Monomolecular sheets of propeller-shaped triethyl 4,4′,4′′-[benzene-1,3,5-triyltris(ethyne-2,1-di­yl)]tribenzoate deuterochloroform monosolvate

The title compound, C₃₉H₃₀O₆·CDCl₃, has a chemical threefold axis and an approximately planar structure, with an eth­oxy­carbonyl substituent on each of the terminal benzenes oriented in the same direction, thus forming a propeller-shaped mol­ecule. This mol­ecule is of particular inter­est in the field of metal–organic frameworks (MOFs), where its hydrolyzed analogue forms MOF structures with high surface areas. The benzene ring which occupies the centre of the mol­ecule forms π–π inter­actions to the equivalent benzene ring at a perpendicular distance of 3.32 (1) Å. Centrosymmetric dimers formed in this way are inter­connected by inter­molecular C—H...π inter­actions with a rather short H...CgA distance of 2.51 Å (CgA is the centroid of the central benzene ring). The mol­ecules are arranged in regular parallel sheets. Within a sheet, mol­ecules are inter­connected via C—H...O inter­actions where all carbonyl O atoms participate in weak hydrogen bonds as hydrogen-bond acceptors. Neighbouring sheets are connected through the above-mentioned π–π and C—H...π inter­actions.

S1. Introduction

Symmetrical substituted benzenes have found widespread application as building units for the construction of attractive new metal–organic framework (MOF) structures (Kim et al., 2001; Hee et al., 2004; Kozachuk et al., 2014). In particular 4,4',4''-[benzene-1,3,5-triyltris(ethyne-2,1-diyl)]tribenzoate [benzoic acid?], which can be readily obtained by the hydrolysis of the herein reported triester, have been recently shown to produce MOF structures (MOF-180 and MOF-210; Furukawa et al., 2010) with surface areas up to 10400 m² g^-1. These materials exhibit exceptional porosities and gas (hydrogen, methane and carbon dioxide) uptake capacities. Analogous planar symmetrical benzene-based molecules have also sparked inter­est in the construction of new functional materials due to their adsorption on flat gold or graphite surfaces (Gutzler et al., 2009; Dienstmaier et al., 2010; Madueno et al., 2008). Clearly the structure of the title molecule is of inter­est in a variety of emerging research areas, and even though the organic backbones of MOFs have been structurally characterized, we report here the first crystal structure of the tri­ethyl ester building block tri­ethyl 4,4',4''-[benzene-1,3,5-triyltris(ethyne-2,1-diyl)]tribenzoate, (I).

S2. Experimental

S2.1. Synthesis and crystallization

Copper(I) iodide, 1,3,5-tri­bromo­benzene and dichloridobis(tri­phenyl­phosphane)palladium were commercially available (Aldrich). 1,3,5-Triethynyl­benzene (Demessence et al., 2009) and the title compound (Castellano & Rebek, 1998; Kuroda et al., 2006) were synthesized according to slight modifications of published procedures. Solid 1,3,5-tri­bromo­benzene (9.45 g, 30.00 mmol), copper(I) iodide (50 mg, 0.26 mmol) and dichloridobis(tri­phenyl­phosphane)palladium(II) (400 mg, 0.57 mmol) were dissolved in freshly distilled tri­ethyl­amine (200 ml) under a nitro­gen atmosphere. Trimethysilyl­acetyl­ene (10.6 g, 108 mmol) was added and the mixture was heated at 323 K for 24 h. After cooling, the resulting precipitate of tri­ethyl­amine hydro­bromide was removed by filtration and washed with ether. The combined filtrates were evaporated to dryness under reduced pressure and the residue was chromatographed on a column (SiO₂, hexane) to yield 9.4 g (87%) of 1,3,5-tris­(tri­methyl­silylethynyl)benzene. Aqueous NaOH (1 M, 50 ml) was then added to a solution of tris­(tri­methyl­silylethynyl)benzene (315.6 mg, 0.862 mmol) in ethanol (80 ml), and the reaction mixture was heated with stirring at 313 K for 12 h. The solvent was evaporated and the residue was extracted with di­ethyl ether. The organic layer was dried over anhydrous magnesium sulfate and evaporated to dryness to yield the product. Crude 1,3,5-triethynyl­benzene (123 mg, 0.82 mmol) was dissolved in dry tri­ethyl­amine (40 ml) and added to a Schlenk flask containing ethyl 4-bromo­benzoate (751 mg, 3.28 mmol), dichloridobis(tri­phenyl­phosphane)palladium(II) (70 mg, 0.1 mmol) and cuprous iodide (19 mg, 0.1 mmol). The reaction mixture was degassed and then stirred at 323 K for 3 d. The solution was evaporated and the residue was dissolved in ethyl acetate, washed with water and the organic layer was dried with anhydrous magnesium sulfate. The solvent was removed by evaporation and the residue was subjected to chromatography on silica gel with ethyl acetate/hexane (1:6) as the eluent to yield the product (yield 70 mg, 0.118 mmol, 14.4%). Single crystals of (I) were obtained by slow evaporation from a CDCl₃ solution.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bonded to C atoms were placed at calculated positions, with C—H distances fixed at 0.93 Å for aromatic, and at 0.96 and 0.97 Å for methyl and methyl­ene C atoms. The corresponding isotropic displacement parameters of H atoms were set equal to 1.2U_eq of the parent aromatic and methyl­ene, and at 1.5U_eq of the methyl C atoms.

