of the essential oil of the Atlas cedar (Cedrus atlantica) (El Haib et al., 2011 ). The reactivity of this sesquiterpene (and its derivatives) has been studied extensively by our team in order to prepare new products having biological properties (El Jamili et al., 2002 ; Benharref et al., 2013 , 2015 , 2016 ; Zaki et al., 2014 ). Indeed, these compounds were tested, using the food-poisoning technique, for their potential antifungal activity against the phytopathogen Botrytis cinerea (Daoubi et al., 2004 ). In this paper, we present the crystal structure of the title compound.

The asymmetric unit (Fig. 1) includes two crystallographically independent molecules (A and B). A least-squares overlay of the two molecules (Spek, 2009 ) is shown in Fig. 2 and reveals that the most important difference between them is the relative orientation of the two acetonic methyl atoms C16 and C29. In both molecules, one of the six-membered rings (C1–C6 and C17–C22) has a chair conformation, as indicated by the total puckering amplitude Q_T = 0.539 (3)/0.542 (3) Å and spherical polar angle θ₂ = 178.2 (3)/175.3 (2)°, with φ₂ = −42 (8)/−22 (4)°, whereas the other six-membered ring (C1/C6–C10 and C17/C22–C26) displays a boat conformation, with Q_T = 0.735 (3)/0.727 (4) Å, θ₂ = 92.13 (18)/93.01 (18)° and φ₂ = −0.6 (2)/63.6 (2)°. In addition, the dihedral angle between the least-squares mean planes through the two six-membered rings is 57.98 (13)° in molecule A and 55.29 (13)° in molecule B. Weak intramolecular C—H⋯Cl interactions (Table 1) stabilize the molecular conformation. Owing to the presence of Cl atoms, the absolute configuration could be fully confirmed by refining the Flack parameter. The title compound is isostructural with the corresponding dibromo derivative (Zaki et al., 2014).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cl1	0.98	2.64	3.227 (2)	118
C8—H8B⋯Cl1	0.97	2.61	3.184 (3)	118
C22—H22⋯Cl3	0.98	2.61	3.205 (2)	120
C25—H25B⋯Cl3	0.97	2.63	3.196 (3)	117

Figure 1
The asymmetric unit of the title compound, with displacement ellipsoids drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.

Figure 2
AutoMolFit (PLATON; Spek, 2009

) of molecule B (red) on molecule A (white).

Synthesis and crystallization

BF₃–Et₂O (1 ml) was added dropwise to a solution of (1S,3R,8S)-2,2-dichloro-3,7,7,10-tetramethyltricyclo[6.4.0.0^1,3]dodec-9-ene (1 g, 3.3 mmol; Lassaba et al., 1997 ) in dichloromethane (60 ml) at 195 K under nitrogen. The reaction mixture was stirred for 2 h at a constant temperature of 195 K and then left at ambient temperature for 24 h. Water (60 ml) was added in order to separate the two phases, and the organic phase was dried and concentrated. The residue obtained was chromatographed on silica gel, eluting with hexane–ethyl acetate (97:3 v/v), which allowed the isolation of the title compound (yield: 34.7 mg, 1 mmol, 30%). Crystals suitable for X-ray analysis were obtained by slow evaporation from a hexane solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were fixed geometrically and treated as riding, with C—H = 0.96 (methyl), 0.97 (methylene) or 0.98 Å (methine), and with U_iso(H) = 1.5U_eq(C) for methyl H atoms or 1.2U_eq(C) otherwise. A rotating model was used for the methyl groups. Two outliers (011 and 101) were omitted in the final cycles of refinement.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₂₄Cl₂O
M_r	303.25
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	13.373 (3), 13.996 (3), 17.219 (4)
V (Å³)	3222.9 (12)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.39
Crystal size (mm)	0.24 × 0.2 × 0.15

Data collection
Diffractometer	Bruker X8 APEX
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008 )
T_min, T_max	0.679, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	42837, 6602, 6117
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.084, 1.04
No. of reflections	6602
No. of parameters	351
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.15
Absolute structure	Flack x determined using 2562 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.003 (11)
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXS2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1531481

