Methoxy-ether and crown-ether ­derivatives of tetrahomodioxa- and octahomotetraoxacalix­[4]­arenes

Three methoxy­-ether and one methoxy-­ether/crown-ether derivatives of p-tert-butyl­tetrahomodioxa- and p-R-octahomo­tetraoxacalix­[4]­arenes (R = methyl, tert-butyl, H) have been investigated. The first three compounds, 7,15,21,27-tetra-tert-butyl-29,30,31,32-tetra­methoxy-3,11-dioxapenta­cyclo­[23.3.­1.1^5,9.1^13,17.1^19,23]­ditriaconta-1(29),5,7,­9(30),­13,15,-17(31),­19,21,23(32),25,27-dodecaene, C₅₀H₆₈O₆, 33,34,35,36-tetra­methoxy-7,15,23,31-tetra­methyl-3,11,19,27-tetra­oxa­penta­cyclo[27.3.1.1^5,9.1^13,17.1^21,25]­hexa­tri­aconta-1(33),5,7,9(34),13,15,­17(35),21,23,25(36),29,31-dodecaene, C₄₀H₄₈O₈, and 7,23-di-tert-butyl-33,34,35,36-tetra­methoxy-3,11,19,27-tetraoxapenta­cyclo­[27.3.1.1^5,9.1^13,17.1^21,25]­hexatriaconta-1(33),5,7,9(34),13,15,­17(35),- 21,23,25(36),29,31-dodecaene, C₄₄H₅₆O₈, in the partial-cone or 1,2-alternate conformations, present the common feature of methoxy-­ether self-inclusion, while the fourth, 42,43-di­methoxy-7,15,23,31-tetra­methyl-3,11,19,27,34,37,40-heptaoxahexa­cyclo[15.15.9.1^5,9.1^21,25.0^13,41.0^29,33]­tritetra­conta-5(42),6,8,13(41),­14,16,21(43),22,24,29(33),30,32-dodecaene, C₄₂H₅₀O₉, adopts the 1,3-alternate conformation owing to the presence of a 1,3-polyether chain.

S1. Comment

Homooxacalixarenes are expanded calixarenes in which at least one methylene C atom is replaced by an ether –CH₂—O—CH₂– bridge (Masci, 2001). In the course of our investigation of the crystal structures of homooxacalix[n]arenes (n = 3–8) and of their uranyl ion complexes (Thuéry et al., 1999; Thuéry, Nierlich, Vicens, Masci & Takemura et al., 2001; Thuéry et al., 2001a,b,c) or O-substituted derivatives (Oueslati et al., 2001), we have synthesized four methoxyether and one methoxyether/crown-ether derivatives, the structures of which are reported herein. Two different homooxacalixarene skeletons have been used: tetrahomodioxacalix[4]arene and the larger octahomotetraoxacalix[4]arene, denoted [3.3.1.1]- and [3.3.3.3]-homooxacalixarene, respectively, in the notation of Masci et al. (1998). The three first compounds bear four methoxyether groups, with different homooxacalixarene cores: p-tert-butyltetrahomodioxacalix[4]arene, (I), p-methyloctahomotetraoxacalix[4]arene, (II), and octahomotetraoxacalix[4]arene with two diametrically located p-tert-butyl groups only (III). The last compound, (IV), features two methoxyether groups and a –O-(CH₂)₂-O-(CH₂)₂-O– bridge linking two opposite phenolic units of p-methyloctahomotetraoxacalix[4]arene. \sch

The asymmetric unit in (I) is composed of one calixarene molecule, which adopts a partial cone conformation, the three phenolic rings bound by methylene bridges being in cone conformation, and the last one, bound to the others by the ether bridges, being turned upside-down. The definition of a proper reference plane for homooxacalixarene molecules is not as straightforward as in classical small calixarenes. In compound (I), the six C atoms of the bridges define a plane with a highest deviation of 0.311 (3) Å, which can be used as a reference plane. The dihedral angles between this plane and those defined by the four aromatic rings are 80.85 (6), 53.52 (6), 84.87 (6) and 38.36 (6)°, which indicates that the reversed phenolic ring is closer to the mean plane than the three other ones. In the notation of Kanamathareddy & Gutsche (1993), this conformation can be denoted as (u, u, u, do). As a result, the methoxyether substituent bound to this last ring is subject to self-inclusion, being directed towards the cavity centre. Such a self-inclusion phenomenon, which will be encountered also with compounds (II) and (III), has previously been observed with ester substituents in another compound of the same family, tetrahomodioxacalix[6]arene (Oueslati et al., 2001). In calix[6]arene derivatives, the self-inclusion of three 1,3,5-methoxy groups was ascribed to weak CH···π interactions (van Duynhoven et al., 1994). Such interactions have however been questioned in the case of a calix[4]arene derivative presenting a similar self-inclusion (Harrowfield et al., 1994). In the present case, there is no H atom···ring centroid distance shorter than 3.15 Å, which precludes any CH···π interaction (Jeffrey & Saenger, 1994). As previously noted, two kinds of ether links can be distinguished in this family of compounds, corresponding to anti/anti or to anti/gauche C—O—C—C torsion angles (Thuéry et al., 2001 d). Both bridges in (I) are of the second type [80.4 (3) and -174.0 (2)° around O4, 165.9 (2) and -81.2 (3)° around O6].

The centrosymmetric molecule (II), with four ether linkages, is in the 1,2-alternate conformation. The best reference plane in this compound, as well as in the two following ones, is given by the four ether O atoms. The dihedral angles between this plane and the two aromatic rings are 22.77 (7) and 81.97 (5)°, indicating a (u, uo, d, do) conformation. The two methoxyether substituents of the rings closer to the mean plane are self-included, with a shorter distance C8···C13' of 3.727 (3) Å (symmetry code: ' = 1 - x, -y, -z). There is no H atom···ring centroid distance shorter than 3.05 Å. C8 is not equally distant from the two nearest aromatic rings, the distortion of the calixarene being due to different ether bridge conformations. The bridge containing O2 is of the anti/anti type [torsion angles -176.1 (2) and 176.6 (2)°] whereas that containing O4 is of the anti/gauche type [-172.3 (2) and 82.3 (2)°]. The latter brings C8 in closer proximity to the bound aromatic ring than the former.

The main overall shape is encountered in compound (III), in which the molecule does not possess any crystallographic symmetry. The conformation is 1,2-alternate, but even more irregular than in compound (II). The four ether O atoms of the ring define a plane with a maximum deviation of 0.084 (2) Å, which cuts the four planes defined by the aromatic rings with dihedral angles of 81.06 (6), 32.00 (5), 85.45 (6) and 31.74 (5)°. In this case also, the methoxyether groups of the two rings closer to the reference plane (which are those without p-tert-butyl substituent) are self-included, with no H atom···ring centroid distance shorter than 3.13 Å. One of the ether bridges is different from the three other ones, which brokes the pseudo-symmetry centre of the molecule. The bridges associated with O2, O4 and O8 are of the anti/gauche type [torsion angles 72.6 (3) and -174.1 (2)° around O2, 173.0 (2) and -84.4 (3)° around O4, 175.7 (2) and 81.9 (3)° around O8], whereas the bridge containing O6 is of the anti/anti type [-179.7 (2) and -177.4 (3)°]. One of the H atom···ring centroid distance, involving the C36—C41 ring and a methoxy hydrogen atom of a neighbouring molecule, is 2.42 Å and can be considered, on geometrical basis, to indicate a possible CH···π interaction.

The situation in compound (IV) is quite different. This molecule, related to the calixcrown family, for which a lot of structural information has been gathered (Thuéry et al., 2000 and references therein), lacks any symmetry element and is in the 1,3-alternate conformation. The plane defined by the four ether O atoms has a maximum deviation of 0.580 (2) Å, but will be considered as the reference plane in spite of this large value in the absence of any better choice. The dihedral angles between this plane and those defined by the aromatic rings are 48.58 (7), 79.73 (7), 48.97 (6) and 80.56 (8)°, the rings closer to the mean plane being those linked by the polyether bridge O1···O3. The two methoxyether groups are therefore directed away from the cavity. Two out of the four ether bridges, diametrically located, correspond to usual anti/gauche conformations [torsion angles -174.9 (2) and -79.9 (3)° around O4, -177.3 (2) and -72.7 (3)° around O7], but the two other ones correspond to a third type not encountered up to now in this family of compounds, which is gauche/gauche [73.1 (3) and 72.9 (3)° around O6, 78.8 (3) and 70.0 (3)° around O9]. This unusual conformation is likely due to the constraints arising from the O1···O3 polyether link bridging two aromatic rings. A self-inclusion phenomenon, different from the one observed in the previous compounds and involving two molecules related by the symmetry centre, appears in the packing. The p-methyl C atom C30 of each molecule is included between the two polyether-linked aromatic rings of the neighbouring molecule, giving rise to dimers with shortest contacts between C30 and C7'' [3.480 (4) Å, symmetry code: '' = 2 - x, -y, -z] and O1'' [3.419 (4) Å]. However, there is no H atom···ring centroid distance shorter than 3.00 Å. It has been shown that calix[4]arene-mono- or bis-(crown-6) s in the 1,3-alternate conformation were selective extractants for caesium ions (Ungaro et al., 1994; Asfari et al., 1995). However, it is doubtful that, even provided with an adequate polyether link containing six O atoms, compounds like (IV) could be better extractants than the latter compounds, owing to the increased cavity size and flexibility.