The deuterium atom from the deuterated solvent solvent molecule, CDCl₃, was located in a difference Fourier map and was refined isotropically. H and D atoms were included in the SFAC and UNIT instructions separately, while both atom types employed the `H' scattering factor number.

S3. Comment

The molecule of (I) (Fig. 1) is almost planar and has a chemical threefold axis. However, the three terminal benzene rings [B (atoms C9–C14), C (atoms C20–C25) and D (atoms C31–C36)] have slightly different orientations with respect to to the central ring A (atoms C1–C6). The planes of rings C and A exhibit the largest dihedral angle [7.3 (1)°], while the planes of rings B and D are almost coplanar with that of the central ring [dihedral angles = 3.1 (1) and 2.5 (1)°, respectively]. Bond lengths and angles (Table 2) are very similar for all three aromatic fragments in (I).

Each of the three pendent benzene rings is substituted by an eth­oxy­carbonyl group in the para position. The orientation of this substituent is the same in all three cases giving rise to a propeller-shaped molecule. Also in these ethyl ester groups, all non-H atoms are essentially coplanar (r.m.s. deviation of fitted atoms = 0.034, 0.017 and 0.007 Å for B, C and D, respectively). The dihedral angle between the mean plane through the eth­oxy­carbonyl group and the attached aromatic ring varies from 13.0 (2)° for ring B to 6.6 (2)° for ring D ring and 1.6 (2)° for ring C. Ring B exhibits the largest deviation of the eth­oxy­carbonyl group from coplanarity with the aromatic ring; a possible explanation for this structural difference can be found in the fact that ring B forms a C—H···O hydrogen bond to the CDCl₃ solvent molecule. Considering the H···O distance as a criterion, this hydrogen bond (C40—D40···O1; symmetry code: x, y+1, z) is the most important hydrogen bond in the structure of (I) (Table 3). All carbonyl O atoms in (I) participate in weak C—H···O hydrogen bonds with neighboring molecules in the same layer, but the H···O distances in all cases are longer than 2.50 Å (Table 3).

The central benzene ring plays a significant role in the crystal packing of (I). This ring forms the most important π–π stacking inter­action, with a perpendicular inter­planar distance to the neighboring ring Aⁱ at [symmetry code: (i) -x+1, -y+1, -z+1] of 3.32 (1) Å [the distance between the centroids (Cg) of the two rings is 3.549 (1) Å]. The centrosymmetric dimer formed via this inter­molecular inter­action is shown in Fig. 2. Within the dimer, atom C5 is almost perfectly located above the centroid of the neighboring ring (C5···CgA = 3.35 Å), while atoms C1 and C3 are positioned approximately one above the other, with a C1···C3ⁱ distance of 3.362 (3) Å. Besides the π–π inter­actions, ring A also participates in a relatively strong C—H···π inter­molecular inter­action as π-acceptor of the C27 methyl­ene group. Atom H27B bonded to C27 is directed towards the centroid of ring A, forming a rather short H···CgA distance of 2.64 Å [perpendicular distance of H27B to ring A is 2.62 Å and the C27—H27B···CgA angle is 157°).

When the C27—H27B distance is corrected to a standard distance of ca 1.10 Å the H27B···CgA distance becomes 2.53 Å (orthogonal distance = 2.51 Å) which qualifies this inter­action as a relatively strong inter­molecular C—H···π inter­action (Desiraju & Steiner, 2001). Molecules of (I) form parallel sheets in the crystal packing. Within a sheet, molecules are inter­connected by C—H···O hydrogen bonds (see Table 3 for geometrical parameters and Fig. 3 for illustration), while the molecules in parallel neighbouring layers are inter­connected by the above-described π–π and C—H···π inter­actions formed by ring A (Fig. 4). Ring C also participates in π–π inter­actions between sheets [CgC···CgCⁱⁱ = 3.781 (1) Å; symmetry code: (ii) -x+1, -y, -z+1, while the perpendicular inter­planar distance between two C rings is 3.50 (1) Å].