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617001985/rz4010sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617001985/rz4010Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617001985/rz4010Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

1-[(1R,2S,4R,7S)-3,3-Dichloro-4,11,11-trimethyltricyclo[5.4.0.0^2,4]undecan-7-yl]ethanone top

Crystal data top

C₁₆H₂₄Cl₂O	D_x = 1.250 Mg m⁻³
M_r = 303.25	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 6602 reflections
a = 13.373 (3) Å	θ = 2.1–26.4°
b = 13.996 (3) Å	µ = 0.39 mm⁻¹
c = 17.219 (4) Å	T = 296 K
V = 3222.9 (12) Å³	Prismatic, colourless
Z = 8	0.24 × 0.2 × 0.15 mm
F(000) = 1296

Data collection top

Bruker X8 APEX diffractometer	6117 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.027
φ and ω scans	θ_max = 26.4°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −16→16
T_min = 0.679, T_max = 0.747	k = −17→17
42837 measured reflections	l = −21→21
6602 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0451P)² + 0.5607P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
6602 reflections	Δρ_max = 0.25 e Å⁻³
351 parameters	Δρ_min = −0.15 e Å⁻³
0 restraints	Absolute structure: Flack x determined using 2562 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.003 (11)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.36988 (6)	0.29957 (5)	0.55069 (4)	0.05611 (18)
Cl3	0.95794 (5)	0.53104 (6)	0.79873 (4)	0.0617 (2)
Cl2	0.17235 (7)	0.21684 (5)	0.54209 (6)	0.0714 (2)
Cl4	0.98018 (6)	0.32934 (6)	0.76753 (6)	0.0755 (3)
O2	0.3205 (2)	0.73129 (15)	0.45534 (15)	0.0799 (7)
C1	0.25547 (17)	0.50152 (15)	0.53392 (11)	0.0317 (4)
H1	0.3249	0.4834	0.5447	0.038*
C22	0.72518 (16)	0.49498 (15)	0.76550 (12)	0.0340 (4)
H22	0.7646	0.5487	0.7853	0.041*
C10	0.19975 (17)	0.41104 (16)	0.51128 (13)	0.0356 (5)
H10	0.1278	0.4117	0.5221	0.043*
C9	0.22970 (19)	0.36088 (17)	0.43609 (14)	0.0400 (5)
C23	0.79869 (17)	0.42024 (16)	0.73703 (13)	0.0370 (5)
H23	0.7747	0.3541	0.7387	0.044*
C17	0.66252 (17)	0.53344 (17)	0.69536 (13)	0.0401 (5)
C15	0.3382 (2)	0.64824 (18)	0.46980 (15)	0.0505 (6)
C24	0.86437 (18)	0.44530 (18)	0.66748 (14)	0.0418 (5)
C25	0.8422 (2)	0.54421 (19)	0.63672 (14)	0.0463 (6)
H25A	0.8789	0.5551	0.5889	0.056*
H25B	0.8627	0.5920	0.6743	0.056*
C21	0.6619 (2)	0.45593 (18)	0.83496 (14)	0.0446 (5)
O1	0.5301 (2)	0.6488 (2)	0.69931 (19)	0.0942 (9)
C6	0.25692 (19)	0.57096 (16)	0.46278 (13)	0.0390 (5)
C2	0.2116 (2)	0.54496 (19)	0.60989 (14)	0.0451 (6)
C26	0.7303 (2)	0.5520 (2)	0.62175 (14)	0.0484 (6)
H26A	0.7122	0.5064	0.5817	0.058*
H26B	0.7160	0.6154	0.6019	0.058*