Related literature

For related literature, see: Asfari et al. (1995); Duynhoven et al. (1994); Harrowfield et al. (1994); Jeffrey & Saenger (1994); Kanamathareddy & Gutsche (1993); Masci (2001); Masci & Saccheo (1993); Masci et al. (1998); Oueslati et al. (2001); Thuéry et al. (1999, 2000, 2001); Ungaro et al. (1994).

S2. Experimental

Compound (I) was synthesized as reported elsewhere (Masci et al., 1998). Compounds (II) and (IV) were also obtained as previously reported (Masci & Saccheo, 1993). Compound (III) was synthesized as reported for (II), from 2,6-bis(bromomethyl)anisole and 2,6-bis(hydroxymethyl)-4-tert-butylanisole (yield 12%, m.p. 475–476 K).

S3. Refinement

All H atoms were introduced at calculated positions as riding atoms with a displacement parameter equal to 1.2 (CH, CH₂) or 1.5 (CH₃) times that of the parent atom.

Computing details

For all compounds, data collection: Kappa-CCD Software (Nonius, 1998); 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 (Sheldrick, 1999); software used to prepare material for publication: SHELXTL and PARST97 (Nardelli, 1995).

Figures

	Fig. 1. Molecule (I) with the atomic numbering scheme. H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Molecule (II) with the atomic numbering scheme. H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level (symmetry code: ' = 1 - x, -y, -z).
	Fig. 3. Molecule (III) with the atomic numbering scheme. H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 4. Molecule (IV) with the atomic numbering scheme. H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level.

(I)

Crystal data

C50H68O6	Z = 2
Mr = 765.04	F(000) = 832
Triclinic, P1	Dx = 1.118 Mg m^−3
a = 11.3148 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.2488 (5) Å	Cell parameters from 17232 reflections
c = 15.3512 (11) Å	θ = 2.7–25.7°
α = 84.280 (4)°	µ = 0.07 mm^−1
β = 69.132 (2)°	T = 100 K
γ = 79.683 (4)°	Parallelepipedic, colourless
V = 2273.5 (2) Å^3	0.25 × 0.25 × 0.25 mm

Data collection

Nonius Kappa-CCD diffractometer	5246 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.072
Graphite monochromator	θmax = 25.7°, θmin = 2.7°
Detector resolution: 18 pixels mm^-1	h = 0→13
ϕ scans	k = −14→15
7972 measured reflections	l = −17→18
7972 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0533P)^2 + 1.6661P] where P = (Fo^2 + 2Fc^2)/3
7972 reflections	(Δ/σ)max < 0.001
521 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

