2,4-Di­hydroxy-1,3-bis­(methoxy­carbonyl­methoxy)­calix­[4]­arene and 1,3-bis­(ethoxy­carbonyl­methoxy)-2,4-di­hydroxy­calix­[4]­arene chloro­form solvate

The two title calix­[4]­arene compounds, C₃₄H₃₂O₈, (I), and C₃₆H₃₆O₈·CH₃Cl, (II), respectively, which differ only in the size of the alkyl function on the pendant ester group, are compared. Compound (I) forms a novel supramolecular array, whilst (II) fails to do so due to accommodating a chloro­form guest molecule in the lower-rim cavity.

S1. Comment

There is much current interest in the design of supramolecular structures where the guest–host assembly is formed by non-covalent interactions (Lehn, 1995; Gutsche, 1998). Calixarenes are a promising platform as good candidates for self-assembly (Mandolini & Ungaro, 2000), owing to their high symmetry and ease of chemical modification. The title calix[4]arenes, 2,4-dihydroxy-1,3-bis(methoxycarbonylmethoxy)calix[4]arene, (I), and 2,4-dihydroxy-1,3-bis(ethoxycarbonylmethoxy)calix[4]arene chloroform solvate, (II), are well established in the literature as building blocks for more elaborate calixarenes (Beer et al., 1998). In addition, compound (I) has been shown to extract Cs⁺ and Sr²⁺ (Arena et al., 1999; Grunder et al., 1999), however, their crystal structures have not been reported in the literature.

The molecular structures of (I) and (II) are shown in Figs. 1 and 2, respectively, whilst the supramolecular structure of (I) is shown in Fig. 3. The crystal structure of (I) is unusual in that it forms a honeycomb structure of columnar hexagonal tubes. These tubes have an internal diameter of 4.83 (9) Å and are constructed by the stacking of three calixarenes alternatively offset by 60°, giving overall C₃ symmetry. The driving force to the formation of this structure is π–π-stacking/interlocking between the calixarene rings and dipole–dipole interactions between the lower rim methyl ester groups. This is demonstrated by the head-to-tail arrangement of the carbonyl groups on the lower rim. To our knowledge, this is the first example of a honeycomb structure for a purely organic calixarene. Calixarene (II) failed to form a nanotubular array, a result of the carbonyl groups on the ethyl ester pendant arms being directed away from each other due to their conformational rearrangement in order to accommodate the chloroform guest.

The structures of (I) and (II) are best described comparatively, and hence the values in brackets refer to the equivalent parameter in (II) to that stated for (I). The angles about the meso-C atoms [C1, C8, C17 and C24 for (I), and C7, C14, C21 and C28 for (II)], given in Tables 1 and 2, are reasonably close to ideal tetrahedral geometry, indicating a strain-free macrocycle. The upper rim of calixarene (I) forms a cavity with separations between meso-C atoms of 5.067 (2), 5.075 (2), 5.079 (2) and 5.070 (2) Å [5.066 (3), 5.090 (3), 5.067 (3) and 5.099 (3) Å] and cross-ring distances between meso-C atoms of 7.312 (2) and 7.031 (2) Å [7.352 (3) and 7.008 (3) Å]. The asymmetry of the macrocycle is caused by the lower-rim substituents, which form a number of intramolecular hydrogen bonds with each other. In addition, the angles of the aromatic rings in the calixarene with respect to the mean plane of the macrocyle (defined by the meso-C atoms) are 71.70 (4) and 68.46 (3)° [73.68 (7) and 68.42 (6)°] for the alkyl ester functionalized rings, whilst those for the hydroxy-substituted rings are 42.35 (4) and 37.86 (5)° [45.52 (7) and 49.17 (6)°]. Thus, the hydroxy-substituted rings are allowed to lie more in the plane of the macrocycle due to their relatively small functional groups on the lower rim and the intramolecular interactions in which they are involved. The separation of the terminal methyl groups of the ester function is 6.475 (2) Å [7.141 (3) Å], reflecting the dilation of the lower rim substituents in calixarene (II) in order to accommodate the chloroform moiety.

Pertinent hydrogen-bonding parameters are given in Tables 2 and 4. The pendant ester groups are locked in position by strong hydrogen bonding between the hydroxy substituent and the oxy-linkage between the calixarene and the ester and these are of comparable strength in (I) and (II). There is a further interaction between the carbonyl group of the ester and the hydroxy substituent, making it a bifurcated donor. This interaction is weaker in (I) compared with (II) as the arms are allowed to adopt the most favourable conformation, as opposed to those of (II) which interact with the chloroform guest molecule. Non-classical interactions, presumably electrostatic, occur in (II) between the guest and host [D···A = Cl2···O5 = 3.316 (2) Å, Cl1···O8 = 3.349 (2) Å, C37···O4 = 3.221 (3) Å and C37···O5 = 3.075 (3) Å].

S2. Experimental

Calixarenes (I) and (II) were synthesized by reaction of calix[4]arene with the appropriate bromoalkyl acetate according to previously described procedures (Aoki et al., 1992). Calixarene (I) was recrystallized from a methanol/chloroform mixture. Crystals of (II) suitable for diffraction analysis were obtained by recrystallization from an ethyl acetate/chloroform mixture and immediately transferred to the diffractometer, as the crystals degraded, losing solvent, after standing for a short time in air.

S3. Refinement

All H atoms were included in idealized positions with X—H distances of 0.84, 0.95, 0.99 and 0.98 Å for hydroxyl, methine, methylene and methyl H, respectively. The coordinates of these fixed atoms were allowed to ride on those of the parent atoms. The displacement parameters of the H atoms were constrained to be a factor of 1.2 greater than those of the parent atoms for those associated with aromatic moities and 1.5 greater than the parent values for the others. A Flack (1983) parameter of -0.10 (4), determined by refinement using 3510 Friedel pairs, indicated that the correct absolute structure of (II) has been identified.

Computing details

For both compounds, cell refinement: DENZO (Hooft 1998) and COLLECT (Otwinowski & Minor, 1997); data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990).

Figures

	Fig. 1. View of (I) shown with 50% probability displacement ellipsoids.
	Fig. 2. View of (II) shown with 50% probability displacement ellipsoids.
	Fig. 3. The supramolecular structure exhibited by (I).

(I)

Crystal data

C34H32O8	F(000) = 5400
Mr = 568.6	Dx = 1.307 Mg m^−3
Rhombohedral, R3	Mo Kα radiation, λ = 0.71073 Å
a = 32.840 (5) Å	Cell parameters from 13396 reflections
c = 13.918 (3) Å	θ = 1.0–30.5°
α = 90°	µ = 0.09 mm^−1
γ = 120°	T = 150 K
V = 13000 (4) Å^3	Block, colourless
Z = 18	0.3 × 0.2 × 0.2 mm

Data collection

Nonius KappaCCD area-detector diffractometer	4617 reflections with I > 2σ(I)
ϕ and ω scans	Rint = 0.044
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	θmax = 27.5°, θmin = 2.2°
Tmin = 0.973, Tmax = 0.982	h = −42→33
25617 measured reflections	k = −30→42
6609 independent reflections	l = −17→18

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0542P)^2 + 5.423P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.044	(Δ/σ)max = 0.002
wR(F^2) = 0.114	Δρmax = 0.24 e Å^−3
S = 1.04	Δρmin = −0.20 e Å^−3
6609 reflections	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
384 parameters	Extinction coefficient: 0.00040 (7)
0 restraints