C8	0.3150 (2)	0.41262 (18)	0.39601 (14)	0.0454 (6)
H8A	0.3280	0.3838	0.3458	0.054*
H8B	0.3752	0.4080	0.4271	0.054*
C11	0.24772 (19)	0.31444 (17)	0.51377 (15)	0.0424 (5)
C7	0.2858 (2)	0.51667 (19)	0.38574 (13)	0.0486 (6)
H7A	0.2295	0.5198	0.3503	0.058*
H7B	0.3412	0.5501	0.3615	0.058*
C18	0.5816 (2)	0.4601 (2)	0.67344 (17)	0.0559 (7)
H18A	0.5374	0.4886	0.6352	0.067*
H18B	0.6136	0.4055	0.6493	0.067*
C28	0.6174 (2)	0.6318 (2)	0.71223 (17)	0.0552 (7)
C5	0.1527 (2)	0.6152 (2)	0.45342 (18)	0.0587 (7)
H5A	0.1558	0.6640	0.4135	0.070*
H5B	0.1070	0.5661	0.4356	0.070*
C30	0.7319 (3)	0.4090 (2)	0.89434 (16)	0.0613 (8)
H30A	0.6937	0.3875	0.9382	0.092*
H30B	0.7809	0.4546	0.9112	0.092*
H30C	0.7649	0.3554	0.8708	0.092*
C27	0.90911 (19)	0.43261 (19)	0.74687 (15)	0.0459 (6)
C16	0.4435 (2)	0.6165 (3)	0.4879 (2)	0.0647 (8)
H16A	0.4900	0.6542	0.4585	0.097*
H16B	0.4511	0.5503	0.4744	0.097*
H16C	0.4563	0.6247	0.5424	0.097*
C3	0.1089 (2)	0.5890 (2)	0.59315 (19)	0.0625 (8)
H3A	0.0620	0.5382	0.5810	0.075*
H3B	0.0851	0.6211	0.6395	0.075*
C20	0.5847 (2)	0.3842 (2)	0.80557 (18)	0.0570 (7)
H20A	0.6191	0.3282	0.7859	0.068*
H20B	0.5428	0.3642	0.8486	0.068*
C31	0.6090 (3)	0.5389 (2)	0.87730 (17)	0.0615 (8)
H31A	0.5644	0.5706	0.8420	0.092*
H31B	0.6580	0.5836	0.8958	0.092*
H31C	0.5716	0.5142	0.9205	0.092*
C13	0.2015 (3)	0.4657 (3)	0.67104 (15)	0.0666 (9)
H13A	0.2657	0.4371	0.6800	0.100*
H13B	0.1557	0.4180	0.6527	0.100*
H13C	0.1769	0.4926	0.7187	0.100*
C12	0.1507 (2)	0.3210 (2)	0.38231 (18)	0.0618 (8)
H12A	0.1773	0.2671	0.3548	0.093*
H12B	0.1309	0.3693	0.3458	0.093*
H12C	0.0937	0.3013	0.4122	0.093*
C32	0.8843 (2)	0.3703 (2)	0.60542 (17)	0.0616 (8)
H0A	0.9474	0.3832	0.5809	0.092*
H0B	0.8320	0.3722	0.5673	0.092*
H0C	0.8862	0.3081	0.6290	0.092*
C19	0.5189 (2)	0.4252 (3)	0.7417 (2)	0.0694 (9)
H19A	0.4801	0.4780	0.7623	0.083*
H19B	0.4727	0.3765	0.7239	0.083*
C4	0.1105 (3)	0.6595 (2)	0.5268 (2)	0.0705 (9)
H4A	0.1508	0.7143	0.5413	0.085*
H4B	0.0430	0.6818	0.5169	0.085*
C14	0.2817 (3)	0.6214 (2)	0.64349 (17)	0.0617 (8)
H14A	0.2882	0.6730	0.6071	0.093*
H14B	0.3463	0.5939	0.6530	0.093*
H14C	0.2545	0.6452	0.6913	0.093*
C29	0.6857 (3)	0.7112 (2)	0.7387 (2)	0.0675 (8)
H29A	0.6538	0.7717	0.7300	0.101*
H29B	0.7471	0.7086	0.7098	0.101*
H29C	0.6998	0.7038	0.7930	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0571 (4)	0.0460 (3)	0.0652 (4)	0.0108 (3)	−0.0111 (3)	0.0052 (3)
Cl3	0.0468 (4)	0.0750 (5)	0.0635 (4)	−0.0098 (3)	−0.0161 (3)	−0.0089 (4)
Cl2	0.0777 (5)	0.0410 (3)	0.0954 (6)	−0.0158 (3)	0.0135 (4)	0.0114 (4)
Cl4	0.0587 (5)	0.0715 (5)	0.0962 (6)	0.0261 (4)	−0.0045 (4)	0.0146 (4)
