Self-inclusion in 5,11,17,23-tetra-tert-butyl-26,27,28-tri­hydroxy­-25-(methoxy­carbonyl­methoxy)calix­[4]­arene chloro­form trisolvate

The title compound, C₄₇H₆₀O₆·3CHCl₃, is the first example of a lower-rim mono-ester calixarene derivative to be crystallographically characterized. The cone conformation adopted by the macrocycle is stabilized by three intramolecular hydrogen bonds. Self-inclusion of the methyl ester chain in the cavity of an adjacent mol­ecule gives rise to infinite chains parallel to the c axis. C-H...[pi] interactions involving the methyl group most imbedded in the cavity contribute to the stabilization of the system.

S1. Comment

Lower-rim ester derivatives of calixarenes (Thondorf, Shivanyuk & Böhmer, 2001) have been the subject of much attention, in particular for their ionophoric properties (Arnaud-Neu et al., 2001). Numerous di- and tetra-ester derivatives of R-calix[4]arene have been synthesized and characterized, but to the best of our knowledge, no crystal structure of a mono-ester derivative has been reported. The mono-ester (I) was prepared to be used in the synthesis of new dendrimers (Cheriaa et al., 2004). We have reported previously the syntheses and crystal structures of the related compound 5,11,17,23-tetra-tert-butyl-25,27-di(methoxycarbonylmethoxy)- 26,28-dimethoxycalix[4]arene and its complexes with Na⁺ and K⁺ (Oueslati et al., 2000); the absence of hydroxy groups in the former prevents stabilization of the cone conformation by intramolecular hydrogen bonding, as usual for calix[4]arene derivatives (Gutsche, 1998), and it crystallizes in the partial cone conformation. In contrast, the di-methylester derivative of calix[4]arene, unsubstituted at the para positions, 1,3-di(methoxycarbonylmethoxy)-2,4-dihydroxycalix[4]arene, is in the cone conformation (Coles et al., 2002) as is 5,11,17,23-tetra-tert-butyl-25,26,27,28- tetra(methoxycarbonylmethoxy)calix[4]arene and the corresponding tetra-ethyl ester derivative (Arnaud-Neu et al., 1989). A search of the Cambridge Structural Database (CSD; Version 5.25; Allen, 2002) identifies several crystal structures of diethyl ester derivatives, with tert-butyl or H substituents in the para positions (Creaven et al., 2001; Genorio et al., 2003; Bolte et al., 2003; Dudič et al., 2003), but only two triethyl ester compounds have been described (Cooper et al., 2000).

Compound (I) crystallizes as a chloroform trisolvate, with one complete molecule in the asymmetric unit (Fig. 1). The macrocycle adopts a cone conformation, as expected from the intramolecular homodromic hydrogen bonds (Steiner, 2002) involving the three phenol hydroxide groups and the substituted phenol O atom. The mean plane defined by the four methylene C-atom bridges (r.m.s. deviation 0.042 Å) was chosen as a reference plane. The plane defined by the four phenol O atoms (O1, O4, O5 and O6; r.m.s. deviation 0.007 Å) makes a dihedral angle of 2.82 (8)° with this reference plane, whereas the four aromatic rings make dihedral angles of 66.43 (8), 54.24 (10), 56.30 (10) and 62.23 (9)°. The cone conformation thus appears to be regular, but the aromatic ring that bears the ester substituent is more inclined with respect to the reference plane than the other three rings. Comparable conformations were found in diethyl ester derivatives (Creaven et al., 2001; Bolte et al., 2003), whereas the cone conformation is much more distorted in tetra-ester derivatives (Arnaud-Neu et al., 1989) as a result of increased steric interactions. The conformation of the ester chain in (I) is extended and roughly perpendicular to the reference plane. Atom C1 points towards the exterior of the macrocycle [the torsion angles around the C_arom—O1 bond are −93.8 (4) and 87.7 (4)°], whereas the torsion angles around the O1—C1, C1—C2 and C2—O3 bonds do not deviate from syn or anti ideal values by more than 19°. An additional close interaction, possibly a weak hydrogen bond, between atoms O4 and O2 may stabilize this conformation of the chain, the H atom bound to atom O4 being thus involved in a dissymmetric bifurcated hydrogen bond.