In the Cambridge Structural Database (Allen, 2002), we found only five crystal structures with organic molecules having the same aromatic core as molecule (I) [see structure (II) in the Scheme]: OCUKEC (Day et al., 2001); PUBDOF (Bochkarev et al., 1998); PUBDOF01, WEVYIF and WEVYOL (Ponzini et al., 2000); ZABQUO and ZABQUO01 (Gardner et al., 1995). Unfortunately, the early crystal structures (refcodes ZABQUO and ZABQUO01) are without atomic coordinates. Nevertheless, a brief comparison of geometrical parameters and accessible information for all crystal structures confirms very similar bond distances within fragment (II), while some conformational characteristics (such as mutual orientation of terminal and central benzene rings) were found to differ significantly. Only in WEVYIF were all three terminal benzene rings approximately coplanar with the central ring (dihedral angles = 2.5–9.1°). This crystal structure is also the only case where structures form parallel layers similar to that observed in the crystal packing of (I). The central ring forms π–π inter­actions to a neighbouring central ring in OCUKEC and WEVYIF, while in no case does this ring participate as a π-acceptor in C—H···π inter­actions.

Related literature

For related literature, see: Allen (2002); Bochkarev et al. (1998); Castellano & Rebek (1998); Day et al. (2001); Demessence et al. (2009); Desiraju & Steiner (2001); Dienstmaier et al. (2010); Furukawa et al. (2010); Gardner et al. (1995); Gutzler et al. (2009); Hee et al. (2004); Kim et al. (2001); Kozachuk et al. (2014); Kuroda et al. (2006); Madueno et al. (2008); Ponzini et al. (2000).

Computing details

Data collection: APEX2 (Bruker–Nonius, 2005); cell refinement: SAINT (Bruker–Nonius, 2005); data reduction: SAINT (Bruker–Nonius, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2014); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012), PLATON (Spek, 2009) and PARST (Nardelli, 1995).

Figures

	Fig. 1. View of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Nonperspective view showing the overlap between molecules in adjacent layers.
	Fig. 3. View of a section of one layer showing the arrangement of molecules and solvent. All carbonyl O atoms participate in weak C—H···O hydrogen bonds. H atoms have been omitted.
	Fig. 4. Packing of (I) in the unit cell. C—H···π and π–π interactions between the layers are indicated by single dashed and dotted lines, respectively. CgA indicates the centroid of ring A.

Triethyl 4,4',4''-[benzene-1,3,5-triyltris(ethyne-2,1-diyl)]tribenzoate deuterochloroform monosolvate

Crystal data

C39H30O6·CDCl3	Z = 2
Mr = 715.00	F(000) = 740
Triclinic, P1	Dx = 1.324 Mg m^−3
a = 8.6557 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.0058 (7) Å	Cell parameters from 4066 reflections
c = 16.4804 (11) Å	θ = 1.6–25.1°
α = 111.036 (1)°	µ = 0.30 mm^−1
β = 99.971 (1)°	T = 223 K
γ = 97.835 (1)°	Block, colorless
V = 1793.28 (17) Å^3	0.40 × 0.35 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer	6305 independent reflections
Radiation source: fine-focus sealed tube	4659 reflections with I > 2σ(I)
Detector resolution: 8.3 pixels mm^-1	Rint = 0.025
CCD scans	θmax = 25.1°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker–Nonius, 2005)	h = −10→10
Tmin = 0.817, Tmax = 0.999	k = −16→15
9224 measured reflections	l = 0→19