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.56335 (5)	0.78110 (5)	0.16352 (10)	0.0320 (3)
H1A	0.5298	0.7715	0.1715	0.038*
H1B	0.5732	0.7948	0.0985	0.038*
C2	0.56859 (5)	0.73802 (5)	0.17118 (10)	0.0311 (3)
C3	0.59427 (5)	0.72950 (6)	0.10245 (11)	0.0375 (4)
H3	0.6084	0.7511	0.0509	0.045*
C4	0.59978 (5)	0.69053 (6)	0.10721 (12)	0.0420 (4)
H4	0.6173	0.6853	0.0593	0.050*
C5	0.57964 (5)	0.65926 (6)	0.18224 (12)	0.0396 (4)
H5	0.5835	0.6325	0.1857	0.048*
C6	0.55384 (5)	0.66618 (5)	0.25266 (11)	0.0341 (4)
C7	0.54816 (5)	0.70557 (5)	0.24602 (10)	0.0300 (3)
C8	0.53106 (6)	0.63158 (5)	0.33435 (12)	0.0367 (4)
H8A	0.4984	0.6251	0.3426	0.044*
H8B	0.5296	0.6016	0.3171	0.044*
C9	0.55699 (5)	0.64900 (5)	0.42880 (11)	0.0322 (3)
C10	0.59991 (6)	0.65119 (5)	0.44250 (13)	0.0401 (4)
H10	0.6124	0.6410	0.3926	0.048*
C11	0.62482 (5)	0.66790 (6)	0.52713 (13)	0.0426 (4)
H11	0.6534	0.6678	0.5363	0.051*
C12	0.60802 (5)	0.68476 (6)	0.59812 (12)	0.0389 (4)
H12	0.6258	0.6974	0.6552	0.047*
C13	0.56553 (5)	0.68366 (5)	0.58774 (11)	0.0319 (3)
C14	0.53999 (5)	0.66399 (5)	0.50432 (11)	0.0295 (3)
C15	0.54940 (6)	0.70594 (6)	0.66286 (11)	0.0373 (4)
H15A	0.5152	0.6934	0.6560	0.045*
H15B	0.5552	0.6975	0.7277	0.045*
C16	0.57482 (5)	0.75888 (5)	0.65322 (10)	0.0329 (3)
C17	0.61101 (6)	0.78698 (6)	0.71592 (11)	0.0426 (4)
H17	0.6198	0.7725	0.7646	0.051*
C18	0.63446 (6)	0.83522 (6)	0.70923 (12)	0.0467 (4)
H18	0.6586	0.8538	0.7537	0.056*
C19	0.62265 (5)	0.85650 (6)	0.63738 (11)	0.0378 (4)
H19	0.6388	0.8898	0.6331	0.045*
C20	0.58757 (5)	0.82999 (5)	0.57129 (10)	0.0296 (3)
C21	0.56329 (5)	0.78108 (5)	0.58095 (10)	0.0286 (3)
C22	0.57563 (5)	0.85367 (5)	0.49139 (10)	0.0311 (3)
H22A	0.5864	0.8866	0.5101	0.037*
H22B	0.5410	0.8374	0.4837	0.037*
C23	0.59770 (5)	0.85348 (5)	0.39546 (10)	0.0263 (3)
C24	0.64517 (5)	0.88396 (5)	0.37778 (10)	0.0285 (3)
H24	0.6637	0.9064	0.4253	0.034*
C25	0.66603 (5)	0.88238 (5)	0.29275 (10)	0.0291 (3)
H25	0.6983	0.9042	0.2816	0.035*
C26	0.63988 (5)	0.84906 (5)	0.22396 (10)	0.0283 (3)
H26	0.6547	0.8471	0.1669	0.034*
C27	0.59210 (5)	0.81839 (5)	0.23756 (10)	0.0266 (3)
C28	0.57179 (5)	0.82241 (5)	0.32210 (10)	0.0252 (3)
C29	0.49624 (5)	0.81350 (5)	0.30570 (12)	0.0321 (3)
H29A	0.5073	0.8293	0.2428	0.039*
H29B	0.4997	0.8373	0.3537	0.039*
C30	0.44584 (5)	0.77557 (5)	0.29865 (10)	0.0265 (3)
C31	0.36809 (5)	0.76153 (6)	0.28930 (12)	0.0428 (4)
H31A	0.3619	0.7452	0.2275	0.064*
H31B	0.3509	0.7787	0.2924	0.064*
H31C	0.3577	0.7385	0.3416	0.064*
C32	0.45809 (5)	0.61746 (5)	0.52656 (13)	0.0378 (4)
H32A	0.4654	0.6084	0.5893	0.045*
H32B	0.4521	0.5926	0.4792	0.045*
C33	0.41585 (5)	0.62333 (5)	0.53537 (10)	0.0304 (3)
C34	0.33309 (5)	0.58229 (7)	0.54553 (13)	0.0472 (4)
H34A	0.3329	0.5970	0.6066	0.071*
H34B	0.3065	0.5500	0.5437	0.071*
H34C	0.3304	0.6003	0.4923	0.071*
O2	0.52051 (4)	0.70860 (4)	0.31499 (7)	0.0357 (3)
H2	0.5191	0.7332	0.3067	0.054*
O1	0.49634 (3)	0.66134 (3)	0.49579 (7)	0.0319 (3)
O3	0.52325 (3)	0.79260 (3)	0.33383 (7)	0.0281 (2)
O4	0.52754 (4)	0.75722 (4)	0.51796 (8)	0.0363 (3)
H4A	0.5166	0.7282	0.5253	0.054*
O5	0.41717 (4)	0.66008 (4)	0.54139 (9)	0.0470 (3)
O6	0.37676 (4)	0.58146 (4)	0.53655 (8)	0.0402 (3)
O7	0.43258 (4)	0.73475 (4)	0.29201 (9)	0.0451 (3)
O8	0.41804 (3)	0.79429 (4)	0.29878 (8)	0.0367 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0305 (8)	0.0292 (8)	0.0334 (8)	0.0127 (7)	−0.0068 (6)	0.0002 (6)
C2	0.0255 (8)	0.0271 (8)	0.0351 (8)	0.0090 (7)	−0.0108 (6)	−0.0092 (6)
C3	0.0253 (8)	0.0359 (9)	0.0412 (9)	0.0077 (7)	−0.0078 (7)	−0.0103 (7)
C4	0.0267 (8)	0.0406 (10)	0.0544 (10)	0.0136 (8)	−0.0051 (7)	−0.0202 (8)
C5	0.0278 (8)	0.0293 (9)	0.0608 (11)	0.0135 (7)	−0.0118 (7)	−0.0178 (8)
C6	0.0290 (8)	0.0260 (8)	0.0469 (9)	0.0135 (7)	−0.0130 (7)	−0.0111 (7)
C7	0.0282 (8)	0.0258 (8)	0.0359 (8)	0.0134 (7)	−0.0093 (6)	−0.0091 (6)
C8	0.0329 (9)	0.0206 (8)	0.0572 (10)	0.0138 (7)	−0.0090 (7)	−0.0081 (7)
C9	0.0259 (8)	0.0182 (7)	0.0527 (9)	0.0111 (6)	−0.0046 (7)	0.0009 (6)
C10	0.0309 (9)	0.0310 (9)	0.0639 (11)	0.0196 (7)	−0.0035 (8)	−0.0044 (8)
C11	0.0235 (8)	0.0340 (9)	0.0718 (12)	0.0155 (7)	−0.0069 (8)	0.0020 (8)
C12	0.0286 (9)	0.0336 (9)	0.0521 (10)	0.0138 (7)	−0.0102 (7)	0.0025 (7)
C13	0.0265 (8)	0.0254 (8)	0.0424 (9)	0.0118 (7)	0.0003 (6)	0.0091 (6)
C14	0.0199 (7)	0.0198 (7)	0.0490 (9)	0.0101 (6)	−0.0011 (6)	0.0077 (6)
C15	0.0367 (9)	0.0393 (9)	0.0348 (8)	0.0183 (8)	0.0024 (7)	0.0104 (7)
C16	0.0316 (8)	0.0368 (9)	0.0305 (8)	0.0173 (7)	0.0052 (6)	0.0038 (6)
C17	0.0473 (10)	0.0492 (11)	0.0308 (8)	0.0237 (9)	−0.0035 (7)	0.0026 (7)
C18	0.0452 (10)	0.0481 (11)	0.0375 (9)	0.0164 (9)	−0.0097 (8)	−0.0082 (8)
C19	0.0340 (9)	0.0339 (9)	0.0392 (9)	0.0121 (7)	0.0009 (7)	−0.0063 (7)
C20	0.0285 (8)	0.0319 (8)	0.0306 (7)	0.0168 (7)	0.0046 (6)	−0.0018 (6)
C21	0.0245 (8)	0.0306 (8)	0.0300 (7)	0.0131 (7)	0.0029 (6)	−0.0021 (6)
C22	0.0292 (8)	0.0241 (8)	0.0418 (9)	0.0148 (7)	0.0010 (6)	−0.0038 (6)
C23	0.0245 (7)	0.0211 (7)	0.0367 (8)	0.0140 (6)	−0.0023 (6)	0.0017 (6)
C24	0.0247 (8)	0.0205 (7)	0.0386 (8)	0.0101 (6)	−0.0075 (6)	−0.0024 (6)
C25	0.0203 (7)	0.0235 (7)	0.0416 (8)	0.0094 (6)	−0.0026 (6)	0.0045 (6)
C26	0.0270 (8)	0.0283 (8)	0.0320 (8)	0.0156 (7)	−0.0005 (6)	0.0048 (6)
C27	0.0270 (8)	0.0220 (7)	0.0327 (7)	0.0138 (6)	−0.0065 (6)	0.0030 (6)
C28	0.0189 (7)	0.0175 (7)	0.0390 (8)	0.0088 (6)	−0.0032 (6)	0.0051 (6)
C29	0.0233 (8)	0.0236 (8)	0.0506 (9)	0.0127 (6)	−0.0035 (6)	0.0076 (6)
C30	0.0240 (7)	0.0267 (8)	0.0273 (7)	0.0116 (6)	−0.0007 (6)	0.0037 (6)
C31	0.0203 (8)	0.0534 (11)	0.0504 (10)	0.0152 (8)	−0.0034 (7)	0.0028 (8)
C32	0.0229 (8)	0.0270 (8)	0.0600 (10)	0.0098 (7)	0.0015 (7)	0.0127 (7)
C33	0.0251 (8)	0.0340 (9)	0.0298 (7)	0.0131 (7)	−0.0002 (6)	0.0053 (6)
C34	0.0222 (8)	0.0604 (12)	0.0525 (10)	0.0158 (8)	0.0048 (7)	0.0040 (9)
O2	0.0453 (7)	0.0253 (6)	0.0426 (6)	0.0221 (5)	0.0027 (5)	0.0029 (4)
O1	0.0185 (5)	0.0251 (5)	0.0512 (6)	0.0102 (4)	0.0012 (4)	0.0105 (4)
O3	0.0185 (5)	0.0205 (5)	0.0441 (6)	0.0088 (4)	−0.0038 (4)	0.0056 (4)
O4	0.0340 (6)	0.0251 (6)	0.0475 (6)	0.0131 (5)	−0.0082 (5)	0.0013 (5)
O5	0.0359 (7)	0.0363 (7)	0.0718 (8)	0.0204 (6)	0.0098 (6)	0.0041 (6)
O6	0.0217 (6)	0.0368 (6)	0.0543 (7)	0.0089 (5)	0.0032 (5)	0.0048 (5)
O7	0.0308 (6)	0.0250 (6)	0.0738 (8)	0.0098 (5)	−0.0114 (5)	−0.0039 (5)
O8	0.0222 (5)	0.0360 (6)	0.0526 (7)	0.0149 (5)	−0.0040 (5)	0.0010 (5)