The methyl ester chain is included in the cavity of the neighbouring calixarene along the c axis, which gives rise to infinite chains of parallel calixarenes held together by weak interactions directed along this axis (Fig. 2). The chloroform solvent molecules are located in the voids between these chains. Such self-inclusion phenomena are not uncommon in calixarene structures, but very often they involve the para substituents and, as a consequence, the upper rims of adjacent molecules are facing each other and offset (Gallagher et al., 1994; Böhmer et al., 1996; Brouwer et al., 2001). Self-inclusion of an ethyl ester residue in 5,11,17,23-tetra-tert-butyl-25,27-di(ethoxycarbonylmethoxy)- 26,28-dihydroxycalix[4]arene has, however, also been reported recently (Bolte et al., 2003). The C3 methyl group in (I) is located near the centre of the cavity of the neighbouring molecule. Atom C3 is located 4.002 (6)–4.178 (6) Å from the four aromatic para C atoms of the host molecule and 0.416 (4) Å (on the outer side) from the mean plane defined by these four aromatic C atoms (r.m.s. deviation 0.042 Å). This methyl group is thus well imbedded in the cavity, as evidenced by the shortest C3···C_arom distance, 3.657 (6) Å, which involves atom C26 in an ortho position with respect to O5. This value is comparable to that found in the diethyl ester derivative (Bolte et al., 2003), 3.685 (6) Å, but the latter involves a C atom bearing a phenol O atom. Apart from van der Waals contacts, CH–π interactions seem to play an important role in this self-inclusion phenomenon in (I). The three H atoms bound to atom C3 could not be found satisfactorily in difference Fourier maps, but refinement of this group as a rotating methyl group so as to maximize the sum of the electron density at the H-atom positions gave H atoms possibly involved in CH–π interactions with three aromatic rings [H3A···Cg1 = 2.91 Å and C3—H3A···Cg1 = 144°, H3B···Cg2 = 2.93 Å and C3—H3B···Cg2 = 149°, and H3C···Cg3 = 2.77 Å and C3—H3C···Cg3 = 144°, where Cg1, Cg2 and Cg3 are the centroids of the aromatic rings attached to atoms O4ⁱ, O1ⁱ and O5ⁱ, respectively; symmetry code (i) x, y, 1 + z]. In the case of host–guest complexes of calixarenes, it has been suggested that the CH–π interactions could be second to other interactions, such as packing forces (Brouwer, Enright & Ripmeester 1996; Brouwer, Ripmeester & Enright 1996). The relative contributions of such weak interactions cannot be separated on the basis of structural data alone (dipole–dipole interactions may also be present), but the arrangement observed in (I) supports the hypothesis that CH–π interactions are important components in the stabilization of the system.

S2. Experimental

p-tert-Butylcalix[4]arene was refluxed in acetonitrile with three equivalents of bromomethyl acetate and 0.5 equivalents of potassium carbonate for a period of 18 h. After acidification, two-phase extraction with chloroform and evaporation of the solvents, the crude mixture was precipitated with methanol to give the title compound in 55% yield. Mp > 421–422 K. Single crystals were obtained from methanol diffusion in a chloroform solution of (I).

S3. Refinement

Hydroxy H atoms were found in a difference Fourier map and were introduced as riding atoms, with U_iso(H) values of 1.2U_eq(O). All other H atoms were introduced at calculated positions as riding atoms, with C–H bond lengths of 0.93 (aromatic CH), 0.98 (aliphatic CH), 0.97 (CH₂) and 0.96 Å (CH₃), and with U_iso(H) values of 1.2U_eq(parent atom) for CH and CH₂ H atoms and 1.5U_eq(parent atom) for CH₃ Ha toms. The H atoms bound to atom C3, which are probably involved in CH–π interactions, could not be found satisfyingly, but this methyl group was treated as a rotating group and its position was calculated so as to maximize the sum of the electron density at the H-atom positions. The absolute structure was determined from the value of the Flack (1983) parameter [0.03 (5)].

Computing details

Data collection: KappaCCD Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL (Bruker, 1999) and PLATON (Spek, 2000).

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. H atoms have been omitted, except for those involved in hydrogen bonds, which are drawn as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
	Fig. 2. A view showing the self-inclusion in (I). Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted, except for those involved in hydrogen bonds and CH–π interactions, which are drawn as small spheres of arbitrary radii. Solvent molecules have been omitted. [Symmetry code: (') x, y, 1 + z.]

5,11,17,23-tetra-tert-butyl-25-methoxycarbonylmethoxy-26,27,28- trihydroxycalix[4]arene chloroform trisolvate

Crystal data

C47H60O6·3CHCl3	Dx = 1.331 Mg m^−3
Mr = 1079.05	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 35034 reflections
a = 23.7595 (9) Å	θ = 2.3–25.7°
b = 24.2234 (8) Å	µ = 0.51 mm^−1
c = 9.3546 (3) Å	T = 100 K
V = 5383.9 (3) Å^3	Parallelepiped, colourless
Z = 4	0.26 × 0.14 × 0.12 mm
F(000) = 2256

Data collection

Nonius KappaCCD diffractometer	9864 independent reflections
Radiation source: fine-focus sealed tube	7715 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.081
ϕ scans	θmax = 25.7°, θmin = 2.3°
Absorption correction: part of the refinement model (ΔF) (DELABS in PLATON; Spek, 2000)	h = −28→27
Tmin = 0.891, Tmax = 0.936	k = −29→28
35034 measured reflections	l = −11→11

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.125	w = 1/[σ^2(Fo^2) + (0.0582P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
9864 reflections	Δρmax = 0.33 e Å^−3
600 parameters	Δρmin = −0.43 e Å^−3
1 restraint	Absolute structure: Flack (1983), 4416 Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (5)

Special details

Experimental. The unit-cell parameters have been determined from 10 frames, then refined on all data. The crystal-to-detector distance was fixed to 30 mm. One-half of the diffraction sphere was scanned (90 frames, ϕ scans, 2° by frame).