O2	0.113 (2)	0.0382 (11)	0.0888 (16)	−0.0112 (12)	−0.0047 (15)	0.0144 (11)
C1	0.0328 (10)	0.0319 (10)	0.0303 (10)	0.0008 (8)	0.0021 (8)	−0.0004 (8)
C22	0.0348 (11)	0.0313 (10)	0.0360 (10)	−0.0029 (9)	−0.0018 (9)	−0.0012 (8)
C10	0.0332 (11)	0.0340 (11)	0.0397 (11)	−0.0009 (9)	0.0043 (9)	−0.0009 (9)
C9	0.0428 (12)	0.0357 (11)	0.0415 (12)	0.0006 (10)	−0.0013 (10)	−0.0064 (9)
C23	0.0362 (11)	0.0341 (11)	0.0408 (12)	−0.0001 (9)	−0.0013 (9)	−0.0010 (9)
C17	0.0354 (11)	0.0423 (12)	0.0425 (11)	−0.0003 (10)	−0.0047 (9)	−0.0001 (10)
C15	0.0699 (18)	0.0381 (13)	0.0435 (13)	−0.0105 (12)	0.0003 (12)	0.0036 (10)
C24	0.0366 (12)	0.0450 (13)	0.0438 (12)	−0.0013 (10)	0.0018 (10)	−0.0038 (10)
C25	0.0473 (14)	0.0528 (14)	0.0387 (12)	−0.0057 (12)	0.0050 (10)	0.0057 (11)
C21	0.0492 (14)	0.0403 (12)	0.0443 (12)	−0.0044 (11)	0.0091 (10)	−0.0006 (10)
O1	0.0635 (15)	0.0844 (18)	0.135 (2)	0.0334 (14)	−0.0193 (16)	−0.0021 (17)
C6	0.0482 (13)	0.0342 (11)	0.0347 (11)	−0.0002 (10)	−0.0057 (10)	0.0033 (9)
C2	0.0487 (14)	0.0489 (14)	0.0378 (12)	0.0015 (12)	0.0080 (10)	−0.0089 (10)
C26	0.0528 (15)	0.0534 (15)	0.0391 (12)	0.0011 (12)	−0.0055 (11)	0.0060 (11)
C8	0.0536 (15)	0.0492 (14)	0.0334 (11)	−0.0016 (12)	0.0092 (10)	−0.0078 (10)
C11	0.0428 (13)	0.0322 (11)	0.0522 (13)	−0.0041 (10)	0.0033 (10)	0.0036 (10)
C7	0.0649 (16)	0.0484 (14)	0.0325 (11)	−0.0077 (13)	0.0022 (11)	0.0043 (10)
C18	0.0465 (14)	0.0605 (17)	0.0608 (16)	−0.0076 (13)	−0.0138 (12)	−0.0071 (14)
C28	0.0565 (16)	0.0521 (15)	0.0572 (15)	0.0159 (13)	−0.0039 (13)	0.0044 (12)
C5	0.0636 (18)	0.0466 (14)	0.0658 (17)	0.0117 (13)	−0.0223 (14)	0.0047 (13)
C30	0.079 (2)	0.0618 (18)	0.0433 (14)	−0.0028 (16)	0.0049 (14)	0.0144 (12)
C27	0.0382 (12)	0.0465 (14)	0.0530 (14)	0.0041 (11)	−0.0052 (10)	0.0002 (11)
C16	0.0553 (17)	0.0665 (19)	0.0724 (19)	−0.0230 (15)	0.0036 (15)	0.0022 (16)
C3	0.0478 (15)	0.0632 (18)	0.0764 (19)	0.0103 (14)	0.0148 (14)	−0.0240 (15)
C20	0.0551 (16)	0.0506 (15)	0.0652 (17)	−0.0151 (13)	0.0176 (14)	−0.0010 (13)
C31	0.0688 (19)	0.0599 (18)	0.0558 (15)	−0.0006 (15)	0.0206 (14)	−0.0106 (14)
C13	0.086 (2)	0.077 (2)	0.0370 (13)	−0.0027 (18)	0.0186 (14)	−0.0001 (13)
C12	0.0664 (19)	0.0543 (16)	0.0646 (17)	−0.0038 (14)	−0.0169 (15)	−0.0172 (13)
C32	0.0594 (17)	0.0658 (18)	0.0597 (16)	0.0008 (15)	0.0126 (14)	−0.0160 (14)
C19	0.0435 (15)	0.077 (2)	0.087 (2)	−0.0209 (15)	−0.0014 (15)	−0.0084 (18)
C4	0.0552 (18)	0.0583 (18)	0.098 (2)	0.0257 (15)	−0.0131 (17)	−0.0148 (17)
C14	0.0718 (19)	0.0671 (18)	0.0463 (14)	−0.0036 (16)	−0.0012 (14)	−0.0212 (13)
C29	0.092 (2)	0.0382 (13)	0.0719 (19)	0.0098 (15)	−0.0013 (17)	0.0010 (13)