Geometric parameters (Å, º)

C31—O8	1.4495 (18)	C12—H12	0.9500
C31—H31A	0.9800	C13—C14	1.388 (2)
C31—H31B	0.9800	C13—C15	1.515 (2)
C31—H31C	0.9800	C14—O1	1.3969 (17)
C32—O1	1.4241 (17)	C15—C16	1.512 (2)
C32—C33	1.498 (2)	C15—H15A	0.9900
C32—H32A	0.9900	C15—H15B	0.9900
C32—H32B	0.9900	C16—C17	1.389 (2)
C33—O5	1.1889 (18)	C16—C21	1.401 (2)
C33—O6	1.3317 (18)	C17—C18	1.375 (2)
C34—O6	1.4534 (19)	C17—H17	0.9500
C34—H34A	0.9800	C18—C19	1.382 (2)
C34—H34B	0.9800	C18—H18	0.9500
C34—H34C	0.9800	C19—C20	1.389 (2)
C1—C2	1.512 (2)	C19—H19	0.9500
C1—C27	1.516 (2)	C20—C21	1.397 (2)
C1—H1A	0.9900	C20—C22	1.516 (2)
C1—H1B	0.9900	C21—O4	1.3569 (17)
C2—C3	1.393 (2)	C22—C23	1.521 (2)
C2—C7	1.398 (2)	C22—H22A	0.9900
C3—C4	1.381 (2)	C22—H22B	0.9900
C3—H3	0.9500	C23—C24	1.390 (2)
C4—C5	1.380 (2)	C23—C28	1.3925 (19)
C4—H4	0.9500	C24—C25	1.381 (2)
C5—C6	1.387 (2)	C24—H24	0.9500
C5—H5	0.9500	C25—C26	1.383 (2)
C6—C7	1.399 (2)	C25—H25	0.9500
C6—C8	1.514 (2)	C26—C27	1.390 (2)
C7—O2	1.3587 (18)	C26—H26	0.9500
C8—C9	1.514 (2)	C27—C28	1.391 (2)
C8—H8A	0.9900	C28—O3	1.4018 (16)
C8—H8B	0.9900	C29—O3	1.4212 (16)
C9—C10	1.388 (2)	C29—C30	1.496 (2)
C9—C14	1.391 (2)	C29—H29A	0.9900
C10—C11	1.382 (2)	C29—H29B	0.9900
C10—H10	0.9500	C30—O7	1.1883 (17)
C11—C12	1.376 (2)	C30—O8	1.3314 (17)
C11—H11	0.9500	O2—H2	0.8400
C12—C13	1.385 (2)	O4—H4A	0.8400
O8—C31—H31A	109.5	C13—C14—C9	122.73 (13)
O8—C31—H31B	109.4	C13—C14—O1	117.55 (13)
H31A—C31—H31B	109.5	C9—C14—O1	119.66 (13)
O8—C31—H31C	109.5	C16—C15—C13	111.63 (12)
H31A—C31—H31C	109.5	C16—C15—H15A	109.3
H31B—C31—H31C	109.5	C13—C15—H15A	109.3
O1—C32—C33	107.43 (12)	C16—C15—H15B	109.3
O1—C32—H32A	110.2	C13—C15—H15B	109.3
C33—C32—H32A	110.2	H15A—C15—H15B	108.0
O1—C32—H32B	110.2	C17—C16—C21	117.99 (15)
C33—C32—H32B	110.2	C17—C16—C15	120.36 (14)
H32A—C32—H32B	108.5	C21—C16—C15	121.64 (14)
O5—C33—O6	125.06 (14)	C18—C17—C16	121.55 (15)
O5—C33—C32	124.77 (14)	C18—C17—H17	119.2
O6—C33—C32	110.16 (13)	C16—C17—H17	119.2
O6—C34—H34A	109.5	C17—C18—C19	119.63 (15)
O6—C34—H34B	109.5	C17—C18—H18	120.2
H34A—C34—H34B	109.5	C19—C18—H18	120.2
O6—C34—H34C	109.5	C18—C19—C20	121.13 (15)
H34A—C34—H34C	109.5	C18—C19—H19	119.4
H34B—C34—H34C	109.5	C20—C19—H19	119.4
C2—C1—C27	113.07 (11)	C19—C20—C21	118.33 (14)
C2—C1—H1A	109.0	C19—C20—C22	120.69 (14)
C27—C1—H1A	109.0	C21—C20—C22	120.98 (13)
C2—C1—H1B	109.0	O4—C21—C20	115.68 (12)
C27—C1—H1B	109.0	O4—C21—C16	122.97 (13)
H1A—C1—H1B	107.8	C20—C21—C16	121.33 (13)
C3—C2—C7	117.80 (14)	C20—C22—C23	113.31 (12)
C3—C2—C1	120.21 (14)	C20—C22—H22A	108.9
C7—C2—C1	121.99 (13)	C23—C22—H22A	108.9
C4—C3—C2	121.75 (16)	C20—C22—H22B	108.9
C4—C3—H3	119.1	C23—C22—H22B	108.9
C2—C3—H3	119.1	H22A—C22—H22B	107.7
C5—C4—C3	119.34 (15)	C24—C23—C28	116.89 (13)
C5—C4—H4	120.3	C24—C23—C22	121.17 (13)
C3—C4—H4	120.3	C28—C23—C22	121.93 (13)
C4—C5—C6	121.18 (15)	C25—C24—C23	121.55 (13)
C4—C5—H5	119.4	C25—C24—H24	119.2
C6—C5—H5	119.4	C23—C24—H24	119.2
C5—C6—C7	118.67 (15)	C24—C25—C26	119.96 (13)
C5—C6—C8	121.39 (14)	C24—C25—H25	120.0
C7—C6—C8	119.93 (14)	C26—C25—H25	120.0
O2—C7—C2	123.64 (13)	C25—C26—C27	120.57 (13)
O2—C7—C6	115.08 (13)	C25—C26—H26	119.7
C2—C7—C6	121.24 (14)	C27—C26—H26	119.7
C9—C8—C6	113.26 (12)	C26—C27—C28	117.88 (12)
C9—C8—H8A	108.9	C26—C27—C1	120.96 (13)
C6—C8—H8A	108.9	C28—C27—C1	121.15 (13)
C9—C8—H8B	108.9	C27—C28—C23	122.91 (13)
C6—C8—H8B	108.9	C27—C28—O3	117.64 (12)
H8A—C8—H8B	107.7	C23—C28—O3	119.42 (12)
C10—C9—C14	117.06 (14)	O3—C29—C30	108.29 (11)
C10—C9—C8	120.24 (14)	O3—C29—H29A	110.0
C14—C9—C8	122.70 (13)	C30—C29—H29A	110.1
C11—C10—C9	121.46 (15)	O3—C29—H29B	110.0
C11—C10—H10	119.3	C30—C29—H29B	110.0
C9—C10—H10	119.3	H29A—C29—H29B	108.4
C12—C11—C10	119.70 (15)	O7—C30—O8	124.88 (13)
C12—C11—H11	120.2	O7—C30—C29	124.97 (13)
C10—C11—H11	120.1	O8—C30—C29	110.13 (12)
C11—C12—C13	121.06 (15)	C7—O2—H2	109.5
C11—C12—H12	119.5	C14—O1—C32	113.33 (10)
C13—C12—H12	119.5	C28—O3—C29	113.38 (10)
C12—C13—C14	117.77 (14)	C21—O4—H4A	109.5
C12—C13—C15	120.40 (14)	C33—O6—C34	115.62 (13)
C14—C13—C15	121.73 (13)	C30—O8—C31	116.11 (12)
O1—C32—C33—O5	−18.6 (2)	C17—C18—C19—C20	−0.3 (3)
O1—C32—C33—O6	162.14 (12)	C18—C19—C20—C21	2.0 (2)
C27—C1—C2—C3	−107.33 (15)	C18—C19—C20—C22	−178.63 (14)
C27—C1—C2—C7	72.80 (18)	C19—C20—C21—O4	176.15 (13)
C7—C2—C3—C4	−0.1 (2)	C22—C20—C21—O4	−3.18 (19)
C1—C2—C3—C4	179.99 (13)	C19—C20—C21—C16	−2.2 (2)
C2—C3—C4—C5	−0.4 (2)	C22—C20—C21—C16	178.52 (13)
C3—C4—C5—C6	0.3 (2)	C17—C16—C21—O4	−177.63 (14)
C4—C5—C6—C7	0.5 (2)	C15—C16—C21—O4	3.1 (2)
C4—C5—C6—C8	179.08 (14)	C17—C16—C21—C20	0.5 (2)
C3—C2—C7—O2	−176.85 (13)	C15—C16—C21—C20	−178.70 (13)
C1—C2—C7—O2	3.0 (2)	C19—C20—C22—C23	99.81 (16)
C3—C2—C7—C6	0.9 (2)	C21—C20—C22—C23	−80.88 (17)
C1—C2—C7—C6	−179.21 (13)	C20—C22—C23—C24	−76.00 (17)
C5—C6—C7—O2	176.84 (13)	C20—C22—C23—C28	102.80 (15)
C8—C6—C7—O2	−1.75 (19)	C28—C23—C24—C25	−2.2 (2)
C5—C6—C7—C2	−1.1 (2)	C22—C23—C24—C25	176.61 (13)
C8—C6—C7—C2	−179.70 (13)	C23—C24—C25—C26	−1.8 (2)
C5—C6—C8—C9	104.44 (16)	C24—C25—C26—C27	3.0 (2)
C7—C6—C8—C9	−77.01 (17)	C25—C26—C27—C28	0.0 (2)
C6—C8—C9—C10	−72.20 (18)	C25—C26—C27—C1	−178.71 (12)
C6—C8—C9—C14	106.82 (16)	C2—C1—C27—C26	80.57 (17)
C14—C9—C10—C11	−0.5 (2)	C2—C1—C27—C28	−98.09 (16)
C8—C9—C10—C11	178.55 (14)	C26—C27—C28—C23	−4.3 (2)
C9—C10—C11—C12	−2.9 (2)	C1—C27—C28—C23	174.40 (12)
C10—C11—C12—C13	2.5 (2)	C26—C27—C28—O3	177.63 (11)
C11—C12—C13—C14	1.5 (2)	C1—C27—C28—O3	−3.67 (18)
C11—C12—C13—C15	−174.99 (14)	C24—C23—C28—C27	5.4 (2)
C12—C13—C14—C9	−5.1 (2)	C22—C23—C28—C27	−173.47 (12)
C15—C13—C14—C9	171.26 (13)	C24—C23—C28—O3	−176.58 (11)
C12—C13—C14—O1	177.63 (12)	C22—C23—C28—O3	4.57 (19)
C15—C13—C14—O1	−6.0 (2)	O3—C29—C30—O7	−18.4 (2)
C10—C9—C14—C13	4.7 (2)	O3—C29—C30—O8	162.94 (11)
C8—C9—C14—C13	−174.40 (13)	C13—C14—O1—C32	−94.09 (15)
C10—C9—C14—O1	−178.17 (12)	C9—C14—O1—C32	88.58 (16)
C8—C9—C14—O1	2.8 (2)	C33—C32—O1—C14	167.04 (12)
C12—C13—C15—C16	77.23 (17)	C27—C28—O3—C29	−95.19 (14)
C14—C13—C15—C16	−99.07 (17)	C23—C28—O3—C29	86.68 (15)
C13—C15—C16—C17	−102.87 (17)	C30—C29—O3—C28	166.48 (11)
C13—C15—C16—C21	76.36 (18)	O5—C33—O6—C34	0.3 (2)
C21—C16—C17—C18	1.3 (2)	C32—C33—O6—C34	179.61 (13)
C15—C16—C17—C18	−179.49 (15)	O7—C30—O8—C31	−0.5 (2)
C16—C17—C18—C19	−1.4 (3)	C29—C30—O8—C31	178.17 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.84	1.92	2.7273 (14)	160
O4—H4A···O1	0.84	1.99	2.7987 (15)	161
O2—H2···O7	0.84	2.88	3.4142 (16)	124
O4—H4A···O5	0.84	2.90	3.4434 (16)	124