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. Structure solved by direct methods and subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. The H atoms bound to O atoms were found on a Fourier-difference map and all the other ones were introduced at calculated positions. All H atoms were treated as riding atoms with an isotropic displacement parameter equal to 1.2 (OH, CH, CH₂) or 1.5 (CH₃) times that of the parent atom. 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
O1	0.84998 (11)	0.37195 (11)	1.0158 (2)	0.0261 (6)
O2	0.78661 (12)	0.34530 (13)	1.2415 (3)	0.0393 (7)
O3	0.85779 (12)	0.36756 (11)	1.3917 (3)	0.0315 (6)
O4	0.74012 (11)	0.34386 (10)	0.9239 (3)	0.0287 (6)
H4	0.7679	0.3544	0.9817	0.034*
O5	0.76656 (11)	0.24116 (11)	0.8486 (3)	0.0282 (6)
H5	0.7522	0.2752	0.8864	0.034*
O6	0.87691 (11)	0.25542 (10)	0.9253 (3)	0.0279 (6)
H6	0.8385	0.2471	0.9239	0.033*
C1	0.86951 (18)	0.39005 (17)	1.1525 (4)	0.0296 (9)
H1A	0.8675	0.4300	1.1588	0.036*
H1B	0.9083	0.3789	1.1666	0.036*
C2	0.83246 (16)	0.36409 (15)	1.2646 (4)	0.0257 (8)
C3	0.82578 (19)	0.34695 (19)	1.5119 (4)	0.0370 (10)
H3A	0.7896	0.3646	1.5141	0.055*
H3B	0.8456	0.3548	1.5989	0.055*
H3C	0.8208	0.3078	1.5024	0.055*
C4	0.84143 (15)	0.44835 (15)	0.8555 (4)	0.0237 (8)
C5	0.87297 (16)	0.40331 (15)	0.9042 (4)	0.0258 (8)
C6	0.92450 (16)	0.38912 (15)	0.8424 (4)	0.0235 (8)
C7	0.94548 (16)	0.42335 (15)	0.7358 (4)	0.0274 (8)
H7	0.9801	0.4147	0.6951	0.033*
C8	0.91715 (16)	0.46973 (15)	0.6874 (4)	0.0248 (8)
C9	0.86455 (16)	0.48097 (15)	0.7482 (4)	0.0271 (8)
H9	0.8443	0.5113	0.7156	0.032*
C10	0.94119 (17)	0.50817 (17)	0.5738 (4)	0.0315 (9)
C11	0.9021 (2)	0.5089 (2)	0.4439 (5)	0.0562 (14)
H11A	0.8968	0.4719	0.4097	0.084*
H11B	0.9185	0.5310	0.3698	0.084*
H11C	0.8663	0.5242	0.4709	0.084*
C12	0.9995 (2)	0.4910 (2)	0.5274 (6)	0.0569 (15)
H12A	1.0231	0.4869	0.6100	0.085*
H12B	1.0150	0.5187	0.4655	0.085*
H12C	0.9974	0.4565	0.4773	0.085*
C13	0.9456 (2)	0.56757 (18)	0.6334 (5)	0.0463 (12)
H13A	0.9092	0.5797	0.6647	0.069*
H13B	0.9592	0.5918	0.5598	0.069*
H13C	0.9713	0.5681	0.7126	0.069*
C14	0.78198 (15)	0.45866 (16)	0.9077 (4)	0.0289 (9)
H14A	0.7773	0.4425	1.0019	0.035*
H14B	0.7755	0.4981	0.9155	0.035*
C15	0.73955 (16)	0.43375 (15)	0.8059 (4)	0.0253 (8)
C16	0.72352 (16)	0.37851 (16)	0.8138 (4)	0.0264 (8)
C17	0.68808 (15)	0.35511 (15)	0.7097 (4)	0.0256 (8)
C18	0.66887 (16)	0.38882 (16)	0.5989 (4)	0.0280 (9)
H18	0.6453	0.3737	0.5299	0.034*
C19	0.68380 (16)	0.44453 (16)	0.5877 (4)	0.0272 (8)
C20	0.71893 (16)	0.46534 (16)	0.6930 (4)	0.0280 (8)
H20	0.7293	0.5023	0.6880	0.034*
C21	0.66268 (17)	0.47833 (16)	0.4605 (4)	0.0325 (9)
C22	0.6933 (2)	0.45768 (19)	0.3238 (5)	0.0438 (11)