Experimental. crystal-to-detector distance 28 mm

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 expanded by subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atoms were introduced at calculated positions as riding atoms with an isotropic displacement parameter equal to 1.2 (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	0.28292 (17)	0.94163 (12)	0.34605 (12)	0.0318 (4)
O2	0.03724 (16)	0.75319 (11)	0.43538 (12)	0.0268 (4)
O3	−0.32777 (17)	0.77399 (12)	0.51535 (12)	0.0285 (4)
O4	−0.39710 (17)	0.98518 (12)	0.39958 (12)	0.0294 (4)
O5	−0.0965 (2)	1.00563 (12)	0.21553 (13)	0.0389 (5)
O6	0.12367 (17)	1.12625 (12)	0.25967 (12)	0.0316 (4)
C1	0.2751 (2)	0.98587 (18)	0.19222 (18)	0.0287 (6)
C2	0.2807 (2)	0.91539 (18)	0.26177 (17)	0.0262 (6)
C3	0.2900 (2)	0.81941 (17)	0.24577 (18)	0.0258 (6)
C4	0.2898 (2)	0.79566 (18)	0.15980 (18)	0.0269 (6)
H4	0.2932	0.7319	0.1494	0.032*
C5	0.2845 (2)	0.86360 (18)	0.08882 (17)	0.0273 (6)
C6	0.2799 (3)	0.95836 (18)	0.10687 (18)	0.0302 (6)
H6	0.2801	1.0049	0.0598	0.036*
C7	0.2805 (3)	0.83782 (19)	−0.00448 (18)	0.0342 (6)
C8	0.4039 (3)	0.8581 (2)	−0.0830 (2)	0.0539 (9)
H8A	0.4101	0.9246	−0.0852	0.081*
H8B	0.4021	0.8415	−0.1415	0.081*
H8C	0.4765	0.8207	−0.0712	0.081*
C9	0.1635 (4)	0.8991 (2)	−0.0219 (2)	0.0566 (9)
H9A	0.1741	0.9651	−0.0291	0.085*
H9B	0.0874	0.8907	0.0302	0.085*
H9C	0.1561	0.8795	−0.0775	0.085*
C10	0.2691 (3)	0.7331 (2)	−0.0064 (2)	0.0458 (8)
H10A	0.2680	0.7204	−0.0663	0.069*
H10B	0.1913	0.7196	0.0412	0.069*
H10C	0.3409	0.6936	0.0047	0.069*
C11	0.1597 (3)	0.9603 (2)	0.41790 (19)	0.0353 (7)
H11A	0.1136	1.0194	0.4030	0.053*
H11B	0.1706	0.9647	0.4765	0.053*
H11C	0.1124	0.9093	0.4222	0.053*
C12	0.3015 (3)	0.74117 (17)	0.31939 (18)	0.0278 (6)
H12A	0.3906	0.7127	0.3043	0.033*
H12B	0.2737	0.7696	0.3797	0.033*
C13	0.2226 (2)	0.66389 (17)	0.32578 (17)	0.0262 (6)
C14	0.0938 (2)	0.67313 (17)	0.38135 (17)	0.0247 (5)
C15	0.0168 (2)	0.60630 (17)	0.38159 (17)	0.0252 (6)
C16	0.0739 (2)	0.52869 (18)	0.32490 (17)	0.0275 (6)
H16	0.0245	0.4827	0.3260	0.033*
C17	0.2020 (2)	0.51653 (17)	0.26642 (18)	0.0274 (6)
C18	0.2749 (3)	0.58457 (17)	0.26968 (17)	0.0272 (6)
H18	0.3613	0.5770	0.2333	0.033*
C19	0.2561 (3)	0.43263 (18)	0.20080 (18)	0.0305 (6)
C20	0.3904 (3)	0.4396 (2)	0.1320 (2)	0.0380 (7)
H20A	0.3893	0.4987	0.0961	0.057*
H20B	0.4185	0.3872	0.0910	0.057*
H20C	0.4480	0.4374	0.1657	0.057*
C21	0.1690 (3)	0.4313 (2)	0.1440 (2)	0.0441 (8)
H21A	0.1685	0.4889	0.1059	0.066*
H21B	0.0836	0.4267	0.1856	0.066*
H21C	0.2005	0.3773	0.1048	0.066*
C22	0.2599 (3)	0.33868 (19)	0.2589 (2)	0.0410 (7)
H22A	0.2984	0.2864	0.2179	0.061*
H22B	0.1743	0.3300	0.2971	0.061*
H22C	0.3093	0.3409	0.2979	0.061*
C23	0.0454 (3)	0.73828 (19)	0.52721 (18)	0.0335 (6)
H23A	0.0142	0.6801	0.5552	0.050*
H23B	−0.0056	0.7908	0.5649	0.050*
H23C	0.1329	0.7340	0.5229	0.050*
C24	−0.1255 (2)	0.62262 (18)	0.43510 (18)	0.0283 (6)
H24A	−0.1414	0.6525	0.4931	0.034*
H24B	−0.1560	0.5615	0.4504	0.034*
C25	−0.1998 (2)	0.68551 (17)	0.37983 (17)	0.0244 (5)
C26	−0.2958 (2)	0.76036 (17)	0.42077 (17)	0.0247 (5)
C27	−0.3660 (2)	0.81670 (17)	0.36990 (17)	0.0252 (6)
C28	−0.3417 (2)	0.79333 (17)	0.27867 (18)	0.0287 (6)
H28	−0.3905	0.8287	0.2456	0.034*
C29	−0.2469 (2)	0.71901 (18)	0.23475 (18)	0.0276 (6)
C30	−0.1763 (2)	0.66748 (18)	0.28625 (18)	0.0278 (6)
H30	−0.1108	0.6190	0.2577	0.033*
C31	−0.2255 (3)	0.69654 (19)	0.13412 (18)	0.0326 (6)
C32	−0.2053 (4)	0.7871 (3)	0.0714 (2)	0.0677 (11)
H32A	−0.2797	0.8348	0.0931	0.102*
H32B	−0.1915	0.7726	0.0085	0.102*
H32C	−0.1320	0.8107	0.0733	0.102*
C33	−0.3439 (3)	0.6595 (3)	0.1328 (2)	0.0559 (9)
H33A	−0.3585	0.6044	0.1744	0.084*
H33B	−0.3303	0.6423	0.0707	0.084*
H33C	−0.4171	0.7085	0.1525	0.084*
C34	−0.1086 (3)	0.6208 (3)	0.0944 (2)	0.0538 (9)
H34A	−0.0341	0.6418	0.0972	0.081*
H34B	−0.0968	0.6110	0.0307	0.081*
H34C	−0.1214	0.5620	0.1303	0.081*
C35	−0.2764 (3)	0.85128 (18)	0.53627 (19)	0.0323 (6)
H35A	−0.1869	0.8466	0.4997	0.049*
H35B	−0.2870	0.8474	0.6014	0.049*
H35C	−0.3209	0.9112	0.5217	0.049*
C36	−0.4611 (2)	0.90285 (17)	0.41072 (19)	0.0288 (6)
H36A	−0.5240	0.9163	0.3798	0.035*
H36B	−0.5057	0.8900	0.4765	0.035*
C37	−0.3691 (3)	1.02982 (18)	0.30819 (18)	0.0324 (6)
H37A	−0.4480	1.0571	0.2976	0.039*
H37B	−0.3216	0.9831	0.2614	0.039*
C38	−0.2909 (3)	1.10710 (18)	0.30149 (17)	0.0293 (6)
C39	−0.1576 (3)	1.09124 (18)	0.25720 (18)	0.0306 (6)
C40	−0.0862 (3)	1.16464 (18)	0.24799 (18)	0.0294 (6)
C41	−0.1504 (3)	1.25292 (18)	0.28456 (18)	0.0303 (6)
H41	−0.1030	1.3019	0.2779	0.036*
C42	−0.2821 (3)	1.27099 (17)	0.33056 (18)	0.0281 (6)
C43	−0.3503 (3)	1.19586 (18)	0.33747 (18)	0.0287 (6)
H43	−0.4386	1.2059	0.3673	0.034*
C44	−0.3535 (3)	1.36743 (18)	0.37140 (19)	0.0308 (6)
C45	−0.4577 (3)	1.4043 (2)	0.3288 (3)	0.0548 (9)
H45A	−0.5000	1.4662	0.3517	0.082*
H45B	−0.5190	1.3610	0.3459	0.082*
H45C	−0.4194	1.4088	0.2621	0.082*
C46	−0.4164 (3)	1.35488 (19)	0.4771 (2)	0.0391 (7)
H46A	−0.4653	1.4145	0.5021	0.059*
H46B	−0.3515	1.3345	0.5045	0.059*