(II)

Crystal data

C36H36O8·CH3Cl	F(000) = 748
Mr = 716.02	Dx = 1.397 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 10.027 (2) Å	Cell parameters from 14325 reflections
b = 10.243 (2) Å	θ = 1–27.5°
c = 16.852 (3) Å	µ = 0.32 mm^−1
β = 100.39 (3)°	T = 100 K
V = 1702.6 (6) Å^3	Block, colourless
Z = 2	0.10 × 0.08 × 0.06 mm

Data collection

Nonius KappaCCD area-detector diffractometer	6130 reflections with I > 2σ(I)
ϕ and ω scans	Rint = 0.052
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	θmax = 27.5°, θmin = 2.5°
Tmin = 0.969, Tmax = 0.981	h = −13→13
24715 measured reflections	k = −13→13
7629 independent reflections	l = −21→21

Refinement

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.0566P)^2] where P = (Fo^2 + 2Fc^2)/3
Least-squares matrix: full	(Δ/σ)max = 0.03
R[F^2 > 2σ(F^2)] = 0.041	Δρmax = 0.29 e Å^−3
wR(F^2) = 0.100	Δρmin = −0.25 e Å^−3
S = 0.95	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
7629 reflections	Extinction coefficient: 0.0153 (14)
438 parameters	Absolute structure: Flack (1983)
1 restraint	Absolute structure parameter: −0.10 (4)
H-atom parameters constrained