H22A	0.7332	0.4619	0.3356	0.066*
H22B	0.6810	0.4789	0.2430	0.066*
H22C	0.6846	0.4194	0.3084	0.066*
C23	0.67517 (19)	0.53989 (17)	0.4793 (5)	0.0404 (10)
H23A	0.6580	0.5528	0.5659	0.061*
H23B	0.6602	0.5600	0.3995	0.061*
H23C	0.7151	0.5454	0.4844	0.061*
C24	0.59894 (18)	0.47107 (18)	0.4403 (5)	0.0405 (10)
H24A	0.5906	0.4328	0.4235	0.061*
H24B	0.5867	0.4926	0.3599	0.061*
H24C	0.5797	0.4833	0.5248	0.061*
C25	0.67126 (15)	0.29458 (15)	0.7125 (4)	0.0252 (8)
H25A	0.6689	0.2826	0.8112	0.030*
H25B	0.6341	0.2909	0.6707	0.030*
C26	0.71144 (16)	0.25691 (15)	0.6335 (4)	0.0246 (8)
C27	0.75663 (16)	0.23207 (15)	0.7039 (4)	0.0244 (8)
C28	0.79347 (16)	0.19611 (16)	0.6336 (4)	0.0256 (8)
C29	0.78374 (15)	0.18547 (15)	0.4903 (4)	0.0257 (8)
H29	0.8075	0.1610	0.4431	0.031*
C30	0.73967 (15)	0.20996 (15)	0.4131 (4)	0.0245 (8)
C31	0.70470 (16)	0.24568 (15)	0.4879 (4)	0.0259 (8)
H31	0.6755	0.2629	0.4390	0.031*
C32	0.73149 (16)	0.19458 (16)	0.2554 (4)	0.0294 (9)
C33	0.78782 (17)	0.19568 (19)	0.1762 (4)	0.0348 (10)
H33A	0.8036	0.2321	0.1812	0.052*
H33B	0.7820	0.1857	0.0780	0.052*
H33C	0.8132	0.1699	0.2198	0.052*
C34	0.69181 (18)	0.23457 (19)	0.1790 (4)	0.0355 (10)
H34A	0.6551	0.2326	0.2217	0.053*
H34B	0.6893	0.2247	0.0798	0.053*
H34C	0.7061	0.2715	0.1874	0.053*
C35	0.7075 (2)	0.13616 (17)	0.2471 (5)	0.0414 (11)
H35A	0.7333	0.1108	0.2912	0.062*
H35B	0.7021	0.1261	0.1488	0.062*
H35C	0.6720	0.1349	0.2962	0.062*
C36	0.84456 (15)	0.17306 (15)	0.7085 (4)	0.0263 (8)
H36A	0.8546	0.1377	0.6668	0.032*
H36B	0.8362	0.1673	0.8089	0.032*
C37	0.89356 (15)	0.21324 (15)	0.6935 (4)	0.0246 (8)
C38	0.90523 (16)	0.25303 (15)	0.7985 (4)	0.0261 (8)
C39	0.94807 (16)	0.29137 (15)	0.7771 (4)	0.0250 (8)
C40	0.97927 (16)	0.28966 (15)	0.6502 (4)	0.0284 (9)
H40	1.0080	0.3152	0.6369	0.034*
C41	0.96875 (16)	0.25091 (16)	0.5430 (4)	0.0267 (8)
C42	0.92524 (15)	0.21300 (16)	0.5689 (4)	0.0262 (8)
H42	0.9173	0.1866	0.4996	0.031*
C43	1.00031 (16)	0.24939 (17)	0.4011 (4)	0.0297 (9)
C44	1.0390 (2)	0.29940 (19)	0.3823 (6)	0.0519 (13)
H44A	1.0173	0.3327	0.3901	0.078*
H44B	1.0565	0.2979	0.2899	0.078*
H44C	1.0675	0.2990	0.4551	0.078*
C45	1.03587 (19)	0.19695 (18)	0.3916 (5)	0.0383 (10)
H45A	1.0633	0.1969	0.4669	0.057*
H45B	1.0546	0.1958	0.3008	0.057*
H45C	1.0120	0.1652	0.4012	0.057*
C46	0.95818 (19)	0.2497 (2)	0.2756 (4)	0.0427 (11)
H46A	0.9349	0.2174	0.2806	0.064*
H46B	0.9784	0.2498	0.1868	0.064*
H46C	0.9350	0.2821	0.2814	0.064*
C47	0.95712 (16)	0.33717 (15)	0.8855 (4)	0.0270 (8)
H47A	0.9969	0.3457	0.8917	0.032*
H47B	0.9446	0.3249	0.9789	0.032*
Cl1	0.87051 (6)	0.65385 (5)	0.29993 (16)	0.0611 (4)
Cl2	0.78031 (5)	0.57748 (6)	0.23818 (19)	0.0680 (4)
Cl3	0.87814 (6)	0.58005 (6)	0.06059 (14)	0.0575 (3)