H46C	−0.4721	1.3077	0.4909	0.059*
C47	−0.2645 (3)	1.44206 (19)	0.3507 (2)	0.0422 (7)
H47A	−0.2240	1.4503	0.2845	0.063*
H47B	−0.2003	1.4211	0.3788	0.063*
H47C	−0.3132	1.5017	0.3760	0.063*
C48	−0.0633 (3)	0.93163 (19)	0.2781 (2)	0.0385 (7)
H48A	−0.0080	0.9529	0.3045	0.058*
H48B	−0.0200	0.8751	0.2441	0.058*
H48C	−0.1397	0.9178	0.3271	0.058*
C49	0.0552 (3)	1.1506 (2)	0.19595 (19)	0.0348 (6)
H49A	0.0777	1.1001	0.1523	0.042*
H49B	0.0791	1.2088	0.1606	0.042*
C50	0.2560 (3)	1.09002 (18)	0.21264 (19)	0.0309 (6)
H50A	0.3051	1.0980	0.2512	0.037*
H50B	0.2877	1.1265	0.1546	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0323 (11)	0.0358 (11)	0.0310 (10)	−0.0073 (8)	−0.0131 (9)	−0.0067 (8)
O2	0.0291 (10)	0.0269 (9)	0.0250 (10)	−0.0009 (7)	−0.0107 (8)	−0.0051 (7)
O3	0.0310 (11)	0.0297 (10)	0.0252 (10)	−0.0053 (7)	−0.0089 (8)	−0.0052 (7)
O4	0.0374 (11)	0.0246 (10)	0.0286 (10)	−0.0053 (7)	−0.0136 (9)	−0.0020 (7)
O5	0.0542 (13)	0.0266 (10)	0.0313 (11)	0.0050 (9)	−0.0137 (10)	−0.0039 (8)
O6	0.0314 (11)	0.0301 (10)	0.0318 (10)	−0.0043 (8)	−0.0094 (9)	−0.0017 (8)
C1	0.0266 (15)	0.0274 (14)	0.0317 (15)	−0.0050 (10)	−0.0087 (12)	−0.0028 (11)
C2	0.0253 (15)	0.0296 (15)	0.0255 (14)	−0.0071 (10)	−0.0089 (11)	−0.0033 (10)
C3	0.0199 (14)	0.0285 (14)	0.0289 (14)	−0.0053 (10)	−0.0077 (11)	−0.0010 (10)
C4	0.0256 (14)	0.0265 (14)	0.0292 (14)	−0.0041 (10)	−0.0098 (12)	−0.0018 (10)
C5	0.0239 (14)	0.0294 (15)	0.0262 (14)	−0.0019 (10)	−0.0060 (11)	−0.0045 (10)
C6	0.0296 (16)	0.0295 (15)	0.0290 (15)	−0.0040 (11)	−0.0084 (12)	0.0028 (11)
C7	0.0424 (18)	0.0340 (16)	0.0251 (15)	−0.0040 (12)	−0.0113 (13)	−0.0010 (11)
C8	0.066 (2)	0.059 (2)	0.0282 (17)	−0.0170 (17)	−0.0022 (16)	−0.0042 (14)
C9	0.074 (3)	0.056 (2)	0.048 (2)	0.0022 (18)	−0.0363 (19)	−0.0079 (16)
C10	0.068 (2)	0.0436 (18)	0.0318 (17)	−0.0136 (15)	−0.0213 (16)	−0.0058 (13)
C11	0.0408 (18)	0.0361 (16)	0.0283 (15)	−0.0098 (12)	−0.0083 (13)	−0.0049 (11)
C12	0.0274 (15)	0.0294 (14)	0.0281 (14)	−0.0044 (11)	−0.0113 (12)	−0.0010 (10)
C13	0.0261 (15)	0.0283 (14)	0.0259 (14)	−0.0018 (10)	−0.0127 (12)	0.0016 (10)
C14	0.0267 (15)	0.0248 (14)	0.0230 (13)	−0.0016 (10)	−0.0097 (11)	−0.0018 (10)
C15	0.0252 (14)	0.0263 (14)	0.0232 (13)	−0.0022 (10)	−0.0086 (11)	0.0003 (10)
C16	0.0299 (15)	0.0288 (14)	0.0257 (14)	−0.0086 (11)	−0.0102 (12)	0.0001 (10)
C17	0.0284 (15)	0.0270 (14)	0.0266 (14)	−0.0023 (10)	−0.0105 (12)	0.0006 (10)
C18	0.0241 (14)	0.0294 (14)	0.0254 (14)	−0.0017 (10)	−0.0071 (11)	0.0004 (10)
C19	0.0309 (16)	0.0288 (15)	0.0316 (15)	0.0002 (11)	−0.0116 (12)	−0.0065 (11)
C20	0.0351 (17)	0.0345 (16)	0.0381 (17)	−0.0036 (12)	−0.0036 (14)	−0.0095 (12)
C21	0.0433 (19)	0.0505 (19)	0.0409 (18)	−0.0031 (14)	−0.0153 (15)	−0.0168 (14)
C22	0.0443 (19)	0.0286 (16)	0.0480 (19)	−0.0034 (12)	−0.0133 (15)	−0.0062 (12)
C23	0.0373 (17)	0.0391 (16)	0.0243 (14)	−0.0030 (12)	−0.0117 (13)	−0.0037 (11)
C24	0.0297 (15)	0.0268 (14)	0.0294 (14)	−0.0060 (11)	−0.0106 (12)	−0.0009 (10)
C25	0.0233 (14)	0.0261 (14)	0.0231 (13)	−0.0080 (10)	−0.0052 (11)	−0.0003 (10)
C26	0.0255 (14)	0.0277 (14)	0.0207 (13)	−0.0075 (10)	−0.0055 (11)	−0.0028 (10)
C27	0.0249 (14)	0.0234 (13)	0.0285 (14)	−0.0075 (10)	−0.0085 (11)	−0.0017 (10)
C28	0.0292 (15)	0.0275 (14)	0.0325 (15)	−0.0074 (11)	−0.0136 (12)	0.0012 (11)
C29	0.0275 (15)	0.0280 (14)	0.0275 (14)	−0.0079 (11)	−0.0079 (12)	−0.0025 (10)
C30	0.0280 (15)	0.0257 (14)	0.0280 (14)	−0.0054 (10)	−0.0064 (12)	−0.0032 (10)
C31	0.0344 (16)	0.0371 (16)	0.0257 (15)	−0.0034 (12)	−0.0098 (12)	−0.0035 (11)
C32	0.098 (3)	0.061 (2)	0.0349 (19)	−0.010 (2)	−0.015 (2)	0.0069 (16)
C33	0.051 (2)	0.084 (3)	0.0401 (19)	−0.0127 (18)	−0.0182 (17)	−0.0200 (17)
C34	0.053 (2)	0.074 (2)	0.0312 (17)	0.0056 (17)	−0.0151 (16)	−0.0162 (16)
C35	0.0367 (17)	0.0312 (15)	0.0337 (16)	−0.0046 (11)	−0.0159 (13)	−0.0089 (11)
C36	0.0302 (15)	0.0247 (14)	0.0332 (15)	−0.0062 (11)	−0.0115 (12)	−0.0019 (11)
C37	0.0426 (17)	0.0291 (15)	0.0298 (15)	−0.0090 (12)	−0.0168 (13)	0.0015 (11)
C38	0.0393 (17)	0.0267 (14)	0.0236 (14)	−0.0046 (11)	−0.0137 (12)	0.0002 (10)
C39	0.0414 (17)	0.0269 (14)	0.0232 (14)	−0.0005 (11)	−0.0129 (13)	−0.0013 (10)
C40	0.0301 (15)	0.0318 (15)	0.0233 (14)	−0.0003 (11)	−0.0086 (12)	0.0014 (10)
C41	0.0367 (17)	0.0281 (15)	0.0279 (15)	−0.0077 (11)	−0.0133 (13)	0.0036 (10)
C42	0.0330 (16)	0.0268 (14)	0.0268 (14)	−0.0032 (11)	−0.0146 (12)	0.0020 (10)
C43	0.0303 (15)	0.0297 (14)	0.0269 (14)	−0.0040 (11)	−0.0119 (12)	0.0015 (10)
C44	0.0313 (16)	0.0257 (14)	0.0361 (16)	−0.0033 (11)	−0.0134 (13)	−0.0001 (11)
C45	0.062 (2)	0.0365 (18)	0.080 (3)	0.0086 (15)	−0.049 (2)	−0.0063 (16)
C46	0.0383 (18)	0.0294 (16)	0.0406 (17)	−0.0010 (12)	−0.0036 (14)	−0.0056 (12)
C47	0.0431 (19)	0.0282 (16)	0.0490 (19)	−0.0054 (12)	−0.0073 (15)	−0.0054 (13)
C48	0.0440 (19)	0.0273 (15)	0.0427 (18)	−0.0007 (12)	−0.0167 (15)	0.0027 (12)
C49	0.0345 (17)	0.0352 (16)	0.0314 (16)	−0.0026 (12)	−0.0093 (13)	0.0018 (11)
C50	0.0286 (15)	0.0264 (14)	0.0362 (16)	−0.0057 (11)	−0.0082 (13)	−0.0034 (11)