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.6949 (2)	0.7611 (2)	0.20101 (13)	0.0240 (5)
C2	0.8342 (2)	0.7631 (2)	0.20199 (13)	0.0274 (5)
H2	0.8674	0.7599	0.1527	0.033*
C3	0.9247 (2)	0.7698 (2)	0.27465 (14)	0.0292 (5)
H3	1.0194	0.7721	0.2748	0.035*
C4	0.8776 (2)	0.7730 (2)	0.34662 (13)	0.0263 (5)
H4	0.9407	0.7761	0.3959	0.032*
C5	0.7389 (2)	0.7717 (2)	0.34842 (13)	0.0238 (5)
C6	0.6497 (2)	0.7684 (2)	0.27421 (12)	0.0226 (5)
C7	0.6919 (2)	0.7688 (2)	0.42875 (12)	0.0264 (5)
H7A	0.5927	0.7833	0.4200	0.032*
H7B	0.7363	0.8403	0.4632	0.032*
C8	0.7250 (2)	0.6401 (2)	0.47125 (12)	0.0249 (5)
C9	0.8421 (2)	0.6223 (2)	0.52891 (13)	0.0296 (5)
H9	0.9022	0.6936	0.5433	0.036*
C10	0.8721 (2)	0.5024 (2)	0.56551 (13)	0.0322 (6)
H10	0.9517	0.4918	0.6051	0.039*
C11	0.7860 (2)	0.3987 (3)	0.54424 (13)	0.0305 (5)
H11	0.8070	0.3168	0.5699	0.037*
C12	0.6687 (2)	0.4105 (2)	0.48588 (13)	0.0262 (5)
C13	0.6389 (2)	0.5334 (2)	0.45111 (12)	0.0245 (5)
C14	0.5782 (2)	0.2921 (2)	0.46107 (13)	0.0290 (5)
H14A	0.5970	0.2248	0.5038	0.035*
H14B	0.4821	0.3184	0.4560	0.035*
C15	0.6005 (2)	0.2338 (2)	0.38182 (13)	0.0254 (5)
C16	0.7087 (2)	0.1504 (2)	0.37861 (14)	0.0290 (5)
H16	0.7672	0.1259	0.4271	0.035*
C17	0.7324 (2)	0.1026 (2)	0.30549 (15)	0.0294 (5)
H17	0.8052	0.0437	0.3043	0.035*
C18	0.6502 (2)	0.1404 (2)	0.23423 (15)	0.0285 (5)
H18	0.6687	0.1089	0.1843	0.034*
C19	0.5406 (2)	0.2240 (2)	0.23463 (13)	0.0238 (5)
C20	0.5159 (2)	0.2657 (2)	0.30901 (13)	0.0228 (5)
C21	0.4574 (2)	0.2692 (2)	0.15481 (13)	0.0247 (5)
H21A	0.4350	0.1930	0.1188	0.030*
H21B	0.3712	0.3076	0.1646	0.030*
C22	0.5326 (2)	0.3693 (2)	0.11360 (12)	0.0237 (5)
C23	0.6129 (2)	0.3321 (3)	0.05827 (13)	0.0282 (5)
H23	0.6186	0.2424	0.0449	0.034*
C24	0.6847 (2)	0.4233 (3)	0.02247 (13)	0.0327 (6)
H24	0.7384	0.3967	−0.0157	0.039*
C25	0.6776 (2)	0.5529 (2)	0.04276 (13)	0.0287 (5)
H25	0.7280	0.6151	0.0185	0.034*
C26	0.5990 (2)	0.5956 (2)	0.09756 (12)	0.0238 (5)
C27	0.5261 (2)	0.5019 (2)	0.13216 (12)	0.0214 (5)
C28	0.5985 (2)	0.7382 (2)	0.12169 (13)	0.0259 (5)
H28A	0.5056	0.7643	0.1273	0.031*
H28B	0.6263	0.7928	0.0790	0.031*
C29	0.4400 (2)	0.8813 (2)	0.27686 (16)	0.0342 (6)
H29A	0.4972	0.9550	0.2651	0.041*
H29B	0.4201	0.8933	0.3318	0.041*
C30	0.3107 (2)	0.8790 (2)	0.21677 (13)	0.0242 (5)
C31	0.1150 (3)	0.9994 (3)	0.16073 (15)	0.0449 (7)
H31A	0.0738	0.9115	0.1520	0.054*
H31B	0.1325	1.0320	0.1083	0.054*
C32	0.0213 (3)	1.0874 (3)	0.19128 (15)	0.0377 (6)
H32A	0.0179	1.0651	0.2474	0.057*
H32B	−0.0694	1.0784	0.1584	0.057*
H32C	0.0526	1.1776	0.1884	0.057*
C33	0.2809 (2)	0.2891 (2)	0.31157 (15)	0.0297 (5)
H33A	0.2923	0.2072	0.3433	0.036*
H33B	0.2387	0.2679	0.2553	0.036*
C34	0.1931 (2)	0.3843 (2)	0.34768 (13)	0.0253 (5)
C35	−0.0389 (2)	0.4354 (3)	0.35154 (14)	0.0318 (6)
H35A	−0.0033	0.5245	0.3644	0.038*
H35B	−0.0608	0.3961	0.4013	0.038*
C36	−0.1627 (2)	0.4406 (2)	0.28741 (14)	0.0311 (5)
H36A	−0.1404	0.4820	0.2390	0.047*
H36B	−0.2331	0.4915	0.3068	0.047*
H36C	−0.1958	0.3518	0.2743	0.047*
C37	−0.1481 (2)	1.0586 (2)	−0.07061 (13)	0.0286 (5)
H37	−0.2299	1.1002	−0.1037	0.034*
O1	0.50990 (14)	0.76174 (15)	0.27263 (8)	0.0231 (3)
O2	0.52623 (16)	0.56023 (16)	0.39538 (9)	0.0300 (4)
H2A	0.4816	0.4913	0.3837	0.045*
O3	0.40849 (14)	0.35053 (15)	0.31349 (9)	0.0232 (3)
O4	0.44131 (15)	0.53302 (15)	0.18481 (9)	0.0255 (3)
H4A	0.4662	0.6039	0.2079	0.038*
O5	0.27314 (19)	0.7906 (2)	0.17372 (12)	0.0494 (5)
O6	0.24262 (17)	0.99057 (17)	0.21792 (10)	0.0361 (4)
O7	0.23446 (16)	0.46840 (19)	0.39445 (10)	0.0375 (4)
O8	0.06216 (15)	0.35562 (16)	0.32079 (9)	0.0276 (4)
Cl1	−0.06484 (8)	0.96828 (8)	−0.13453 (5)	0.0563 (2)
Cl2	−0.04219 (6)	1.18233 (6)	−0.02198 (3)	0.03249 (15)