Geometric parameters (Å, º) top

Cl1—C11	1.765 (3)	C8—H8A	0.9700
Cl3—C27	1.767 (3)	C8—H8B	0.9700
Cl2—C11	1.766 (2)	C7—H7A	0.9700
Cl4—C27	1.766 (3)	C7—H7B	0.9700
O2—C15	1.212 (3)	C18—C19	1.524 (5)
C1—C10	1.520 (3)	C18—H18A	0.9700
C1—C2	1.557 (3)	C18—H18B	0.9700
C1—C6	1.564 (3)	C28—C29	1.508 (5)
C1—H1	0.9800	C5—C4	1.516 (5)
C22—C23	1.517 (3)	C5—H5A	0.9700
C22—C21	1.564 (3)	C5—H5B	0.9700
C22—C17	1.565 (3)	C30—H30A	0.9600
C22—H22	0.9800	C30—H30B	0.9600
C10—C11	1.497 (3)	C30—H30C	0.9600
C10—C9	1.526 (3)	C16—H16A	0.9600
C10—H10	0.9800	C16—H16B	0.9600
C9—C11	1.507 (3)	C16—H16C	0.9600
C9—C12	1.512 (4)	C3—C4	1.510 (5)
C9—C8	1.517 (4)	C3—H3A	0.9700
C23—C27	1.496 (3)	C3—H3B	0.9700
C23—C24	1.526 (3)	C20—C19	1.521 (5)
C23—H23	0.9800	C20—H20A	0.9700
C17—C28	1.531 (4)	C20—H20B	0.9700
C17—C18	1.538 (4)	C31—H31A	0.9600
C17—C26	1.580 (4)	C31—H31B	0.9600
C15—C16	1.508 (5)	C31—H31C	0.9600
C15—C6	1.539 (4)	C13—H13A	0.9600
C24—C27	1.503 (4)	C13—H13B	0.9600
C24—C25	1.512 (4)	C13—H13C	0.9600
C24—C32	1.522 (4)	C12—H12A	0.9600
C25—C26	1.522 (4)	C12—H12B	0.9600
C25—H25A	0.9700	C12—H12C	0.9600
C25—H25B	0.9700	C32—H0A	0.9600
C21—C20	1.526 (4)	C32—H0B	0.9600
C21—C30	1.534 (4)	C32—H0C	0.9600
C21—C31	1.543 (4)	C19—H19A	0.9700
O1—C28	1.213 (4)	C19—H19B	0.9700
C6—C5	1.534 (4)	C4—H4A	0.9700
C6—C7	1.577 (3)	C4—H4B	0.9700
C2—C3	1.533 (4)	C14—H14A	0.9600
C2—C13	1.535 (4)	C14—H14B	0.9600
C2—C14	1.536 (4)	C14—H14C	0.9600
C26—H26A	0.9700	C29—H29A	0.9600
C26—H26B	0.9700	C29—H29B	0.9600
C8—C7	1.518 (4)	C29—H29C	0.9600