Geometric parameters (Å, º)

O1—C2	1.392 (3)	C16—C17	1.397 (4)
O1—C11	1.436 (3)	C17—C18	1.395 (3)
O2—C14	1.396 (3)	C17—C19	1.535 (3)
O2—C23	1.438 (3)	C19—C20	1.524 (4)
O3—C26	1.390 (3)	C19—C21	1.535 (4)
O3—C35	1.445 (3)	C19—C22	1.535 (4)
O4—C37	1.432 (3)	C24—C25	1.522 (3)
O4—C36	1.451 (3)	C25—C26	1.395 (3)
O5—C39	1.383 (3)	C25—C30	1.406 (3)
O5—C48	1.445 (3)	C26—C27	1.405 (3)
O6—C49	1.433 (3)	C27—C28	1.390 (3)
O6—C50	1.434 (3)	C27—C36	1.502 (3)
C1—C6	1.385 (4)	C28—C29	1.395 (4)
C1—C2	1.401 (3)	C29—C30	1.388 (4)
C1—C50	1.509 (3)	C29—C31	1.534 (4)
C2—C3	1.392 (3)	C31—C34	1.528 (4)
C3—C4	1.396 (3)	C31—C32	1.532 (4)
C3—C12	1.529 (3)	C31—C33	1.532 (4)
C4—C5	1.394 (3)	C37—C38	1.506 (4)
C5—C6	1.393 (4)	C38—C43	1.388 (3)
C5—C7	1.532 (4)	C38—C39	1.402 (4)
C7—C10	1.524 (4)	C39—C40	1.399 (4)
C7—C8	1.536 (4)	C40—C41	1.396 (4)
C7—C9	1.542 (4)	C40—C49	1.498 (4)
C12—C13	1.512 (3)	C41—C42	1.391 (4)
C13—C14	1.391 (4)	C42—C43	1.402 (4)
C13—C18	1.400 (3)	C42—C44	1.532 (4)
C14—C15	1.400 (3)	C44—C46	1.528 (4)
C15—C16	1.390 (3)	C44—C47	1.528 (4)
C15—C24	1.511 (4)	C44—C45	1.534 (4)
C2—O1—C11	114.9 (2)	C22—C19—C17	109.3 (2)
C14—O2—C23	112.24 (18)	C15—C24—C25	112.1 (2)
C26—O3—C35	114.83 (19)	C26—C25—C30	117.9 (2)
C37—O4—C36	112.89 (19)	C26—C25—C24	121.4 (2)
C39—O5—C48	114.2 (2)	C30—C25—C24	120.6 (2)
C49—O6—C50	111.9 (2)	O3—C26—C25	118.7 (2)
C6—C1—C2	118.8 (2)	O3—C26—C27	120.1 (2)
C6—C1—C50	120.9 (2)	C25—C26—C27	121.1 (2)
C2—C1—C50	120.2 (2)	C28—C27—C26	118.4 (2)
O1—C2—C3	119.9 (2)	C28—C27—C36	120.3 (2)
O1—C2—C1	119.3 (2)	C26—C27—C36	121.3 (2)
C3—C2—C1	120.7 (2)	C27—C28—C29	122.6 (2)
C2—C3—C4	118.3 (2)	C30—C29—C28	117.2 (2)
C2—C3—C12	121.5 (2)	C30—C29—C31	122.8 (2)
C4—C3—C12	120.3 (2)	C28—C29—C31	120.0 (2)
C5—C4—C3	122.7 (2)	C29—C30—C25	122.7 (2)
C6—C5—C4	116.9 (2)	C34—C31—C32	107.9 (3)
C6—C5—C7	120.4 (2)	C34—C31—C33	108.4 (3)
C4—C5—C7	122.7 (2)	C32—C31—C33	109.8 (3)
C1—C6—C5	122.5 (2)	C34—C31—C29	112.4 (2)
C10—C7—C5	112.6 (2)	C32—C31—C29	109.8 (2)
C10—C7—C8	108.3 (2)	C33—C31—C29	108.5 (2)
C5—C7—C8	109.2 (2)	O4—C36—C27	110.6 (2)
C10—C7—C9	108.0 (3)	O4—C37—C38	108.2 (2)
C5—C7—C9	108.9 (2)	C43—C38—C39	119.0 (2)
C8—C7—C9	109.8 (3)	C43—C38—C37	120.3 (2)
C13—C12—C3	112.5 (2)	C39—C38—C37	120.6 (2)
C14—C13—C18	118.1 (2)	O5—C39—C40	119.1 (2)
C14—C13—C12	121.2 (2)	O5—C39—C38	120.4 (2)
C18—C13—C12	120.5 (2)	C40—C39—C38	120.3 (2)
C13—C14—O2	119.6 (2)	C41—C40—C39	118.6 (2)
C13—C14—C15	121.8 (2)	C41—C40—C49	120.5 (2)
O2—C14—C15	118.5 (2)	C39—C40—C49	120.9 (2)
C16—C15—C14	117.6 (2)	C42—C41—C40	122.9 (2)
C16—C15—C24	121.2 (2)	C41—C42—C43	116.7 (2)
C14—C15—C24	120.9 (2)	C41—C42—C44	123.4 (2)
C15—C16—C17	123.1 (2)	C43—C42—C44	119.9 (2)
C18—C17—C16	116.9 (2)	C38—C43—C42	122.5 (3)
C18—C17—C19	122.9 (2)	C46—C44—C47	108.7 (2)
C16—C17—C19	120.2 (2)	C46—C44—C42	109.5 (2)
C17—C18—C13	122.4 (2)	C47—C44—C42	112.1 (2)
C20—C19—C21	107.6 (2)	C46—C44—C45	109.0 (3)
C20—C19—C22	108.9 (2)	C47—C44—C45	108.4 (2)
C21—C19—C22	109.1 (2)	C42—C44—C45	109.0 (2)
C20—C19—C17	112.6 (2)	O6—C49—C40	110.3 (2)
C21—C19—C17	109.3 (2)	O6—C50—C1	111.7 (2)

(II)

Crystal data

C40H48O8	F(000) = 704
Mr = 656.78	Dx = 1.271 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.6466 (5) Å	Cell parameters from 6275 reflections
b = 11.0343 (7) Å	θ = 2.7–25.7°
c = 15.1801 (7) Å	µ = 0.09 mm^−1
β = 105.842 (3)°	T = 100 K
V = 1715.59 (16) Å^3	Platelet, colourless
Z = 2	0.25 × 0.25 × 0.15 mm