Cl3	−0.20159 (7)	0.95519 (7)	0.00142 (4)	0.04352 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0228 (12)	0.0183 (11)	0.0297 (11)	−0.0010 (10)	0.0012 (9)	0.0036 (9)
C2	0.0266 (13)	0.0247 (12)	0.0301 (12)	−0.0023 (10)	0.0032 (10)	0.0045 (10)
C3	0.0196 (12)	0.0263 (13)	0.0407 (13)	−0.0040 (10)	0.0028 (10)	0.0049 (11)
C4	0.0230 (12)	0.0187 (12)	0.0341 (12)	0.0026 (10)	−0.0030 (9)	0.0001 (10)
C5	0.0226 (12)	0.0158 (11)	0.0307 (12)	−0.0004 (9)	−0.0009 (9)	−0.0023 (9)
C6	0.0197 (12)	0.0163 (11)	0.0303 (12)	−0.0004 (9)	0.0000 (9)	0.0010 (9)
C7	0.0247 (12)	0.0286 (13)	0.0239 (11)	0.0027 (11)	−0.0012 (9)	−0.0040 (10)
C8	0.0241 (12)	0.0305 (13)	0.0197 (10)	0.0046 (10)	0.0032 (8)	−0.0047 (9)
C9	0.0278 (13)	0.0342 (14)	0.0249 (11)	0.0042 (11)	−0.0005 (9)	−0.0082 (10)
C10	0.0316 (14)	0.0389 (15)	0.0225 (11)	0.0105 (12)	−0.0048 (10)	−0.0056 (10)
C11	0.0327 (14)	0.0348 (14)	0.0236 (12)	0.0084 (11)	0.0036 (10)	0.0019 (10)
C12	0.0252 (12)	0.0334 (13)	0.0209 (11)	0.0026 (10)	0.0062 (9)	0.0015 (9)
C13	0.0190 (12)	0.0325 (14)	0.0213 (11)	0.0065 (10)	0.0018 (8)	−0.0003 (9)
C14	0.0276 (13)	0.0314 (14)	0.0281 (12)	0.0048 (11)	0.0051 (9)	0.0097 (10)
C15	0.0219 (12)	0.0214 (12)	0.0325 (12)	−0.0024 (9)	0.0043 (9)	0.0069 (9)
C16	0.0207 (12)	0.0239 (13)	0.0411 (14)	0.0008 (10)	0.0022 (10)	0.0093 (10)
C17	0.0215 (12)	0.0202 (12)	0.0476 (15)	0.0010 (10)	0.0094 (10)	0.0035 (10)
C18	0.0245 (13)	0.0229 (13)	0.0384 (13)	−0.0016 (10)	0.0065 (10)	−0.0012 (10)
C19	0.0218 (12)	0.0163 (11)	0.0334 (12)	−0.0036 (9)	0.0055 (9)	−0.0019 (9)
C20	0.0166 (11)	0.0170 (11)	0.0354 (12)	0.0012 (9)	0.0065 (9)	0.0026 (9)
C21	0.0210 (11)	0.0235 (12)	0.0287 (11)	0.0002 (10)	0.0022 (9)	−0.0076 (9)
C22	0.0203 (12)	0.0295 (14)	0.0196 (11)	0.0000 (10)	−0.0015 (8)	−0.0020 (9)
C23	0.0245 (13)	0.0325 (14)	0.0268 (12)	0.0035 (10)	0.0027 (9)	−0.0094 (10)
C24	0.0299 (14)	0.0478 (17)	0.0218 (11)	0.0041 (12)	0.0087 (10)	−0.0018 (10)
C25	0.0239 (13)	0.0379 (15)	0.0243 (12)	−0.0025 (11)	0.0041 (9)	0.0026 (10)
C26	0.0208 (12)	0.0295 (13)	0.0199 (11)	−0.0006 (10)	0.0003 (9)	0.0013 (9)
C27	0.0170 (11)	0.0283 (13)	0.0178 (10)	0.0029 (9)	0.0003 (8)	−0.0012 (9)
C28	0.0231 (12)	0.0282 (13)	0.0257 (11)	−0.0020 (10)	0.0024 (9)	0.0076 (9)
C29	0.0254 (13)	0.0252 (14)	0.0486 (15)	0.0066 (11)	−0.0024 (11)	−0.0081 (11)
C30	0.0212 (12)	0.0232 (13)	0.0284 (12)	0.0039 (10)	0.0051 (9)	0.0017 (10)
C31	0.0337 (15)	0.065 (2)	0.0325 (14)	0.0191 (14)	−0.0035 (11)	−0.0030 (13)
C32	0.0310 (14)	0.0409 (16)	0.0392 (15)	0.0032 (12)	0.0010 (11)	−0.0085 (12)
C33	0.0200 (12)	0.0278 (14)	0.0419 (14)	−0.0019 (11)	0.0078 (10)	−0.0031 (10)
C34	0.0203 (12)	0.0269 (13)	0.0292 (12)	0.0013 (10)	0.0059 (9)	0.0066 (10)
C35	0.0235 (13)	0.0353 (15)	0.0383 (13)	0.0063 (11)	0.0096 (10)	−0.0036 (11)
C36	0.0236 (13)	0.0281 (14)	0.0416 (14)	0.0009 (11)	0.0060 (10)	0.0021 (11)
C37	0.0260 (13)	0.0302 (14)	0.0289 (12)	−0.0030 (11)	0.0028 (10)	0.0018 (10)
O1	0.0162 (8)	0.0204 (8)	0.0315 (8)	0.0017 (6)	0.0010 (6)	0.0001 (7)
O2	0.0255 (9)	0.0275 (9)	0.0325 (9)	−0.0018 (7)	−0.0065 (7)	0.0043 (7)
O3	0.0163 (8)	0.0221 (8)	0.0312 (8)	−0.0001 (7)	0.0047 (6)	0.0020 (6)
O4	0.0257 (9)	0.0227 (9)	0.0300 (8)	−0.0027 (7)	0.0101 (6)	−0.0035 (6)
O5	0.0357 (11)	0.0448 (12)	0.0581 (12)	0.0122 (9)	−0.0175 (9)	−0.0221 (10)
O6	0.0283 (9)	0.0329 (11)	0.0440 (10)	0.0110 (8)	−0.0016 (7)	−0.0010 (8)
O7	0.0258 (9)	0.0458 (11)	0.0405 (10)	−0.0011 (9)	0.0046 (7)	−0.0167 (9)
O8	0.0192 (8)	0.0278 (9)	0.0360 (9)	0.0025 (7)	0.0056 (6)	−0.0012 (7)
Cl1	0.0497 (4)	0.0625 (5)	0.0613 (5)	−0.0083 (4)	0.0224 (3)	−0.0275 (4)
Cl2	0.0317 (3)	0.0304 (3)	0.0330 (3)	−0.0039 (3)	−0.0004 (2)	0.0026 (2)
Cl3	0.0426 (4)	0.0462 (4)	0.0388 (3)	−0.0154 (3)	−0.0004 (3)	0.0137 (3)