C48	0.83252 (18)	0.61951 (17)	0.1667 (5)	0.0350 (10)
H48	0.8145	0.6473	0.1057	0.042*
Cl4	0.44406 (6)	0.51353 (6)	0.54680 (14)	0.0585 (4)
Cl5	0.44283 (6)	0.44421 (6)	0.29698 (14)	0.0597 (4)
Cl6	0.34256 (4)	0.45547 (5)	0.46941 (13)	0.0435 (3)
C49	0.40308 (19)	0.48882 (18)	0.4040 (4)	0.0390 (10)
H49	0.3912	0.5203	0.3456	0.047*
Cl7	0.56806 (6)	0.32987 (7)	0.96994 (16)	0.0691 (4)
Cl8	0.52589 (7)	0.39355 (5)	0.73349 (14)	0.0613 (4)
Cl9	0.45409 (5)	0.36963 (5)	0.97551 (14)	0.0480 (3)
C50	0.50905 (18)	0.34566 (19)	0.8669 (5)	0.0373 (10)
H50	0.4964	0.3116	0.8202	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0315 (14)	0.0283 (14)	0.0186 (12)	−0.0043 (11)	0.0006 (11)	−0.0002 (10)
O2	0.0339 (16)	0.0517 (18)	0.0323 (15)	−0.0093 (14)	−0.0004 (13)	−0.0006 (14)
O3	0.0338 (15)	0.0390 (17)	0.0219 (13)	−0.0076 (13)	0.0009 (12)	0.0028 (12)
O4	0.0328 (15)	0.0274 (14)	0.0260 (14)	−0.0023 (11)	−0.0047 (12)	−0.0001 (11)
O5	0.0356 (15)	0.0296 (15)	0.0194 (12)	0.0000 (12)	−0.0013 (11)	−0.0017 (10)
O6	0.0286 (14)	0.0300 (15)	0.0251 (13)	−0.0039 (11)	0.0051 (11)	−0.0034 (11)
C1	0.036 (2)	0.036 (2)	0.0166 (18)	−0.0069 (18)	−0.0004 (17)	−0.0001 (16)
C2	0.031 (2)	0.0241 (19)	0.0215 (19)	0.0009 (16)	0.0002 (17)	−0.0031 (14)
C3	0.044 (2)	0.047 (3)	0.0200 (19)	−0.008 (2)	0.0042 (18)	0.0046 (17)
C4	0.0245 (19)	0.0205 (19)	0.0261 (18)	−0.0016 (15)	−0.0020 (16)	−0.0048 (15)
C5	0.030 (2)	0.0232 (19)	0.0245 (19)	−0.0058 (16)	−0.0001 (17)	−0.0001 (15)
C6	0.027 (2)	0.0215 (19)	0.0221 (18)	−0.0006 (15)	−0.0052 (16)	−0.0017 (14)
C7	0.030 (2)	0.025 (2)	0.0272 (19)	0.0017 (16)	0.0021 (17)	−0.0006 (16)
C8	0.029 (2)	0.0211 (19)	0.0240 (19)	−0.0020 (15)	−0.0017 (17)	0.0008 (14)
C9	0.030 (2)	0.0228 (19)	0.0285 (19)	0.0002 (16)	−0.0008 (17)	0.0019 (15)
C10	0.037 (2)	0.031 (2)	0.027 (2)	−0.0011 (18)	0.0050 (19)	0.0039 (16)
C11	0.081 (4)	0.056 (3)	0.031 (2)	−0.020 (3)	−0.011 (3)	0.015 (2)
C12	0.064 (3)	0.049 (3)	0.057 (3)	0.014 (3)	0.031 (3)	0.025 (2)
C13	0.057 (3)	0.036 (3)	0.046 (3)	−0.015 (2)	0.005 (2)	0.003 (2)
C14	0.029 (2)	0.026 (2)	0.032 (2)	0.0038 (16)	0.0021 (17)	−0.0042 (16)
C15	0.0233 (19)	0.024 (2)	0.0283 (19)	−0.0014 (15)	0.0040 (16)	−0.0046 (15)
C16	0.0256 (19)	0.028 (2)	0.0259 (19)	0.0012 (16)	0.0029 (17)	0.0002 (15)
C17	0.0221 (18)	0.023 (2)	0.031 (2)	−0.0026 (14)	0.0030 (17)	−0.0020 (16)
C18	0.028 (2)	0.029 (2)	0.028 (2)	0.0014 (17)	0.0034 (17)	−0.0010 (16)
C19	0.0258 (19)	0.023 (2)	0.032 (2)	0.0012 (16)	0.0052 (18)	0.0024 (16)
C20	0.027 (2)	0.024 (2)	0.034 (2)	−0.0009 (16)	0.0022 (18)	0.0007 (16)
C21	0.036 (2)	0.029 (2)	0.032 (2)	0.0036 (17)	0.0001 (19)	0.0045 (18)
C22	0.054 (3)	0.042 (3)	0.036 (2)	0.007 (2)	0.008 (2)	0.007 (2)