C10—C1—C2	110.86 (18)	C19—C18—C17	114.3 (2)
C10—C1—C6	108.84 (17)	C19—C18—H18A	108.7
C2—C1—C6	114.84 (18)	C17—C18—H18A	108.7
C10—C1—H1	107.3	C19—C18—H18B	108.7
C2—C1—H1	107.3	C17—C18—H18B	108.7
C6—C1—H1	107.3	H18A—C18—H18B	107.6
C23—C22—C21	110.91 (18)	O1—C28—C29	119.7 (3)
C23—C22—C17	109.56 (18)	O1—C28—C17	121.4 (3)
C21—C22—C17	114.86 (19)	C29—C28—C17	118.7 (2)
C23—C22—H22	107.0	C4—C5—C6	114.6 (2)
C21—C22—H22	107.0	C4—C5—H5A	108.6
C17—C22—H22	107.0	C6—C5—H5A	108.6
C11—C10—C1	122.34 (19)	C4—C5—H5B	108.6
C11—C10—C9	59.77 (16)	C6—C5—H5B	108.6
C1—C10—C9	118.18 (19)	H5A—C5—H5B	107.6
C11—C10—H10	115.1	C21—C30—H30A	109.5
C1—C10—H10	115.1	C21—C30—H30B	109.5
C9—C10—H10	115.1	H30A—C30—H30B	109.5
C11—C9—C12	119.8 (2)	C21—C30—H30C	109.5
C11—C9—C8	119.3 (2)	H30A—C30—H30C	109.5
C12—C9—C8	115.0 (2)	H30B—C30—H30C	109.5
C11—C9—C10	59.16 (15)	C23—C27—C24	61.17 (16)
C12—C9—C10	120.4 (2)	C23—C27—Cl4	117.33 (19)
C8—C9—C10	111.31 (19)	C24—C27—Cl4	119.62 (19)
C27—C23—C22	121.5 (2)	C23—C27—Cl3	120.81 (19)
C27—C23—C24	59.62 (16)	C24—C27—Cl3	120.98 (19)
C22—C23—C24	117.92 (19)	Cl4—C27—Cl3	109.73 (14)
C27—C23—H23	115.4	C15—C16—H16A	109.5
C22—C23—H23	115.4	C15—C16—H16B	109.5
C24—C23—H23	115.4	H16A—C16—H16B	109.5
C28—C17—C18	111.7 (2)	C15—C16—H16C	109.5
C28—C17—C22	111.9 (2)	H16A—C16—H16C	109.5
C18—C17—C22	109.7 (2)	H16B—C16—H16C	109.5
C28—C17—C26	103.3 (2)	C4—C3—C2	113.1 (3)
C18—C17—C26	108.4 (2)	C4—C3—H3A	109.0
C22—C17—C26	111.60 (18)	C2—C3—H3A	109.0
O2—C15—C16	120.5 (3)	C4—C3—H3B	109.0
O2—C15—C6	121.3 (3)	C2—C3—H3B	109.0
C16—C15—C6	117.9 (2)	H3A—C3—H3B	107.8
C27—C24—C25	120.3 (2)	C19—C20—C21	112.5 (2)
C27—C24—C32	119.2 (2)	C19—C20—H20A	109.1
C25—C24—C32	114.9 (2)	C21—C20—H20A	109.1
C27—C24—C23	59.21 (16)	C19—C20—H20B	109.1
C25—C24—C23	111.9 (2)	C21—C20—H20B	109.1
C32—C24—C23	119.6 (2)	H20A—C20—H20B	107.8
C24—C25—C26	108.5 (2)	C21—C31—H31A	109.5
C24—C25—H25A	110.0	C21—C31—H31B	109.5
C26—C25—H25A	110.0	H31A—C31—H31B	109.5
C24—C25—H25B	110.0	C21—C31—H31C	109.5