Geometric parameters (Å, º)

C1—C6	1.390 (3)	C22—C27	1.398 (3)
C1—C2	1.395 (3)	C23—C24	1.382 (4)
C1—C28	1.520 (3)	C23—H23	0.9500
C2—C3	1.388 (3)	C24—C25	1.376 (4)
C2—H2	0.9500	C24—H24	0.9500
C3—C4	1.379 (3)	C25—C26	1.388 (3)
C3—H3	0.9500	C25—H25	0.9500
C4—C5	1.396 (3)	C26—C27	1.396 (3)
C4—H4	0.9500	C26—C28	1.517 (3)
C5—C6	1.401 (3)	C27—O4	1.372 (3)
C5—C7	1.512 (3)	C28—H28A	0.9900
C6—O1	1.399 (3)	C28—H28B	0.9900
C7—C8	1.508 (3)	C29—O1	1.419 (3)
C7—H7A	0.9900	C29—C30	1.495 (3)
C7—H7B	0.9900	C29—H29A	0.9900
C8—C9	1.395 (3)	C29—H29B	0.9900
C8—C13	1.396 (3)	C30—O5	1.179 (3)
C9—C10	1.382 (3)	C30—O6	1.333 (3)
C9—H9	0.9500	C31—O6	1.459 (3)
C10—C11	1.375 (4)	C31—C32	1.461 (4)
C10—H10	0.9500	C31—H31A	0.9900
C11—C12	1.396 (3)	C31—H31B	0.9900
C11—H11	0.9500	C32—H32A	0.9800
C12—C13	1.398 (3)	C32—H32B	0.9800
C12—C14	1.527 (3)	C32—H32C	0.9800
C13—O2	1.360 (3)	C33—O3	1.421 (3)
C14—C15	1.516 (3)	C33—C34	1.513 (3)
C14—H14A	0.9900	C33—H33A	0.9900
C14—H14B	0.9900	C33—H33B	0.9900
C15—C16	1.390 (3)	C34—O7	1.191 (3)
C15—C20	1.399 (3)	C34—O8	1.342 (3)
C16—C17	1.386 (3)	C35—O8	1.467 (3)
C16—H16	0.9500	C35—C36	1.492 (3)
C17—C18	1.384 (3)	C35—H35A	0.9900
C17—H17	0.9500	C35—H35B	0.9900
C18—C19	1.395 (3)	C36—H36A	0.9800
C18—H18	0.9500	C36—H36B	0.9800
C19—C20	1.388 (3)	C36—H36C	0.9800
C19—C21	1.522 (3)	C37—Cl1	1.743 (2)
C20—O3	1.396 (3)	C37—Cl2	1.758 (2)
C21—C22	1.514 (3)	C37—Cl3	1.766 (2)
C21—H21A	0.9900	C37—H37	1.0000
C21—H21B	0.9900	O2—H2A	0.8400
C22—C23	1.391 (3)	O4—H4A	0.8400
C6—C1—C2	118.32 (19)	C24—C23—C22	121.2 (2)
C6—C1—C28	122.12 (19)	C24—C23—H23	119.4
C2—C1—C28	119.3 (2)	C22—C23—H23	119.4
C3—C2—C1	120.3 (2)	C25—C24—C23	119.3 (2)
C3—C2—H2	119.8	C25—C24—H24	120.4
C1—C2—H2	119.8	C23—C24—H24	120.4
C4—C3—C2	120.3 (2)	C24—C25—C26	122.0 (2)
C4—C3—H3	119.9	C24—C25—H25	119.0
C2—C3—H3	119.9	C26—C25—H25	119.0
C3—C4—C5	121.3 (2)	C25—C26—C27	117.7 (2)
C3—C4—H4	119.4	C25—C26—C28	120.8 (2)
C5—C4—H4	119.4	C27—C26—C28	121.51 (19)
C4—C5—C6	117.3 (2)	O4—C27—C26	122.9 (2)
C4—C5—C7	119.48 (19)	O4—C27—C22	115.5 (2)
C6—C5—C7	123.2 (2)	C26—C27—C22	121.7 (2)
C1—C6—C5	122.4 (2)	C26—C28—C1	110.62 (18)
C1—C6—O1	117.76 (18)	C26—C28—H28A	109.5
C5—C6—O1	119.64 (19)	C1—C28—H28A	109.5
C5—C7—C8	111.43 (18)	C26—C28—H28B	109.5
C5—C7—H7A	109.3	C1—C28—H28B	109.5
C8—C7—H7A	109.3	H28A—C28—H28B	108.1
C5—C7—H7B	109.3	O1—C29—C30	109.17 (19)
C8—C7—H7B	109.3	O1—C29—H29A	109.8
H7A—C7—H7B	108.0	C30—C29—H29A	109.8
C9—C8—C13	118.2 (2)	O1—C29—H29B	109.8
C9—C8—C7	122.1 (2)	C30—C29—H29B	109.8
C13—C8—C7	119.67 (19)	H29A—C29—H29B	108.3
C10—C9—C8	121.0 (2)	O5—C30—O6	124.1 (2)
C10—C9—H9	119.5	O5—C30—C29	124.8 (2)
C8—C9—H9	119.5	O6—C30—C29	111.13 (19)
C11—C10—C9	119.6 (2)	O6—C31—C32	110.4 (2)
C11—C10—H10	120.2	O6—C31—H31A	109.6
C9—C10—H10	120.2	C32—C31—H31A	109.6
C10—C11—C12	121.7 (2)	O6—C31—H31B	109.6
C10—C11—H11	119.1	C32—C31—H31B	109.6
C12—C11—H11	119.1	H31A—C31—H31B	108.1
C13—C12—C11	117.5 (2)	C31—C32—H32A	109.5
C13—C12—C14	122.0 (2)	C31—C32—H32B	109.5
C11—C12—C14	120.5 (2)	H32A—C32—H32B	109.5
O2—C13—C12	124.0 (2)	C31—C32—H32C	109.5
O2—C13—C8	114.2 (2)	H32A—C32—H32C	109.5
C12—C13—C8	121.8 (2)	H32B—C32—H32C	109.5
C15—C14—C12	112.28 (18)	O3—C33—C34	107.01 (19)
C15—C14—H14A	109.1	O3—C33—H33A	110.3
C12—C14—H14A	109.1	C34—C33—H33A	110.3
C15—C14—H14B	109.1	O3—C33—H33B	110.3
C12—C14—H14B	109.1	C34—C33—H33B	110.3
H14A—C14—H14B	107.9	H33A—C33—H33B	108.6
C16—C15—C20	117.6 (2)	O7—C34—O8	125.8 (2)