C23	0.043 (2)	0.033 (2)	0.045 (2)	0.0009 (19)	0.005 (2)	0.013 (2)
C24	0.039 (2)	0.037 (3)	0.045 (3)	0.0007 (19)	−0.004 (2)	0.0125 (19)
C25	0.0206 (18)	0.028 (2)	0.028 (2)	−0.0031 (15)	0.0000 (16)	0.0019 (15)
C26	0.028 (2)	0.0188 (19)	0.0275 (19)	−0.0047 (16)	0.0032 (16)	−0.0006 (15)
C27	0.030 (2)	0.0198 (18)	0.0229 (18)	−0.0054 (16)	0.0005 (17)	−0.0017 (14)
C28	0.0243 (19)	0.0239 (19)	0.0287 (19)	−0.0031 (16)	0.0020 (16)	0.0033 (16)
C29	0.0253 (18)	0.027 (2)	0.0249 (19)	−0.0060 (15)	0.0004 (17)	−0.0018 (15)
C30	0.0254 (19)	0.0214 (19)	0.027 (2)	−0.0046 (15)	−0.0012 (16)	0.0026 (15)
C31	0.0246 (18)	0.026 (2)	0.0266 (19)	−0.0041 (15)	−0.0021 (16)	0.0038 (16)
C32	0.031 (2)	0.030 (2)	0.027 (2)	−0.0042 (17)	0.0000 (17)	0.0012 (16)
C33	0.037 (2)	0.046 (3)	0.022 (2)	0.0037 (19)	−0.0011 (18)	0.0018 (17)
C34	0.031 (2)	0.045 (3)	0.030 (2)	−0.0011 (19)	−0.0031 (18)	0.0008 (18)
C35	0.060 (3)	0.034 (2)	0.030 (2)	−0.012 (2)	−0.001 (2)	−0.0034 (18)
C36	0.0275 (19)	0.0216 (19)	0.030 (2)	−0.0015 (15)	−0.0024 (17)	−0.0002 (15)
C37	0.0243 (19)	0.026 (2)	0.0240 (19)	0.0003 (15)	−0.0025 (16)	−0.0009 (15)
C38	0.029 (2)	0.026 (2)	0.0234 (18)	−0.0007 (16)	−0.0003 (17)	0.0046 (15)
C39	0.0270 (19)	0.0218 (19)	0.026 (2)	0.0038 (15)	−0.0027 (17)	0.0008 (15)
C40	0.023 (2)	0.025 (2)	0.037 (2)	−0.0009 (16)	−0.0021 (17)	0.0007 (17)
C41	0.0283 (19)	0.024 (2)	0.0275 (19)	0.0016 (16)	0.0005 (17)	0.0035 (15)
C42	0.0250 (19)	0.027 (2)	0.0261 (19)	0.0024 (16)	0.0011 (17)	0.0014 (16)
C43	0.029 (2)	0.030 (2)	0.030 (2)	0.0027 (17)	0.0064 (17)	0.0003 (17)
C44	0.061 (3)	0.041 (3)	0.054 (3)	−0.015 (2)	0.034 (3)	−0.006 (2)
C45	0.040 (2)	0.039 (2)	0.036 (2)	0.006 (2)	0.002 (2)	−0.0051 (19)
C46	0.041 (3)	0.057 (3)	0.030 (2)	0.014 (2)	0.004 (2)	0.009 (2)
C47	0.0238 (19)	0.029 (2)	0.029 (2)	−0.0009 (16)	−0.0037 (16)	0.0016 (16)
Cl1	0.0713 (9)	0.0439 (7)	0.0681 (8)	0.0131 (6)	−0.0327 (7)	−0.0081 (6)
Cl2	0.0369 (6)	0.0669 (9)	0.1003 (11)	−0.0027 (6)	0.0029 (7)	0.0479 (8)
Cl3	0.0652 (8)	0.0591 (8)	0.0481 (7)	0.0307 (7)	0.0085 (6)	0.0072 (6)
C48	0.035 (2)	0.031 (2)	0.039 (2)	0.0063 (18)	0.0001 (19)	0.0023 (18)
Cl4	0.0599 (8)	0.0709 (9)	0.0447 (7)	−0.0218 (7)	−0.0042 (6)	−0.0023 (6)
Cl5	0.0596 (8)	0.0692 (9)	0.0502 (7)	0.0142 (7)	0.0065 (6)	−0.0076 (6)
Cl6	0.0392 (6)	0.0401 (6)	0.0513 (6)	−0.0048 (5)	−0.0035 (5)	0.0119 (5)
C49	0.046 (3)	0.037 (3)	0.035 (2)	−0.006 (2)	−0.001 (2)	0.0055 (19)
Cl7	0.0463 (7)	0.1094 (12)	0.0517 (7)	0.0234 (7)	0.0010 (7)	−0.0079 (8)
Cl8	0.0898 (10)	0.0547 (8)	0.0394 (6)	−0.0283 (7)	0.0045 (7)	−0.0010 (6)
Cl9	0.0381 (6)	0.0479 (7)	0.0580 (7)	−0.0012 (5)	0.0093 (6)	−0.0130 (6)
C50	0.033 (2)	0.040 (3)	0.040 (2)	−0.0040 (19)	0.004 (2)	−0.0041 (19)