C26—C25—H25B	110.0	H31A—C31—H31C	109.5
H25A—C25—H25B	108.4	H31B—C31—H31C	109.5
C20—C21—C30	110.6 (2)	C2—C13—H13A	109.5
C20—C21—C31	110.0 (2)	C2—C13—H13B	109.5
C30—C21—C31	106.7 (2)	H13A—C13—H13B	109.5
C20—C21—C22	110.0 (2)	C2—C13—H13C	109.5
C30—C21—C22	109.2 (2)	H13A—C13—H13C	109.5
C31—C21—C22	110.3 (2)	H13B—C13—H13C	109.5
C5—C6—C15	111.5 (2)	C9—C12—H12A	109.5
C5—C6—C1	108.8 (2)	C9—C12—H12B	109.5
C15—C6—C1	112.59 (19)	H12A—C12—H12B	109.5
C5—C6—C7	109.2 (2)	C9—C12—H12C	109.5
C15—C6—C7	103.4 (2)	H12A—C12—H12C	109.5
C1—C6—C7	111.26 (18)	H12B—C12—H12C	109.5
C3—C2—C13	109.9 (2)	C24—C32—H0A	109.5
C3—C2—C14	109.7 (2)	C24—C32—H0B	109.5
C13—C2—C14	107.4 (2)	H0A—C32—H0B	109.5
C3—C2—C1	109.7 (2)	C24—C32—H0C	109.5
C13—C2—C1	109.1 (2)	H0A—C32—H0C	109.5
C14—C2—C1	111.0 (2)	H0B—C32—H0C	109.5
C25—C26—C17	114.6 (2)	C20—C19—C18	111.1 (2)
C25—C26—H26A	108.6	C20—C19—H19A	109.4
C17—C26—H26A	108.6	C18—C19—H19A	109.4
C25—C26—H26B	108.6	C20—C19—H19B	109.4
C17—C26—H26B	108.6	C18—C19—H19B	109.4
H26A—C26—H26B	107.6	H19A—C19—H19B	108.0
C9—C8—C7	108.5 (2)	C3—C4—C5	111.6 (2)
C9—C8—H8A	110.0	C3—C4—H4A	109.3
C7—C8—H8A	110.0	C5—C4—H4A	109.3
C9—C8—H8B	110.0	C3—C4—H4B	109.3
C7—C8—H8B	110.0	C5—C4—H4B	109.3
H8A—C8—H8B	108.4	H4A—C4—H4B	108.0
C10—C11—C9	61.08 (15)	C2—C14—H14A	109.5
C10—C11—Cl1	120.89 (17)	C2—C14—H14B	109.5
C9—C11—Cl1	121.24 (18)	H14A—C14—H14B	109.5
C10—C11—Cl2	117.51 (17)	C2—C14—H14C	109.5
C9—C11—Cl2	119.17 (18)	H14A—C14—H14C	109.5
Cl1—C11—Cl2	109.73 (13)	H14B—C14—H14C	109.5
C8—C7—C6	115.29 (19)	C28—C29—H29A	109.5
C8—C7—H7A	108.5	C28—C29—H29B	109.5
C6—C7—H7A	108.5	H29A—C29—H29B	109.5
C8—C7—H7B	108.5	C28—C29—H29C	109.5
C6—C7—H7B	108.5	H29A—C29—H29C	109.5
H7A—C7—H7B	107.5	H29B—C29—H29C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl1	0.98	2.64	3.227 (2)	118
C8—H8B···Cl1	0.97	2.61	3.184 (3)	118
C22—H22···Cl3	0.98	2.61	3.205 (2)	120
C25—H25B···Cl3	0.97	2.63	3.196 (3)	117

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

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