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.130	w = 1/[σ^2(Fo^2) + (0.0671P)^2 + 0.4355P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
6305 reflections	Δρmax = 0.66 e Å^−3
449 parameters	Δρmin = −0.55 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.55597 (10)	0.85379 (6)	0.16761 (5)	0.0819 (3)
Cl2	0.83258 (11)	0.77262 (10)	0.20884 (5)	0.1068 (4)
Cl3	0.61616 (10)	0.67337 (6)	0.03549 (5)	0.0846 (3)
O1	0.8339 (2)	−0.07156 (12)	0.02404 (10)	0.0569 (5)
O2	0.72253 (19)	0.00640 (11)	−0.06110 (9)	0.0477 (4)
O3	0.05665 (19)	1.11764 (13)	0.39086 (10)	0.0507 (4)
O4	0.10205 (17)	1.18872 (11)	0.54032 (9)	0.0427 (4)
O5	1.2113 (2)	0.72269 (15)	1.19475 (10)	0.0639 (5)
O6	1.31069 (19)	0.58412 (13)	1.12539 (9)	0.0499 (4)
C1	0.6936 (2)	0.50539 (15)	0.45662 (12)	0.0334 (4)
C2	0.6049 (2)	0.57886 (15)	0.44871 (12)	0.0347 (5)
H2	0.5489	0.5713	0.3925	0.042*
C3	0.5994 (2)	0.66381 (15)	0.52464 (12)	0.0326 (4)
C4	0.6810 (2)	0.67329 (15)	0.60875 (13)	0.0352 (5)
H4	0.6768	0.7293	0.6596	0.042*
C5	0.7686 (2)	0.59991 (15)	0.61750 (13)	0.0342 (4)
C6	0.7759 (2)	0.51645 (16)	0.54107 (13)	0.0368 (5)
H6	0.8360	0.4679	0.5466	0.044*
C7	0.6999 (2)	0.41714 (16)	0.37852 (13)	0.0363 (5)
C8	0.7054 (3)	0.34337 (16)	0.31556 (13)	0.0391 (5)
C9	0.7147 (2)	0.25400 (15)	0.23975 (13)	0.0364 (5)
C10	0.6423 (3)	0.24056 (17)	0.15264 (13)	0.0413 (5)
H10	0.5830	0.2880	0.1436	0.050*
C11	0.6578 (3)	0.15769 (17)	0.08010 (13)	0.0408 (5)
H11	0.6101	0.1498	0.0223	0.049*
C12	0.7448 (3)	0.08580 (16)	0.09319 (13)	0.0377 (5)
C13	0.8143 (3)	0.09778 (16)	0.17990 (13)	0.0414 (5)
H13	0.8709	0.0491	0.1889	0.050*
C14	0.8001 (3)	0.18121 (16)	0.25256 (13)	0.0413 (5)
H14	0.8476	0.1888	0.3103	0.050*
C15	0.7713 (3)	−0.00212 (17)	0.01665 (13)	0.0412 (5)
C16	0.7542 (3)	−0.07135 (18)	−0.13968 (14)	0.0530 (6)
H16A	0.6922	−0.1404	−0.1525	0.064*
H16B	0.8673	−0.0733	−0.1296	0.064*
C17	0.7064 (5)	−0.0391 (2)	−0.21507 (17)	0.0910 (11)
H17A	0.5916	−0.0489	−0.2308	0.136*
H17B	0.7419	−0.0810	−0.2657	0.136*
H17C	0.7548	0.0334	−0.1975	0.136*
C18	0.5107 (2)	0.74037 (16)	0.51521 (13)	0.0361 (5)
C19	0.4414 (2)	0.80532 (16)	0.50673 (13)	0.0375 (5)
C20	0.3584 (2)	0.88391 (15)	0.49637 (13)	0.0349 (5)
C21	0.3385 (3)	0.96449 (16)	0.57114 (13)	0.0399 (5)
H21	0.3798	0.9675	0.6282	0.048*
C22	0.2583 (3)	1.03954 (16)	0.56119 (13)	0.0385 (5)
H22	0.2459	1.0929	0.6115	0.046*
C23	0.1957 (2)	1.03592 (15)	0.47637 (13)	0.0348 (4)
C24	0.2131 (2)	0.95524 (16)	0.40170 (13)	0.0384 (5)
H24	0.1696	0.9517	0.3447	0.046*