Geometric parameters (Å, º)

O1—C5	1.402 (4)	C25—C26	1.513 (5)
O1—C1	1.429 (4)	C25—H25A	0.9700
O2—C2	1.200 (5)	C25—H25B	0.9700
O3—C2	1.335 (5)	C26—C27	1.396 (5)
O3—C3	1.446 (4)	C26—C31	1.398 (5)
O4—C16	1.386 (5)	C27—C28	1.399 (5)
O4—H4	0.8901	C28—C29	1.384 (5)
O5—C27	1.392 (4)	C28—C36	1.509 (5)
O5—H5	0.9594	C29—C30	1.404 (5)
O6—C38	1.365 (4)	C29—H29	0.9300
O6—H6	0.9345	C30—C31	1.389 (5)
C1—C2	1.507 (5)	C30—C32	1.533 (5)
C1—H1A	0.9700	C31—H31	0.9300
C1—H1B	0.9700	C32—C34	1.529 (6)
C3—H3A	0.9600	C32—C35	1.528 (6)
C3—H3B	0.9600	C32—C33	1.530 (6)
C3—H3C	0.9600	C33—H33A	0.9600
C4—C9	1.391 (5)	C33—H33B	0.9600
C4—C5	1.399 (5)	C33—H33C	0.9600
C4—C14	1.515 (5)	C34—H34A	0.9600
C5—C6	1.397 (5)	C34—H34B	0.9600
C6—C7	1.390 (5)	C34—H34C	0.9600
C6—C47	1.532 (5)	C35—H35A	0.9600
C7—C8	1.386 (5)	C35—H35B	0.9600
C7—H7	0.9300	C35—H35C	0.9600
C8—C9	1.399 (5)	C36—C37	1.524 (5)
C8—C10	1.524 (5)	C36—H36A	0.9700
C9—H9	0.9300	C36—H36B	0.9700
C10—C12	1.511 (6)	C37—C42	1.388 (5)
C10—C11	1.530 (6)	C37—C38	1.403 (5)
C10—C13	1.547 (6)	C38—C39	1.392 (5)
C11—H11A	0.9600	C39—C40	1.400 (5)
C11—H11B	0.9600	C39—C47	1.518 (5)
C11—H11C	0.9600	C40—C41	1.396 (5)
C12—H12A	0.9600	C40—H40	0.9300
C12—H12B	0.9600	C41—C42	1.404 (5)
C12—H12C	0.9600	C41—C43	1.525 (5)
C13—H13A	0.9600	C42—H42	0.9300
C13—H13B	0.9600	C43—C45	1.528 (6)
C13—H13C	0.9600	C43—C44	1.531 (6)
C14—C15	1.513 (5)	C43—C46	1.543 (6)
C14—H14A	0.9700	C44—H44A	0.9600
C14—H14B	0.9700	C44—H44B	0.9600
C15—C16	1.393 (5)	C44—H44C	0.9600
C15—C20	1.393 (5)	C45—H45A	0.9600
C16—C17	1.406 (5)	C45—H45B	0.9600
C17—C18	1.396 (5)	C45—H45C	0.9600
C17—C25	1.520 (5)	C46—H46A	0.9600
C18—C19	1.399 (5)	C46—H46B	0.9600
C18—H18	0.9300	C46—H46C	0.9600
C19—C20	1.386 (6)	C47—H47A	0.9700
C19—C21	1.529 (6)	C47—H47B	0.9700
C20—H20	0.9300	Cl1—C48	1.749 (4)
C21—C23	1.531 (6)	Cl2—C48	1.739 (4)
C21—C24	1.536 (6)	Cl3—C48	1.753 (4)
C21—C22	1.554 (6)	C48—H48	0.9800
C22—H22A	0.9600	Cl4—C49	1.758 (4)
C22—H22B	0.9600	Cl5—C49	1.750 (5)
C22—H22C	0.9600	Cl6—C49	1.759 (4)
C23—H23A	0.9600	C49—H49	0.9800
C23—H23B	0.9600	Cl7—C50	1.744 (5)
C23—H23C	0.9600	Cl8—C50	1.750 (5)
C24—H24A	0.9600	Cl9—C50	1.753 (4)
C24—H24B	0.9600	C50—H50	0.9800
C24—H24C	0.9600
C5—O1—C1	112.0 (3)	H25A—C25—H25B	107.6
C2—O3—C3	115.7 (3)	C27—C26—C31	117.6 (3)
C16—O4—H4	119.2	C27—C26—C25	121.0 (3)
C27—O5—H5	115.7	C31—C26—C25	121.4 (3)
C38—O6—H6	117.4	O5—C27—C26	121.4 (3)
O1—C1—C2	107.8 (3)	O5—C27—C28	116.7 (3)
O1—C1—H1A	110.2	C26—C27—C28	121.9 (3)
C2—C1—H1A	110.2	C29—C28—C27	117.8 (4)
O1—C1—H1B	110.2	C29—C28—C36	121.0 (3)
C2—C1—H1B	110.2	C27—C28—C36	121.0 (3)
H1A—C1—H1B	108.5	C28—C29—C30	123.0 (4)
O2—C2—O3	126.4 (4)	C28—C29—H29	118.5
O2—C2—C1	124.3 (3)	C30—C29—H29	118.5
O3—C2—C1	109.3 (3)	C31—C30—C29	116.7 (3)
O3—C3—H3A	109.5	C31—C30—C32	124.1 (3)
O3—C3—H3B	109.5	C29—C30—C32	119.2 (3)
H3A—C3—H3B	109.5	C30—C31—C26	122.9 (4)
O3—C3—H3C	109.5	C30—C31—H31	118.5
H3A—C3—H3C	109.5	C26—C31—H31	118.5
H3B—C3—H3C	109.5	C34—C32—C35	109.5 (3)
C9—C4—C5	117.8 (3)	C34—C32—C33	107.6 (3)
C9—C4—C14	120.5 (3)	C35—C32—C33	108.5 (4)
C5—C4—C14	121.5 (3)	C34—C32—C30	112.0 (3)
C6—C5—C4	121.8 (3)	C35—C32—C30	108.7 (3)
C6—C5—O1	121.1 (3)	C33—C32—C30	110.5 (3)
C4—C5—O1	117.1 (3)	C32—C33—H33A	109.5
C7—C6—C5	117.7 (3)	C32—C33—H33B	109.5
C7—C6—C47	119.8 (3)	H33A—C33—H33B	109.5
C5—C6—C47	122.5 (3)	C32—C33—H33C	109.5
C8—C7—C6	123.0 (4)	H33A—C33—H33C	109.5
C8—C7—H7	118.5	H33B—C33—H33C	109.5
C6—C7—H7	118.5	C32—C34—H34A	109.5
C7—C8—C9	117.3 (3)	C32—C34—H34B	109.5
C7—C8—C10	122.8 (3)	H34A—C34—H34B	109.5