C16—C15—C14	121.1 (2)	O7—C34—C33	125.0 (2)
C20—C15—C14	121.2 (2)	O8—C34—C33	109.2 (2)
C17—C16—C15	120.8 (2)	O8—C35—C36	107.53 (18)
C17—C16—H16	119.6	O8—C35—H35A	110.2
C15—C16—H16	119.6	C36—C35—H35A	110.2
C18—C17—C16	120.1 (2)	O8—C35—H35B	110.2
C18—C17—H17	119.9	C36—C35—H35B	110.2
C16—C17—H17	119.9	H35A—C35—H35B	108.5
C17—C18—C19	121.0 (2)	C35—C36—H36A	109.5
C17—C18—H18	119.5	C35—C36—H36B	109.5
C19—C18—H18	119.5	H36A—C36—H36B	109.5
C20—C19—C18	117.5 (2)	C35—C36—H36C	109.5
C20—C19—C21	123.1 (2)	H36A—C36—H36C	109.5
C18—C19—C21	119.3 (2)	H36B—C36—H36C	109.5
C19—C20—O3	120.34 (19)	Cl1—C37—Cl2	110.74 (13)
C19—C20—C15	122.8 (2)	Cl1—C37—Cl3	110.17 (14)
O3—C20—C15	116.72 (19)	Cl2—C37—Cl3	110.17 (12)
C22—C21—C19	111.87 (18)	Cl1—C37—H37	108.6
C22—C21—H21A	109.2	Cl2—C37—H37	108.6
C19—C21—H21A	109.2	Cl3—C37—H37	108.6
C22—C21—H21B	109.2	C6—O1—C29	117.35 (17)
C19—C21—H21B	109.2	C13—O2—H2A	109.5
H21A—C21—H21B	107.9	C20—O3—C33	115.05 (17)
C23—C22—C27	118.2 (2)	C27—O4—H4A	109.5
C23—C22—C21	121.2 (2)	C30—O6—C31	115.7 (2)
C27—C22—C21	120.5 (2)	C34—O8—C35	117.06 (18)
C6—C1—C2—C3	1.2 (3)	C18—C19—C20—C15	4.1 (3)
C28—C1—C2—C3	−173.1 (2)	C21—C19—C20—C15	−173.7 (2)
C1—C2—C3—C4	0.8 (4)	C16—C15—C20—C19	−4.0 (3)
C2—C3—C4—C5	−1.0 (4)	C14—C15—C20—C19	173.8 (2)
C3—C4—C5—C6	−0.6 (3)	C16—C15—C20—O3	−179.5 (2)
C3—C4—C5—C7	177.1 (2)	C14—C15—C20—O3	−1.7 (3)
C2—C1—C6—C5	−2.9 (3)	C20—C19—C21—C22	104.0 (2)
C28—C1—C6—C5	171.2 (2)	C18—C19—C21—C22	−73.7 (3)
C2—C1—C6—O1	−177.8 (2)	C19—C21—C22—C23	91.8 (2)
C28—C1—C6—O1	−3.8 (3)	C19—C21—C22—C27	−86.3 (2)
C4—C5—C6—C1	2.6 (3)	C27—C22—C23—C24	0.1 (3)
C7—C5—C6—C1	−175.0 (2)	C21—C22—C23—C24	−178.1 (2)
C4—C5—C6—O1	177.45 (19)	C22—C23—C24—C25	0.8 (3)
C7—C5—C6—O1	−0.1 (3)	C23—C24—C25—C26	−0.8 (4)
C4—C5—C7—C8	−68.5 (3)	C24—C25—C26—C27	0.0 (3)
C6—C5—C7—C8	109.0 (2)	C24—C25—C26—C28	177.1 (2)
C5—C7—C8—C9	95.3 (2)	C25—C26—C27—O4	−177.6 (2)
C5—C7—C8—C13	−82.6 (3)	C28—C26—C27—O4	5.4 (3)
C13—C8—C9—C10	−0.3 (3)	C25—C26—C27—C22	0.9 (3)
C7—C8—C9—C10	−178.3 (2)	C28—C26—C27—C22	−176.2 (2)
C8—C9—C10—C11	0.7 (4)	C23—C22—C27—O4	177.69 (18)
C9—C10—C11—C12	0.4 (4)	C21—C22—C27—O4	−4.2 (3)
C10—C11—C12—C13	−1.9 (3)	C23—C22—C27—C26	−0.9 (3)
C10—C11—C12—C14	177.5 (2)	C21—C22—C27—C26	177.26 (19)
C11—C12—C13—O2	−178.0 (2)	C25—C26—C28—C1	−97.6 (2)
C14—C12—C13—O2	2.7 (3)	C27—C26—C28—C1	79.3 (3)
C11—C12—C13—C8	2.3 (3)	C6—C1—C28—C26	−98.7 (3)
C14—C12—C13—C8	−177.0 (2)	C2—C1—C28—C26	75.3 (3)
C9—C8—C13—O2	179.02 (19)	O1—C29—C30—O5	0.8 (3)
C7—C8—C13—O2	−2.9 (3)	O1—C29—C30—O6	−179.08 (18)
C9—C8—C13—C12	−1.3 (3)	O3—C33—C34—O7	−25.3 (3)
C7—C8—C13—C12	176.8 (2)	O3—C33—C34—O8	156.88 (17)
C13—C12—C14—C15	78.2 (3)	C1—C6—O1—C29	−98.8 (2)
C11—C12—C14—C15	−101.2 (2)	C5—C6—O1—C29	86.2 (3)
C12—C14—C15—C16	80.8 (3)	C30—C29—O1—C6	136.33 (19)
C12—C14—C15—C20	−96.9 (2)	C19—C20—O3—C33	85.3 (2)
C20—C15—C16—C17	1.0 (3)	C15—C20—O3—C33	−99.1 (2)
C14—C15—C16—C17	−176.8 (2)	C34—C33—O3—C20	159.09 (18)
C15—C16—C17—C18	1.8 (4)	O5—C30—O6—C31	−0.6 (3)
C16—C17—C18—C19	−1.7 (4)	C29—C30—O6—C31	179.4 (2)
C17—C18—C19—C20	−1.2 (3)	C32—C31—O6—C30	152.1 (2)
C17—C18—C19—C21	176.7 (2)	O7—C34—O8—C35	0.3 (3)
C18—C19—C20—O3	179.40 (19)	C33—C34—O8—C35	178.09 (19)
C21—C19—C20—O3	1.7 (3)	C36—C35—O8—C34	149.92 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O3	0.84	1.92	2.706 (2)	154
O2—H2A···O7	0.84	2.53	3.071 (2)	123
O4—H4A···O1	0.84	1.96	2.790 (2)	172
O4—H4A···O5	0.84	2.71	3.119 (3)	112