C25	0.2944 (2)	0.88013 (16)	0.41120 (13)	0.0387 (5)
H25	0.3065	0.8269	0.3607	0.046*
C26	0.1104 (2)	1.11651 (16)	0.46243 (14)	0.0372 (5)
C27	0.0219 (3)	1.27170 (16)	0.53568 (14)	0.0412 (5)
H27A	−0.0901	1.2431	0.5040	0.049*
H27B	0.0732	1.3093	0.5047	0.049*
C28	0.0359 (3)	1.34363 (18)	0.63130 (16)	0.0557 (6)
H28A	−0.0232	1.3070	0.6594	0.084*
H28B	−0.0071	1.4036	0.6322	0.084*
H28C	0.1469	1.3661	0.6631	0.084*
C29	0.8480 (3)	0.60897 (16)	0.70503 (13)	0.0384 (5)
C30	0.9124 (3)	0.61708 (16)	0.77782 (13)	0.0394 (5)
C31	0.9909 (2)	0.62598 (16)	0.86536 (13)	0.0376 (5)
C32	1.0745 (3)	0.55122 (18)	0.87563 (13)	0.0459 (6)
H32	1.0791	0.4947	0.8253	0.055*
C33	1.1503 (3)	0.55990 (18)	0.95916 (14)	0.0459 (6)
H33	1.2054	0.5093	0.9651	0.055*
C34	1.1446 (2)	0.64424 (17)	1.03503 (13)	0.0397 (5)
C35	1.0624 (3)	0.71912 (17)	1.02519 (14)	0.0435 (5)
H35	1.0588	0.7758	1.0757	0.052*
C36	0.9858 (3)	0.71061 (17)	0.94152 (14)	0.0429 (5)
H36	0.9306	0.7613	0.9358	0.052*
C37	1.2238 (3)	0.65612 (19)	1.12705 (14)	0.0457 (5)
C38	1.3982 (3)	0.5901 (2)	1.21119 (14)	0.0564 (7)
H38A	1.3246	0.5811	1.2474	0.068*
H38B	1.4724	0.6574	1.2436	0.068*
C39	1.4869 (4)	0.5037 (2)	1.19026 (16)	0.0717 (8)
H39A	1.4115	0.4375	1.1617	0.108*
H39B	1.5530	0.5069	1.2447	0.108*
H39C	1.5533	0.5110	1.1509	0.108*
C40	0.7039 (3)	0.7919 (2)	0.12545 (16)	0.0563 (6)
D40	0.766 (3)	0.836 (2)	0.1038 (17)	0.066 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0794 (5)	0.0752 (5)	0.0859 (5)	0.0362 (4)	0.0193 (4)	0.0190 (4)
Cl2	0.0926 (6)	0.1798 (10)	0.0620 (5)	0.0683 (7)	0.0111 (4)	0.0528 (6)
Cl3	0.0902 (6)	0.0761 (5)	0.0676 (5)	0.0150 (4)	0.0176 (4)	0.0072 (4)
O1	0.0883 (13)	0.0444 (9)	0.0481 (9)	0.0364 (9)	0.0281 (9)	0.0165 (8)
O2	0.0667 (10)	0.0439 (9)	0.0306 (8)	0.0237 (8)	0.0160 (7)	0.0064 (7)
O3	0.0604 (10)	0.0557 (10)	0.0433 (9)	0.0278 (8)	0.0079 (7)	0.0244 (8)
O4	0.0517 (9)	0.0388 (8)	0.0440 (8)	0.0234 (7)	0.0122 (7)	0.0186 (7)
O5	0.0729 (12)	0.0831 (13)	0.0284 (8)	0.0366 (10)	0.0071 (8)	0.0090 (8)
O6	0.0595 (10)	0.0613 (10)	0.0293 (7)	0.0251 (8)	0.0040 (7)	0.0170 (7)
C1	0.0394 (11)	0.0322 (10)	0.0291 (10)	0.0108 (9)	0.0110 (8)	0.0102 (8)
C2	0.0391 (11)	0.0377 (11)	0.0273 (10)	0.0110 (9)	0.0064 (8)	0.0124 (9)
C3	0.0355 (11)	0.0304 (10)	0.0328 (10)	0.0103 (9)	0.0090 (8)	0.0120 (8)
C4	0.0414 (12)	0.0301 (10)	0.0291 (10)	0.0090 (9)	0.0080 (8)	0.0055 (8)
C5	0.0379 (11)	0.0325 (11)	0.0299 (10)	0.0077 (9)	0.0051 (8)	0.0111 (8)
C6	0.0422 (12)	0.0344 (11)	0.0358 (11)	0.0158 (9)	0.0087 (9)	0.0138 (9)