C9—C8—C10	119.9 (3)	C32—C34—H34C	109.5
C4—C9—C8	122.4 (3)	H34A—C34—H34C	109.5
C4—C9—H9	118.8	H34B—C34—H34C	109.5
C8—C9—H9	118.8	C32—C35—H35A	109.5
C12—C10—C8	112.1 (3)	C32—C35—H35B	109.5
C12—C10—C11	109.4 (4)	H35A—C35—H35B	109.5
C8—C10—C11	109.5 (3)	C32—C35—H35C	109.5
C12—C10—C13	107.3 (4)	H35A—C35—H35C	109.5
C8—C10—C13	110.0 (3)	H35B—C35—H35C	109.5
C11—C10—C13	108.5 (4)	C28—C36—C37	109.6 (3)
C10—C11—H11A	109.5	C28—C36—H36A	109.7
C10—C11—H11B	109.5	C37—C36—H36A	109.7
H11A—C11—H11B	109.5	C28—C36—H36B	109.7
C10—C11—H11C	109.5	C37—C36—H36B	109.7
H11A—C11—H11C	109.5	H36A—C36—H36B	108.2
H11B—C11—H11C	109.5	C42—C37—C38	118.9 (3)
C10—C12—H12A	109.5	C42—C37—C36	119.3 (3)
C10—C12—H12B	109.5	C38—C37—C36	121.7 (3)
H12A—C12—H12B	109.5	O6—C38—C39	117.2 (3)
C10—C12—H12C	109.5	O6—C38—C37	122.7 (3)
H12A—C12—H12C	109.5	C39—C38—C37	120.1 (3)
H12B—C12—H12C	109.5	C38—C39—C40	119.3 (3)
C10—C13—H13A	109.5	C38—C39—C47	119.7 (3)
C10—C13—H13B	109.5	C40—C39—C47	120.8 (3)
H13A—C13—H13B	109.5	C41—C40—C39	122.3 (4)
C10—C13—H13C	109.5	C41—C40—H40	118.9
H13A—C13—H13C	109.5	C39—C40—H40	118.9
H13B—C13—H13C	109.5	C40—C41—C42	116.6 (4)
C15—C14—C4	110.6 (3)	C40—C41—C43	123.6 (4)
C15—C14—H14A	109.5	C42—C41—C43	119.8 (3)
C4—C14—H14A	109.5	C37—C42—C41	122.8 (4)
C15—C14—H14B	109.5	C37—C42—H42	118.6
C4—C14—H14B	109.5	C41—C42—H42	118.6
H14A—C14—H14B	108.1	C41—C43—C45	110.0 (3)
C16—C15—C20	118.1 (3)	C41—C43—C44	112.1 (3)
C16—C15—C14	122.1 (4)	C45—C43—C44	108.6 (4)
C20—C15—C14	119.5 (3)	C41—C43—C46	110.1 (3)
O4—C16—C15	122.9 (3)	C45—C43—C46	108.6 (3)
O4—C16—C17	116.2 (3)	C44—C43—C46	107.4 (4)
C15—C16—C17	120.9 (4)	C43—C44—H44A	109.5
C18—C17—C16	118.3 (3)	C43—C44—H44B	109.5
C18—C17—C25	119.4 (3)	H44A—C44—H44B	109.5
C16—C17—C25	122.3 (3)	C43—C44—H44C	109.5
C17—C18—C19	122.4 (4)	H44A—C44—H44C	109.5
C17—C18—H18	118.8	H44B—C44—H44C	109.5
C19—C18—H18	118.8	C43—C45—H45A	109.5
C20—C19—C18	116.8 (4)	C43—C45—H45B	109.5
C20—C19—C21	123.8 (3)	H45A—C45—H45B	109.5
C18—C19—C21	119.4 (4)	C43—C45—H45C	109.5
C19—C20—C15	123.4 (4)	H45A—C45—H45C	109.5
C19—C20—H20	118.3	H45B—C45—H45C	109.5
C15—C20—H20	118.3	C43—C46—H46A	109.5
C19—C21—C23	111.6 (3)	C43—C46—H46B	109.5
C19—C21—C24	111.0 (3)	H46A—C46—H46B	109.5
C23—C21—C24	108.5 (3)	C43—C46—H46C	109.5
C19—C21—C22	108.3 (3)	H46A—C46—H46C	109.5
C23—C21—C22	108.5 (4)	H46B—C46—H46C	109.5
C24—C21—C22	108.9 (4)	C39—C47—C6	110.7 (3)
C21—C22—H22A	109.5	C39—C47—H47A	109.5
C21—C22—H22B	109.5	C6—C47—H47A	109.5
H22A—C22—H22B	109.5	C39—C47—H47B	109.5
C21—C22—H22C	109.5	C6—C47—H47B	109.5
H22A—C22—H22C	109.5	H47A—C47—H47B	108.1
H22B—C22—H22C	109.5	Cl2—C48—Cl1	111.9 (2)
C21—C23—H23A	109.5	Cl2—C48—Cl3	109.9 (2)
C21—C23—H23B	109.5	Cl1—C48—Cl3	110.1 (2)
H23A—C23—H23B	109.5	Cl2—C48—H48	108.3
C21—C23—H23C	109.5	Cl1—C48—H48	108.3
H23A—C23—H23C	109.5	Cl3—C48—H48	108.3
H23B—C23—H23C	109.5	Cl5—C49—Cl4	110.2 (3)
C21—C24—H24A	109.5	Cl5—C49—Cl6	110.9 (2)
C21—C24—H24B	109.5	Cl4—C49—Cl6	110.2 (2)
H24A—C24—H24B	109.5	Cl5—C49—H49	108.5
C21—C24—H24C	109.5	Cl4—C49—H49	108.5
H24A—C24—H24C	109.5	Cl6—C49—H49	108.5
H24B—C24—H24C	109.5	Cl7—C50—Cl8	110.8 (2)
C26—C25—C17	114.1 (3)	Cl7—C50—Cl9	110.6 (2)
C26—C25—H25A	108.7	Cl8—C50—Cl9	111.3 (3)
C17—C25—H25A	108.7	Cl7—C50—H50	108.0
C26—C25—H25B	108.7	Cl8—C50—H50	108.0
C17—C25—H25B	108.7	Cl9—C50—H50	108.0

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O1	0.89	2.02	2.831 (4)	151
O4—H4···O2	0.89	2.48	3.170 (4)	135
O5—H5···O4	0.96	1.72	2.661 (4)	164
O6—H6···O5	0.93	1.85	2.740 (4)	157