Data collection

Nonius Kappa-CCD diffractometer	2366 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.041
Graphite monochromator	θmax = 25.7°, θmin = 2.7°
Detector resolution: 18 pixels mm^-1	h = −12→12
ϕ scans	k = −13→13
6275 measured reflections	l = −18→18
3245 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0457P)^2 + 0.4886P] where P = (Fo^2 + 2Fc^2)/3
3245 reflections	(Δ/σ)max < 0.001
221 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

Experimental. crystal-to-detector distance 28 mm

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 expanded by subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atoms were introduced at calculated positions as riding atoms with an isotropic displacement parameter equal to 1.2 (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	0.48703 (13)	0.20399 (12)	0.15015 (8)	0.0304 (3)
O2	0.35428 (12)	−0.02455 (11)	0.19787 (9)	0.0274 (3)
O3	0.07761 (12)	−0.10932 (11)	−0.03507 (8)	0.0263 (3)
O4	0.16657 (12)	−0.24430 (11)	−0.21024 (8)	0.0254 (3)
C1	0.66194 (18)	0.24430 (16)	0.28619 (12)	0.0246 (4)
C2	0.54091 (18)	0.19191 (17)	0.24381 (12)	0.0246 (4)
C3	0.46767 (17)	0.13384 (16)	0.29515 (12)	0.0243 (4)
C4	0.51658 (17)	0.13036 (16)	0.38979 (12)	0.0243 (4)
H4	0.4674	0.0935	0.4243	0.029*
C5	0.63753 (18)	0.18068 (16)	0.43462 (12)	0.0243 (4)
C6	0.70858 (18)	0.23539 (16)	0.38107 (12)	0.0243 (4)
H6	0.7904	0.2673	0.4097	0.029*
C7	0.68400 (19)	0.18219 (18)	0.53770 (12)	0.0295 (4)
H7A	0.6381	0.2439	0.5609	0.044*
H7B	0.7760	0.1989	0.5567	0.044*
H7C	0.6676	0.1047	0.5611	0.044*
C8	0.53714 (19)	0.11934 (19)	0.09557 (13)	0.0324 (5)
H8A	0.6308	0.1224	0.1134	0.049*
H8B	0.5049	0.1404	0.0320	0.049*
H8C	0.5090	0.0389	0.1050	0.049*
C9	0.33634 (18)	0.07981 (17)	0.24933 (13)	0.0268 (4)
H9A	0.2926	0.0567	0.2951	0.032*
H9B	0.2824	0.1390	0.2089	0.032*
C10	0.23144 (18)	−0.07321 (18)	0.14874 (13)	0.0283 (4)
H10A	0.1799	−0.0112	0.1099	0.034*
H10B	0.1841	−0.1005	0.1913	0.034*
C11	0.25307 (17)	−0.17825 (16)	0.09083 (12)	0.0239 (4)
C12	0.17501 (17)	−0.19360 (16)	0.00152 (12)	0.0228 (4)
C13	0.18848 (17)	−0.29514 (16)	−0.05008 (12)	0.0228 (4)
C14	0.28193 (17)	−0.38197 (17)	−0.00989 (12)	0.0250 (4)
H14	0.2896	−0.4512	−0.0429	0.030*
C15	0.36447 (18)	−0.36782 (16)	0.07878 (12)	0.0255 (4)
C16	0.34825 (18)	−0.26472 (17)	0.12743 (12)	0.0256 (4)
H16	0.4027	−0.2533	0.1862	0.031*
C17	0.46534 (19)	−0.46138 (18)	0.12167 (13)	0.0324 (5)
H17A	0.5490	−0.4231	0.1436	0.049*
H17B	0.4694	−0.5216	0.0769	0.049*
H17C	0.4420	−0.4992	0.1719	0.049*
C18	0.12308 (19)	−0.00917 (17)	−0.07863 (14)	0.0316 (5)
H18A	0.2022	0.0223	−0.0385	0.047*
H18B	0.0578	0.0533	−0.0919	0.047*
H18C	0.1395	−0.0362	−0.1346	0.047*
C19	0.10757 (18)	−0.30683 (18)	−0.14816 (12)	0.0272 (4)
H19A	0.0977	−0.3919	−0.1647	0.033*
H19B	0.0213	−0.2737	−0.1540	0.033*
C20	0.26531 (19)	−0.31715 (17)	−0.23216 (13)	0.0289 (4)
H20A	0.2252	−0.3870	−0.2676	0.035*
H20B	0.3259	−0.3461	−0.1762	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0322 (7)	0.0359 (8)	0.0224 (6)	0.0068 (6)	0.0060 (6)	0.0001 (6)
O2	0.0206 (6)	0.0276 (7)	0.0327 (7)	−0.0008 (5)	0.0049 (5)	−0.0093 (6)
O3	0.0217 (6)	0.0254 (7)	0.0313 (7)	−0.0004 (5)	0.0063 (5)	0.0040 (6)
O4	0.0240 (7)	0.0298 (7)	0.0239 (6)	0.0009 (6)	0.0089 (5)	0.0023 (6)
C1	0.0263 (10)	0.0208 (9)	0.0293 (10)	0.0018 (8)	0.0118 (8)	−0.0005 (8)
C2	0.0280 (10)	0.0229 (9)	0.0228 (9)	0.0063 (8)	0.0068 (8)	−0.0003 (8)
C3	0.0233 (9)	0.0220 (9)	0.0273 (9)	0.0023 (8)	0.0062 (8)	−0.0030 (8)
C4	0.0247 (9)	0.0227 (9)	0.0276 (9)	0.0012 (8)	0.0105 (8)	−0.0027 (8)
C5	0.0245 (9)	0.0219 (9)	0.0266 (9)	0.0028 (8)	0.0073 (8)	−0.0030 (8)
C6	0.0210 (9)	0.0231 (9)	0.0283 (9)	−0.0008 (8)	0.0060 (7)	−0.0036 (8)
C7	0.0289 (10)	0.0325 (10)	0.0267 (10)	−0.0026 (9)	0.0069 (8)	−0.0050 (9)
C8	0.0336 (11)	0.0394 (11)	0.0258 (10)	0.0014 (9)	0.0108 (8)	−0.0058 (9)
C9	0.0251 (9)	0.0267 (10)	0.0282 (9)	0.0017 (8)	0.0064 (8)	−0.0066 (8)
C10	0.0216 (9)	0.0325 (10)	0.0290 (10)	−0.0038 (8)	0.0040 (8)	−0.0064 (9)
C11	0.0217 (9)	0.0243 (9)	0.0264 (9)	−0.0042 (8)	0.0079 (8)	−0.0009 (8)
C12	0.0189 (9)	0.0224 (9)	0.0272 (9)	−0.0015 (7)	0.0065 (7)	0.0032 (8)
C13	0.0217 (9)	0.0253 (9)	0.0226 (9)	−0.0055 (8)	0.0080 (7)	0.0007 (8)
C14	0.0262 (9)	0.0234 (9)	0.0261 (9)	−0.0035 (8)	0.0083 (8)	−0.0013 (8)
C15	0.0251 (9)	0.0243 (9)	0.0270 (9)	−0.0022 (8)	0.0068 (8)	0.0032 (8)
C16	0.0242 (9)	0.0291 (10)	0.0221 (9)	−0.0029 (8)	0.0040 (7)	0.0011 (8)
C17	0.0326 (10)	0.0299 (11)	0.0325 (10)	0.0038 (9)	0.0052 (9)	0.0033 (9)
C18	0.0282 (10)	0.0270 (10)	0.0401 (11)	0.0013 (9)	0.0099 (9)	0.0084 (9)
C19	0.0255 (9)	0.0332 (10)	0.0238 (9)	−0.0045 (8)	0.0080 (8)	−0.0001 (8)
C20	0.0320 (10)	0.0263 (9)	0.0316 (10)	0.0010 (8)	0.0138 (9)	−0.0001 (8)

Geometric parameters (Å, º)

O1—C2	1.387 (2)	C4—C5	1.397 (2)
O1—C8	1.444 (2)	C5—C6	1.390 (3)
O2—C10	1.422 (2)	C5—C7	1.507 (2)
O2—C9	1.433 (2)	C10—C11	1.510 (3)
O3—C12	1.391 (2)	C11—C16	1.392 (3)
O3—C18	1.438 (2)	C11—C12	1.394 (2)
O4—C20	1.433 (2)	C12—C13	1.397 (3)
O4—C19	1.443 (2)	C13—C14	1.396 (3)
C1—C6	1.393 (3)	C13—C19	1.508 (2)
C1—C2	1.398 (3)	C14—C15	1.401 (3)
C1—C20^i	1.505 (3)	C15—C16	1.393 (3)
C2—C3	1.399 (3)	C15—C17	1.504 (3)
C3—C4	1.389 (2)	C20—C1^i	1.505 (3)
C3—C9	1.504 (2)
C2—O1—C8	114.33 (14)	O2—C9—C3	108.97 (14)
C10—O2—C9	110.41 (13)	O2—C10—C11	109.30 (15)
C12—O3—C18	112.93 (13)	C16—C11—C12	118.73 (16)
C20—O4—C19	111.17 (14)	C16—C11—C10	120.25 (16)
C6—C1—C2	118.04 (16)	C12—C11—C10	120.96 (16)
C6—C1—C20^i	120.65 (17)	O3—C12—C11	119.27 (16)
C2—C1—C20^i	121.11 (17)	O3—C12—C13	119.47 (15)
O1—C2—C1	120.21 (16)	C11—C12—C13	121.18 (16)
O1—C2—C3	118.53 (16)	C14—C13—C12	118.39 (16)
C1—C2—C3	121.11 (16)	C14—C13—C19	121.30 (17)
C4—C3—C2	118.71 (16)	C12—C13—C19	120.25 (16)
C4—C3—C9	120.40 (17)	C13—C14—C15	121.92 (17)
C2—C3—C9	120.86 (16)	C16—C15—C14	117.68 (17)
C3—C4—C5	121.90 (17)	C16—C15—C17	120.57 (16)
C6—C5—C4	117.65 (17)	C14—C15—C17	121.74 (17)
C6—C5—C7	121.70 (16)	C11—C16—C15	122.03 (17)
C4—C5—C7	120.53 (17)	O4—C19—C13	111.75 (14)
C5—C6—C1	122.54 (17)	O4—C20—C1^i	110.25 (15)

Symmetry code: (i) −x+1, −y, −z.