C7	0.0454 (12)	0.0347 (11)	0.0302 (10)	0.0133 (9)	0.0080 (9)	0.0131 (9)
C8	0.0460 (13)	0.0391 (12)	0.0341 (11)	0.0159 (10)	0.0110 (9)	0.0136 (10)
C9	0.0422 (12)	0.0340 (11)	0.0325 (10)	0.0132 (9)	0.0128 (9)	0.0090 (9)
C10	0.0509 (13)	0.0391 (12)	0.0380 (11)	0.0233 (10)	0.0122 (9)	0.0143 (9)
C11	0.0494 (13)	0.0436 (12)	0.0287 (10)	0.0173 (10)	0.0092 (9)	0.0108 (9)
C12	0.0455 (12)	0.0338 (11)	0.0347 (11)	0.0134 (9)	0.0135 (9)	0.0111 (9)
C13	0.0521 (13)	0.0387 (12)	0.0382 (11)	0.0208 (10)	0.0136 (10)	0.0152 (10)
C14	0.0516 (13)	0.0414 (12)	0.0307 (10)	0.0156 (10)	0.0085 (9)	0.0124 (9)
C15	0.0507 (13)	0.0364 (12)	0.0362 (11)	0.0135 (10)	0.0161 (10)	0.0099 (9)
C16	0.0723 (17)	0.0445 (13)	0.0357 (12)	0.0185 (12)	0.0205 (11)	0.0026 (10)
C17	0.179 (4)	0.0598 (18)	0.0407 (15)	0.047 (2)	0.0408 (18)	0.0131 (13)
C18	0.0409 (12)	0.0326 (11)	0.0323 (10)	0.0093 (9)	0.0089 (9)	0.0094 (9)
C19	0.0390 (12)	0.0357 (11)	0.0358 (11)	0.0103 (10)	0.0087 (9)	0.0112 (9)
C20	0.0360 (11)	0.0313 (11)	0.0375 (11)	0.0101 (9)	0.0086 (9)	0.0128 (9)
C21	0.0476 (13)	0.0413 (12)	0.0317 (10)	0.0173 (10)	0.0053 (9)	0.0143 (9)
C22	0.0471 (12)	0.0357 (11)	0.0325 (11)	0.0158 (10)	0.0105 (9)	0.0103 (9)
C23	0.0339 (11)	0.0343 (11)	0.0390 (11)	0.0106 (9)	0.0083 (9)	0.0168 (9)
C24	0.0434 (12)	0.0423 (12)	0.0316 (10)	0.0135 (10)	0.0073 (9)	0.0160 (9)
C25	0.0455 (12)	0.0362 (11)	0.0329 (11)	0.0138 (10)	0.0106 (9)	0.0095 (9)
C26	0.0366 (11)	0.0378 (12)	0.0411 (12)	0.0124 (9)	0.0096 (9)	0.0183 (10)
C27	0.0407 (12)	0.0379 (12)	0.0519 (13)	0.0182 (10)	0.0114 (10)	0.0220 (10)
C28	0.0700 (17)	0.0450 (14)	0.0565 (14)	0.0302 (13)	0.0138 (12)	0.0191 (12)
C29	0.0447 (12)	0.0358 (11)	0.0332 (11)	0.0134 (10)	0.0062 (9)	0.0115 (9)
C30	0.0442 (12)	0.0382 (12)	0.0339 (11)	0.0127 (10)	0.0071 (9)	0.0116 (9)
C31	0.0387 (12)	0.0423 (12)	0.0294 (10)	0.0099 (9)	0.0055 (8)	0.0122 (9)
C32	0.0582 (14)	0.0454 (13)	0.0277 (10)	0.0218 (11)	0.0059 (9)	0.0050 (9)
C33	0.0549 (14)	0.0478 (13)	0.0355 (11)	0.0246 (11)	0.0071 (10)	0.0140 (10)
C34	0.0398 (12)	0.0479 (13)	0.0291 (10)	0.0124 (10)	0.0068 (9)	0.0122 (9)
C35	0.0505 (13)	0.0436 (12)	0.0309 (11)	0.0170 (11)	0.0098 (9)	0.0060 (9)
C36	0.0497 (13)	0.0431 (13)	0.0371 (11)	0.0195 (10)	0.0098 (9)	0.0139 (10)
C37	0.0452 (13)	0.0571 (15)	0.0317 (11)	0.0136 (11)	0.0073 (9)	0.0140 (11)
C38	0.0644 (16)	0.0741 (17)	0.0305 (11)	0.0234 (14)	0.0024 (10)	0.0213 (11)
C39	0.089 (2)	0.095 (2)	0.0387 (13)	0.0494 (18)	0.0080 (13)	0.0269 (14)
C40	0.0589 (16)	0.0654 (17)	0.0483 (14)	0.0146 (13)	0.0111 (12)	0.0268 (13)