(III)

Crystal data

C44H56O8	F(000) = 1536
Mr = 712.89	Dx = 1.218 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 23.2320 (15) Å	Cell parameters from 14012 reflections
b = 9.0186 (3) Å	θ = 2.6–25.7°
c = 19.6065 (12) Å	µ = 0.08 mm^−1
β = 108.819 (2)°	T = 100 K
V = 3888.4 (4) Å^3	Platelet, colourless
Z = 4	0.20 × 0.20 × 0.10 mm

Data collection

Nonius Kappa-CCD diffractometer	4351 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.078
Graphite monochromator	θmax = 25.7°, θmin = 2.6°
Detector resolution: 18 pixels mm^-1	h = −28→28
ϕ scans	k = −10→10
14012 measured reflections	l = −23→23
7332 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0568P)^2 + 0.2708P] where P = (Fo^2 + 2Fc^2)/3
7332 reflections	(Δ/σ)max < 0.001
479 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Experimental. crystal-to-detector distance 28 mm

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 expanded by subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atoms were introduced at calculated positions as riding atoms with an isotropic displacement parameter equal to 1.2 (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	0.43294 (8)	0.04567 (17)	0.28686 (9)	0.0255 (4)
O2	0.29018 (8)	0.17842 (18)	0.11931 (10)	0.0262 (4)
O3	0.17952 (8)	0.02473 (18)	0.23447 (9)	0.0285 (4)
O4	0.04145 (8)	−0.17132 (17)	0.14758 (9)	0.0260 (4)
O5	0.07096 (8)	−0.53076 (18)	0.20765 (9)	0.0259 (4)
O6	0.22175 (8)	−0.58706 (17)	0.36035 (10)	0.0279 (4)
O7	0.31230 (8)	−0.57545 (18)	0.27421 (9)	0.0281 (4)
O8	0.45064 (8)	−0.33465 (17)	0.34068 (9)	0.0255 (4)
C1	0.43874 (11)	−0.1892 (3)	0.23045 (14)	0.0230 (6)
C2	0.41519 (11)	−0.0452 (3)	0.22629 (14)	0.0223 (6)
C3	0.37796 (11)	0.0124 (3)	0.16137 (14)	0.0232 (6)
C4	0.36291 (12)	−0.0768 (3)	0.10007 (14)	0.0242 (6)
H4	0.3374	−0.0389	0.0568	0.029*
C5	0.38483 (11)	−0.2207 (3)	0.10152 (14)	0.0236 (6)
C6	0.42365 (11)	−0.2730 (3)	0.16792 (14)	0.0247 (6)
H6	0.4399	−0.3678	0.1700	0.030*
C7	0.36610 (12)	−0.3250 (3)	0.03596 (14)	0.0292 (6)
C8	0.42193 (14)	−0.4000 (3)	0.02556 (16)	0.0382 (7)
H8A	0.4089	−0.4724	−0.0122	0.057*
H8B	0.4451	−0.4480	0.0696	0.057*
H8C	0.4467	−0.3268	0.0128	0.057*
C9	0.33129 (15)	−0.2431 (3)	−0.03371 (15)	0.0419 (8)
H9A	0.3563	−0.1652	−0.0423	0.063*
H9B	0.2947	−0.2013	−0.0291	0.063*
H9C	0.3211	−0.3114	−0.0734	0.063*
C10	0.32417 (13)	−0.4439 (3)	0.05038 (16)	0.0356 (7)
H10A	0.3082	−0.5047	0.0083	0.053*
H10B	0.2912	−0.3968	0.0616	0.053*
H10C	0.3468	−0.5044	0.0903	0.053*
C11	0.40012 (13)	0.0200 (3)	0.33636 (15)	0.0310 (7)
H11A	0.3579	0.0430	0.3134	0.047*
H11B	0.4163	0.0819	0.3780	0.047*
H11C	0.4041	−0.0822	0.3508	0.047*
C12	0.35423 (11)	0.1704 (3)	0.15494 (14)	0.0246 (6)
H12A	0.3637	0.2128	0.2028	0.030*
H12B	0.3749	0.2290	0.1284	0.030*
C13	0.25837 (12)	0.1238 (3)	0.16511 (14)	0.0275 (6)
H13A	0.2658	0.1883	0.2066	0.033*
H13B	0.2733	0.0257	0.1822	0.033*
C14	0.19116 (12)	0.1163 (3)	0.12568 (14)	0.0232 (6)
C15	0.15297 (12)	0.0612 (3)	0.16231 (14)	0.0235 (6)
C16	0.09013 (12)	0.0504 (3)	0.12908 (14)	0.0248 (6)
C17	0.06619 (13)	0.1004 (3)	0.05842 (15)	0.0294 (6)
H17	0.0244	0.0967	0.0356	0.035*
C18	0.10290 (12)	0.1556 (3)	0.02116 (15)	0.0298 (6)
H18A	0.0858	0.1881	−0.0261	0.036*
C19	0.16552 (12)	0.1621 (3)	0.05455 (14)	0.0277 (6)
H19	0.1903	0.1973	0.0292	0.033*
C20	0.19399 (13)	−0.1301 (3)	0.24721 (16)	0.0338 (7)
H20A	0.1574	−0.1876	0.2304	0.051*
H20B	0.2130	−0.1465	0.2979	0.051*
H20C	0.2213	−0.1593	0.2219	0.051*
C21	0.05009 (12)	−0.0164 (3)	0.16761 (15)	0.0292 (6)
H21A	0.0691	−0.0070	0.2193	0.035*
H21B	0.0112	0.0343	0.1539	0.035*
C22	0.00956 (11)	−0.2499 (3)	0.18859 (14)	0.0258 (6)
H22A	−0.0111	−0.3348	0.1610	0.031*
H22B	−0.0210	−0.1852	0.1965	0.031*
C23	0.05182 (11)	−0.3025 (3)	0.26055 (14)	0.0238 (6)
C24	0.08344 (11)	−0.4364 (3)	0.26692 (14)	0.0230 (6)
C25	0.12378 (11)	−0.4819 (3)	0.33309 (14)	0.0232 (6)
C26	0.13298 (11)	−0.3899 (3)	0.39277 (15)	0.0248 (6)
H26	0.1603	−0.4196	0.4368	0.030*
C27	0.10292 (11)	−0.2555 (3)	0.38901 (14)	0.0232 (6)
C28	0.06159 (11)	−0.2152 (3)	0.32194 (14)	0.0252 (6)
H28	0.0400	−0.1272	0.3183	0.030*
C29	0.11606 (12)	−0.1486 (3)	0.45335 (15)	0.0271 (6)
C30	0.15609 (12)	−0.2203 (3)	0.52375 (14)	0.0319 (7)
H30A	0.1356	−0.3052	0.5345	0.048*
H30B	0.1637	−0.1498	0.5623	0.048*
H30C	0.1940	−0.2506	0.5184	0.048*
C31	0.15024 (13)	−0.0146 (3)	0.43609 (16)	0.0340 (7)
H31A	0.1605	0.0534	0.4759	0.051*
H31B	0.1247	0.0344	0.3936	0.051*
H31C	0.1867	−0.0482	0.4280	0.051*
C32	0.05693 (12)	−0.0953 (3)	0.46476 (15)	0.0327 (7)
H32A	0.0390	−0.1756	0.4830	0.049*
H32B	0.0290	−0.0621	0.4197	0.049*
H32C	0.0659	−0.0150	0.4987	0.049*
C33	0.11251 (13)	−0.5170 (3)	0.16785 (16)	0.0351 (7)
H33A	0.1088	−0.4201	0.1467	0.053*
H33B	0.1033	−0.5907	0.1305	0.053*
H33C	0.1533	−0.5311	0.1996	0.053*
C34	0.15881 (11)	−0.6248 (3)	0.34180 (15)	0.0266 (6)
H34A	0.1519	−0.6847	0.3795	0.032*
H34B	0.1459	−0.6810	0.2972	0.032*
C35	0.25910 (11)	−0.7165 (3)	0.36956 (15)	0.0265 (6)
H35A	0.2488	−0.7714	0.3247	0.032*
H35B	0.2522	−0.7803	0.4060	0.032*
C36	0.32464 (11)	−0.6709 (2)	0.39219 (14)	0.0228 (6)
C37	0.34932 (12)	−0.6009 (2)	0.34482 (13)	0.0219 (6)
C38	0.41099 (12)	−0.5640 (2)	0.36478 (14)	0.0228 (6)
C39	0.44777 (12)	−0.6014 (3)	0.43424 (15)	0.0274 (6)
H39	0.4892	−0.5809	0.4481	0.033*
C40	0.42437 (12)	−0.6679 (3)	0.48289 (15)	0.0293 (6)
H40A	0.4495	−0.6900	0.5293	0.035*
C41	0.36292 (12)	−0.7015 (3)	0.46167 (15)	0.0273 (6)
H41	0.3469	−0.7454	0.4945	0.033*
C42	0.29034 (13)	−0.4251 (3)	0.26117 (16)	0.0329 (7)
H42A	0.2641	−0.4046	0.2891	0.049*
H42B	0.2681	−0.4128	0.2109	0.049*
H42C	0.3242	−0.3579	0.2748	0.049*
C43	0.43839 (12)	−0.4856 (3)	0.31529 (15)	0.0269 (6)
H43A	0.4758	−0.5342	0.3158	0.032*
H43B	0.4104	−0.4869	0.2664	0.032*
C44	0.48138 (11)	−0.2503 (3)	0.30041 (14)	0.0245 (6)
H44A	0.5113	−0.3132	0.2899	0.029*
H44B	0.5029	−0.1686	0.3299	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0326 (11)	0.0233 (9)	0.0205 (10)	−0.0032 (8)	0.0083 (8)	−0.0040 (7)
O2	0.0249 (10)	0.0252 (9)	0.0263 (10)	0.0002 (8)	0.0053 (8)	0.0036 (8)
O3	0.0316 (11)	0.0265 (9)	0.0243 (11)	0.0016 (8)	0.0047 (9)	0.0011 (8)
O4	0.0281 (10)	0.0213 (9)	0.0281 (11)	−0.0005 (8)	0.0084 (8)	0.0006 (8)
O5	0.0252 (10)	0.0261 (9)	0.0259 (11)	−0.0040 (7)	0.0077 (8)	−0.0056 (8)
O6	0.0224 (10)	0.0187 (9)	0.0408 (12)	0.0014 (7)	0.0078 (9)	0.0000 (8)
O7	0.0320 (11)	0.0237 (9)	0.0236 (11)	0.0016 (8)	0.0021 (9)	0.0015 (7)
O8	0.0334 (10)	0.0192 (8)	0.0236 (10)	−0.0002 (8)	0.0086 (8)	0.0005 (7)
C1	0.0210 (13)	0.0213 (12)	0.0260 (15)	−0.0004 (10)	0.0065 (11)	0.0018 (11)
C2	0.0242 (14)	0.0220 (12)	0.0219 (14)	−0.0041 (10)	0.0091 (12)	−0.0026 (10)
C3	0.0244 (14)	0.0202 (12)	0.0252 (15)	−0.0003 (11)	0.0083 (12)	−0.0004 (11)
C4	0.0258 (14)	0.0238 (13)	0.0213 (15)	−0.0004 (11)	0.0052 (12)	0.0019 (11)
C5	0.0260 (14)	0.0220 (12)	0.0228 (15)	−0.0016 (11)	0.0078 (12)	−0.0001 (11)
C6	0.0275 (15)	0.0197 (12)	0.0280 (16)	0.0012 (11)	0.0104 (12)	0.0024 (11)
C7	0.0369 (16)	0.0247 (13)	0.0235 (16)	0.0028 (12)	0.0064 (13)	−0.0035 (11)
C8	0.0429 (18)	0.0375 (16)	0.0339 (18)	−0.0017 (14)	0.0118 (15)	−0.0104 (13)
C9	0.061 (2)	0.0303 (15)	0.0263 (17)	0.0015 (14)	0.0023 (15)	−0.0026 (12)
C10	0.0374 (17)	0.0263 (14)	0.0383 (18)	0.0004 (12)	0.0058 (14)	−0.0057 (12)
C11	0.0405 (17)	0.0289 (14)	0.0258 (16)	0.0014 (12)	0.0137 (13)	−0.0029 (12)
C12	0.0196 (13)	0.0245 (13)	0.0280 (15)	0.0005 (11)	0.0053 (12)	−0.0010 (11)
C13	0.0281 (15)	0.0289 (14)	0.0242 (15)	−0.0011 (11)	0.0067 (12)	−0.0009 (11)
C14	0.0273 (14)	0.0173 (12)	0.0225 (14)	0.0018 (10)	0.0043 (12)	−0.0029 (10)
C15	0.0284 (15)	0.0194 (12)	0.0212 (14)	0.0020 (10)	0.0058 (12)	0.0000 (10)
C16	0.0295 (15)	0.0175 (12)	0.0267 (15)	0.0005 (11)	0.0083 (12)	−0.0030 (11)
C17	0.0257 (15)	0.0258 (13)	0.0302 (16)	0.0013 (11)	−0.0001 (13)	−0.0023 (11)
C18	0.0331 (16)	0.0238 (13)	0.0284 (16)	0.0016 (12)	0.0041 (13)	0.0021 (11)
C19	0.0318 (16)	0.0239 (13)	0.0264 (15)	−0.0005 (11)	0.0079 (13)	0.0029 (11)
C20	0.0367 (17)	0.0286 (14)	0.0339 (17)	0.0027 (12)	0.0083 (14)	0.0089 (12)
C21	0.0309 (15)	0.0232 (13)	0.0328 (17)	−0.0008 (11)	0.0092 (13)	−0.0037 (11)
C22	0.0232 (14)	0.0240 (13)	0.0268 (16)	−0.0019 (11)	0.0035 (12)	0.0005 (11)
C23	0.0196 (13)	0.0255 (13)	0.0264 (15)	−0.0012 (10)	0.0073 (12)	0.0019 (11)
C24	0.0224 (14)	0.0229 (13)	0.0239 (15)	−0.0044 (10)	0.0079 (12)	−0.0020 (11)
C25	0.0217 (13)	0.0204 (12)	0.0279 (15)	−0.0024 (10)	0.0088 (12)	−0.0008 (11)
C26	0.0216 (14)	0.0247 (13)	0.0253 (15)	−0.0025 (11)	0.0035 (11)	0.0020 (11)
C27	0.0211 (13)	0.0229 (13)	0.0262 (15)	−0.0016 (10)	0.0085 (12)	0.0012 (11)
C28	0.0243 (14)	0.0201 (12)	0.0306 (16)	−0.0004 (11)	0.0081 (12)	−0.0006 (11)
C29	0.0290 (15)	0.0226 (13)	0.0284 (16)	−0.0006 (11)	0.0076 (12)	−0.0009 (11)
C30	0.0344 (16)	0.0313 (14)	0.0269 (16)	0.0011 (12)	0.0059 (13)	−0.0019 (12)
C31	0.0396 (17)	0.0273 (14)	0.0348 (17)	−0.0087 (12)	0.0115 (14)	−0.0044 (12)
C32	0.0336 (16)	0.0307 (14)	0.0317 (17)	0.0037 (12)	0.0078 (13)	−0.0062 (12)
C33	0.0422 (18)	0.0326 (15)	0.0351 (17)	−0.0051 (13)	0.0189 (15)	−0.0074 (13)
C34	0.0252 (15)	0.0242 (13)	0.0299 (16)	0.0008 (11)	0.0084 (12)	−0.0012 (11)
C35	0.0259 (14)	0.0194 (12)	0.0336 (16)	0.0013 (10)	0.0089 (12)	−0.0008 (11)
C36	0.0248 (14)	0.0147 (11)	0.0279 (15)	0.0015 (10)	0.0072 (12)	−0.0012 (10)
C37	0.0268 (14)	0.0186 (12)	0.0195 (14)	0.0034 (10)	0.0063 (12)	−0.0011 (10)
C38	0.0267 (15)	0.0170 (12)	0.0242 (15)	−0.0002 (10)	0.0075 (12)	−0.0028 (10)
C39	0.0210 (14)	0.0244 (13)	0.0320 (16)	0.0003 (11)	0.0020 (12)	−0.0005 (11)
C40	0.0301 (15)	0.0261 (13)	0.0261 (16)	0.0007 (12)	0.0013 (12)	0.0027 (11)
C41	0.0318 (15)	0.0224 (13)	0.0285 (16)	−0.0011 (11)	0.0107 (13)	0.0001 (11)
C42	0.0343 (16)	0.0262 (14)	0.0331 (17)	0.0052 (12)	0.0038 (13)	0.0083 (12)
C43	0.0321 (15)	0.0194 (12)	0.0309 (16)	−0.0017 (11)	0.0126 (13)	−0.0037 (11)
C44	0.0241 (14)	0.0217 (13)	0.0264 (15)	−0.0013 (11)	0.0066 (12)	0.0014 (11)