Geometric parameters (Å, º)

Cl1—C40	1.747 (3)	C17—H17B	0.9600
Cl2—C40	1.738 (3)	C17—H17C	0.9600
Cl3—C40	1.740 (3)	C18—C19	1.191 (3)
O1—C15	1.209 (2)	C19—C20	1.437 (3)
O2—C15	1.331 (3)	C20—C25	1.396 (3)
O2—C16	1.460 (2)	C20—C21	1.396 (3)
O3—C26	1.197 (2)	C21—C22	1.377 (3)
O4—C26	1.340 (2)	C21—H21	0.9300
O4—C27	1.450 (2)	C22—C23	1.389 (3)
O5—C37	1.204 (3)	C22—H22	0.9300
O6—C37	1.333 (3)	C23—C24	1.388 (3)
O6—C38	1.451 (2)	C23—C26	1.492 (3)
C1—C6	1.393 (3)	C24—C25	1.381 (3)
C1—C2	1.394 (3)	C24—H24	0.9300
C1—C7	1.445 (3)	C25—H25	0.9300
C2—C3	1.397 (3)	C27—C28	1.508 (3)
C2—H2	0.9300	C27—H27A	0.9700
C3—C4	1.393 (3)	C27—H27B	0.9700
C3—C18	1.438 (3)	C28—H28A	0.9600
C4—C5	1.390 (3)	C28—H28B	0.9600
C4—H4	0.9300	C28—H28C	0.9600
C5—C6	1.396 (3)	C29—C30	1.190 (3)
C5—C29	1.439 (3)	C30—C31	1.438 (3)
C6—H6	0.9300	C31—C32	1.393 (3)
C7—C8	1.186 (3)	C31—C36	1.396 (3)
C8—C9	1.440 (3)	C32—C33	1.373 (3)
C9—C14	1.391 (3)	C32—H32	0.9300
C9—C10	1.397 (3)	C33—C34	1.392 (3)
C10—C11	1.377 (3)	C33—H33	0.9300
C10—H10	0.9300	C34—C35	1.385 (3)
C11—C12	1.391 (3)	C34—C37	1.492 (3)
C11—H11	0.9300	C35—C36	1.378 (3)
C12—C13	1.391 (3)	C35—H35	0.9300
C12—C15	1.491 (3)	C36—H36	0.9300
C13—C14	1.379 (3)	C38—C39	1.489 (4)
C13—H13	0.9300	C38—H38A	0.9700
C14—H14	0.9300	C38—H38B	0.9700
C16—C17	1.481 (4)	C39—H39A	0.9600
C16—H16A	0.9700	C39—H39B	0.9600
C16—H16B	0.9700	C39—H39C	0.9600
C17—H17A	0.9600	C40—D40	0.97 (3)
C15—O2—C16	116.53 (17)	C23—C22—H22	119.8
C26—O4—C27	116.92 (15)	C24—C23—C22	119.38 (18)
C37—O6—C38	116.85 (17)	C24—C23—C26	118.45 (18)
C6—C1—C2	119.57 (17)	C22—C23—C26	122.17 (18)
C6—C1—C7	119.50 (17)	C25—C24—C23	120.62 (18)
C2—C1—C7	120.93 (17)	C25—C24—H24	119.7
C1—C2—C3	120.48 (17)	C23—C24—H24	119.7
C1—C2—H2	119.8	C24—C25—C20	120.17 (18)
C3—C2—H2	119.8	C24—C25—H25	119.9
C4—C3—C2	119.30 (17)	C20—C25—H25	119.9
C4—C3—C18	120.86 (17)	O3—C26—O4	123.73 (18)
C2—C3—C18	119.84 (17)	O3—C26—C23	124.63 (19)
C5—C4—C3	120.69 (17)	O4—C26—C23	111.64 (16)
C5—C4—H4	119.7	O4—C27—C28	106.01 (16)
C3—C4—H4	119.7	O4—C27—H27A	110.5
C4—C5—C6	119.54 (17)	C28—C27—H27A	110.5
C4—C5—C29	120.02 (17)	O4—C27—H27B	110.5
C6—C5—C29	120.42 (18)	C28—C27—H27B	110.5
C1—C6—C5	120.39 (18)	H27A—C27—H27B	108.7
C1—C6—H6	119.8	C27—C28—H28A	109.5
C5—C6—H6	119.8	C27—C28—H28B	109.5
C8—C7—C1	178.5 (2)	H28A—C28—H28B	109.5
C7—C8—C9	179.1 (2)	C27—C28—H28C	109.5
C14—C9—C10	119.17 (17)	H28A—C28—H28C	109.5
C14—C9—C8	120.06 (18)	H28B—C28—H28C	109.5
C10—C9—C8	120.75 (18)	C30—C29—C5	179.2 (2)
C11—C10—C9	120.60 (19)	C29—C30—C31	179.4 (2)
C11—C10—H10	119.7	C32—C31—C36	118.93 (18)
C9—C10—H10	119.7	C32—C31—C30	120.76 (18)
C10—C11—C12	120.03 (19)	C36—C31—C30	120.31 (19)
C10—C11—H11	120.0	C33—C32—C31	120.82 (19)
C12—C11—H11	120.0	C33—C32—H32	119.6
C11—C12—C13	119.49 (18)	C31—C32—H32	119.6
C11—C12—C15	121.85 (18)	C32—C33—C34	120.1 (2)
C13—C12—C15	118.62 (18)	C32—C33—H33	119.9
C14—C13—C12	120.54 (19)	C34—C33—H33	119.9
C14—C13—H13	119.7	C35—C34—C33	119.29 (19)
C12—C13—H13	119.7	C35—C34—C37	118.82 (19)
C13—C14—C9	120.15 (19)	C33—C34—C37	121.88 (19)
C13—C14—H14	119.9	C36—C35—C34	120.80 (19)
C9—C14—H14	119.9	C36—C35—H35	119.6
O1—C15—O2	123.57 (18)	C34—C35—H35	119.6
O1—C15—C12	124.35 (19)	C35—C36—C31	120.02 (19)
O2—C15—C12	112.04 (18)	C35—C36—H36	120.0
O2—C16—C17	106.56 (19)	C31—C36—H36	120.0
O2—C16—H16A	110.4	O5—C37—O6	123.92 (19)
C17—C16—H16A	110.4	O5—C37—C34	124.2 (2)
O2—C16—H16B	110.4	O6—C37—C34	111.84 (18)
C17—C16—H16B	110.4	O6—C38—C39	105.84 (18)
H16A—C16—H16B	108.6	O6—C38—H38A	110.6
C16—C17—H17A	109.5	C39—C38—H38A	110.6
C16—C17—H17B	109.5	O6—C38—H38B	110.6
H17A—C17—H17B	109.5	C39—C38—H38B	110.6
C16—C17—H17C	109.5	H38A—C38—H38B	108.7
H17A—C17—H17C	109.5	C38—C39—H39A	109.5
H17B—C17—H17C	109.5	C38—C39—H39B	109.5
C19—C18—C3	177.8 (2)	H39A—C39—H39B	109.5
C18—C19—C20	179.8 (2)	C38—C39—H39C	109.5
C25—C20—C21	118.88 (18)	H39A—C39—H39C	109.5
C25—C20—C19	120.48 (17)	H39B—C39—H39C	109.5
C21—C20—C19	120.64 (17)	Cl2—C40—Cl3	110.72 (16)
C22—C21—C20	120.64 (18)	Cl2—C40—Cl1	110.71 (14)
C22—C21—H21	119.7	Cl3—C40—Cl1	110.38 (15)
C20—C21—H21	119.7	Cl2—C40—D40	108.4 (16)
C21—C22—C23	120.30 (18)	Cl3—C40—D40	107.7 (16)
C21—C22—H22	119.8	Cl1—C40—D40	108.8 (16)
C6—C1—C2—C3	0.7 (3)	C21—C22—C23—C24	0.8 (3)
C7—C1—C2—C3	179.90 (19)	C21—C22—C23—C26	−178.95 (19)
C1—C2—C3—C4	−1.3 (3)	C22—C23—C24—C25	−1.2 (3)
C1—C2—C3—C18	178.45 (19)	C26—C23—C24—C25	178.51 (19)
C2—C3—C4—C5	0.7 (3)	C23—C24—C25—C20	0.8 (3)
C18—C3—C4—C5	−179.07 (19)	C21—C20—C25—C24	0.1 (3)
C3—C4—C5—C6	0.6 (3)	C19—C20—C25—C24	179.28 (19)
C3—C4—C5—C29	−178.0 (2)	C27—O4—C26—O3	0.4 (3)
C2—C1—C6—C5	0.6 (3)	C27—O4—C26—C23	179.88 (17)
C7—C1—C6—C5	−178.65 (19)	C24—C23—C26—O3	−0.9 (3)
C4—C5—C6—C1	−1.2 (3)	C22—C23—C26—O3	178.8 (2)
C29—C5—C6—C1	177.4 (2)	C24—C23—C26—O4	179.58 (18)
C14—C9—C10—C11	−1.4 (3)	C22—C23—C26—O4	−0.7 (3)
C8—C9—C10—C11	176.9 (2)	C26—O4—C27—C28	−177.55 (19)
C9—C10—C11—C12	0.7 (3)	C36—C31—C32—C33	0.3 (4)
C10—C11—C12—C13	0.6 (3)	C30—C31—C32—C33	179.7 (2)
C10—C11—C12—C15	−177.0 (2)	C31—C32—C33—C34	−0.2 (4)
C11—C12—C13—C14	−1.2 (3)	C32—C33—C34—C35	−0.2 (4)
C15—C12—C13—C14	176.5 (2)	C32—C33—C34—C37	179.4 (2)
C12—C13—C14—C9	0.5 (3)	C33—C34—C35—C36	0.4 (3)
C10—C9—C14—C13	0.8 (3)	C37—C34—C35—C36	−179.2 (2)
C8—C9—C14—C13	−177.5 (2)	C34—C35—C36—C31	−0.2 (4)
C16—O2—C15—O1	−2.5 (3)	C32—C31—C36—C35	−0.1 (3)
C16—O2—C15—C12	175.46 (19)	C30—C31—C36—C35	−179.5 (2)
C11—C12—C15—O1	−173.4 (2)	C38—O6—C37—O5	−2.0 (4)
C13—C12—C15—O1	8.9 (3)	C38—O6—C37—C34	177.9 (2)
C11—C12—C15—O2	8.6 (3)	C35—C34—C37—O5	5.9 (4)
C13—C12—C15—O2	−169.1 (2)	C33—C34—C37—O5	−173.7 (2)
C15—O2—C16—C17	−173.8 (2)	C35—C34—C37—O6	−173.9 (2)
C25—C20—C21—C22	−0.5 (3)	C33—C34—C37—O6	6.5 (3)
C19—C20—C21—C22	−179.7 (2)	C37—O6—C38—C39	−178.6 (2)
C20—C21—C22—C23	0.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C40—D40···O1^i	0.97 (3)	2.24 (3)	3.175 (3)	162 (2)
C36—H36···O1^ii	0.93	2.61	3.408 (3)	144
C14—H14···O3^iii	0.93	2.58	3.341 (3)	140
C25—H25···O5^iv	0.93	2.51	3.337 (2)	148

Symmetry codes: (i) x, y+1, z; (ii) x, y+1, z+1; (iii) x+1, y−1, z; (iv) x−1, y, z−1.