Geometric parameters (Å, º)

O1—C2	1.392 (3)	C13—C14	1.504 (4)
O1—C11	1.433 (3)	C14—C19	1.391 (3)
O2—C13	1.422 (3)	C14—C15	1.401 (4)
O2—C12	1.427 (3)	C15—C16	1.397 (4)
O3—C15	1.388 (3)	C16—C17	1.391 (4)
O3—C20	1.439 (3)	C16—C21	1.501 (4)
O4—C22	1.443 (3)	C17—C18	1.382 (4)
O4—C21	1.447 (3)	C18—C19	1.391 (4)
O5—C24	1.394 (3)	C22—C23	1.512 (3)
O5—C33	1.429 (3)	C23—C28	1.394 (4)
O6—C34	1.429 (3)	C23—C24	1.397 (3)
O6—C35	1.431 (3)	C24—C25	1.395 (3)
O7—C37	1.393 (3)	C25—C26	1.394 (4)
O7—C42	1.442 (3)	C25—C34	1.504 (3)
O8—C44	1.441 (3)	C26—C27	1.389 (3)
O8—C43	1.446 (3)	C27—C28	1.403 (3)
C1—C6	1.386 (4)	C27—C29	1.538 (3)
C1—C2	1.401 (3)	C29—C30	1.536 (4)
C1—C44	1.513 (3)	C29—C32	1.538 (4)
C2—C3	1.388 (3)	C29—C31	1.542 (3)
C3—C4	1.394 (3)	C35—C36	1.500 (3)
C3—C12	1.518 (3)	C36—C37	1.390 (4)
C4—C5	1.390 (3)	C36—C41	1.393 (4)
C5—C6	1.405 (3)	C37—C38	1.398 (4)
C5—C7	1.538 (3)	C38—C39	1.396 (4)
C7—C8	1.534 (4)	C38—C43	1.498 (4)
C7—C9	1.534 (4)	C39—C40	1.379 (4)
C7—C10	1.535 (4)	C40—C41	1.385 (4)
C2—O1—C11	113.99 (19)	C17—C18—C19	119.8 (3)
C13—O2—C12	110.21 (19)	C18—C19—C14	120.3 (3)
C15—O3—C20	114.13 (19)	O4—C21—C16	107.8 (2)
C22—O4—C21	112.0 (2)	O4—C22—C23	112.2 (2)
C24—O5—C33	114.01 (19)	C28—C23—C24	118.4 (2)
C34—O6—C35	111.51 (18)	C28—C23—C22	120.3 (2)
C37—O7—C42	113.63 (19)	C24—C23—C22	121.2 (2)
C44—O8—C43	112.68 (19)	O5—C24—C25	119.5 (2)
C6—C1—C2	118.1 (2)	O5—C24—C23	119.4 (2)
C6—C1—C44	120.5 (2)	C25—C24—C23	120.9 (2)
C2—C1—C44	121.3 (2)	C26—C25—C24	118.7 (2)
C3—C2—O1	119.2 (2)	C26—C25—C34	118.9 (2)
C3—C2—C1	121.1 (2)	C24—C25—C34	122.3 (2)
O1—C2—C1	119.6 (2)	C27—C26—C25	122.5 (2)
C2—C3—C4	118.9 (2)	C26—C27—C28	117.1 (2)
C2—C3—C12	122.0 (2)	C26—C27—C29	122.7 (2)
C4—C3—C12	119.1 (2)	C28—C27—C29	120.1 (2)
C5—C4—C3	122.2 (2)	C23—C28—C27	122.3 (2)
C4—C5—C6	117.0 (2)	C30—C29—C32	108.1 (2)
C4—C5—C7	123.4 (2)	C30—C29—C27	112.0 (2)
C6—C5—C7	119.5 (2)	C32—C29—C27	111.4 (2)
C1—C6—C5	122.7 (2)	C30—C29—C31	108.8 (2)
C8—C7—C9	108.6 (2)	C32—C29—C31	109.5 (2)
C8—C7—C10	109.3 (2)	C27—C29—C31	106.9 (2)
C9—C7—C10	108.5 (2)	O6—C34—C25	107.22 (19)
C8—C7—C5	111.0 (2)	O6—C35—C36	109.27 (19)
C9—C7—C5	112.1 (2)	C37—C36—C41	118.2 (2)
C10—C7—C5	107.4 (2)	C37—C36—C35	121.7 (2)
O2—C12—C3	112.45 (19)	C41—C36—C35	120.1 (2)
O2—C13—C14	110.8 (2)	C36—C37—O7	118.9 (2)
C19—C14—C15	118.8 (2)	C36—C37—C38	121.8 (2)
C19—C14—C13	122.7 (2)	O7—C37—C38	119.2 (2)
C15—C14—C13	118.5 (2)	C39—C38—C37	117.7 (2)
O3—C15—C16	120.9 (2)	C39—C38—C43	119.4 (2)
O3—C15—C14	117.4 (2)	C37—C38—C43	122.8 (2)
C16—C15—C14	121.7 (2)	C40—C39—C38	121.8 (2)
C17—C16—C15	117.7 (3)	C39—C40—C41	119.0 (3)
C17—C16—C21	121.2 (2)	C40—C41—C36	121.4 (3)
C15—C16—C21	121.1 (2)	O8—C43—C38	107.4 (2)
C18—C17—C16	121.8 (3)	O8—C44—C1	113.2 (2)

(IV)

Crystal data

C42H50O9	Z = 2
Mr = 698.82	F(000) = 748
Triclinic, P1	Dx = 1.287 Mg m^−3
a = 8.6669 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.7665 (11) Å	Cell parameters from 13815 reflections
c = 16.8072 (9) Å	θ = 2.7–25.7°
α = 113.671 (4)°	µ = 0.09 mm^−1
β = 94.723 (4)°	T = 100 K
γ = 97.119 (3)°	Parallelepipedic, colourless
V = 1803.1 (2) Å^3	0.30 × 0.30 × 0.20 mm

Data collection

Nonius Kappa-CCD diffractometer	4286 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.063
Graphite monochromator	θmax = 25.7°, θmin = 2.7°
Detector resolution: 18 pixels mm^-1	h = 0→10
ϕ scans	k = −16→16
6346 measured reflections	l = −20→19
6346 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0371P)^2 + 1.2698P] where P = (Fo^2 + 2Fc^2)/3
6346 reflections	(Δ/σ)max < 0.001
466 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Experimental. crystal-to-detector distance 28 mm

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 expanded by subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atoms were introduced at calculated positions as riding atoms with an isotropic displacement parameter equal to 1.2 (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	0.93668 (19)	0.03106 (14)	0.34728 (11)	0.0287 (4)
O2	0.5790 (2)	−0.04427 (16)	0.28296 (12)	0.0336 (5)
O3	0.7303 (2)	−0.01658 (14)	0.13467 (11)	0.0282 (4)
O4	1.1515 (2)	−0.17797 (14)	0.33189 (11)	0.0293 (4)
O5	1.1002 (2)	−0.27544 (15)	0.09373 (12)	0.0343 (5)
O6	0.6537 (2)	−0.33091 (14)	−0.04754 (12)	0.0330 (4)
O7	0.7328 (2)	0.22424 (14)	0.09683 (11)	0.0311 (4)
O8	1.0482 (2)	0.35417 (14)	0.28074 (12)	0.0320 (4)
O9	1.0047 (2)	0.34056 (14)	0.52388 (11)	0.0310 (4)
C1	0.8319 (3)	−0.0500 (2)	0.35962 (17)	0.0284 (6)
H1A	0.7857	−0.0172	0.4127	0.034*
H1B	0.8895	−0.1034	0.3655	0.034*
C2	0.7048 (3)	−0.1026 (2)	0.28149 (17)	0.0291 (6)
H2A	0.7520	−0.1132	0.2289	0.035*
H2B	0.6615	−0.1732	0.2774	0.035*
C3	0.6097 (3)	0.0480 (2)	0.26381 (17)	0.0303 (6)
H3A	0.7162	0.0850	0.2900	0.036*
H3B	0.5390	0.0969	0.2912	0.036*
C4	0.5910 (3)	0.0227 (2)	0.16736 (17)	0.0308 (6)
H4A	0.4985	−0.0316	0.1367	0.037*
H4B	0.5792	0.0869	0.1584	0.037*
C5	1.0974 (3)	0.1678 (2)	0.47622 (16)	0.0265 (6)
C6	1.0790 (3)	0.0690 (2)	0.40369 (16)	0.0261 (6)
C7	1.2038 (3)	0.0125 (2)	0.38249 (16)	0.0245 (6)
C8	1.3487 (3)	0.0579 (2)	0.43506 (16)	0.0268 (6)
H8	1.4325	0.0209	0.4216	0.032*
C9	1.3724 (3)	0.1569 (2)	0.50722 (16)	0.0271 (6)
C10	1.2450 (3)	0.2105 (2)	0.52708 (16)	0.0266 (6)
H10	1.2588	0.2765	0.5755	0.032*
C11	1.5311 (3)	0.2051 (2)	0.56245 (18)	0.0351 (7)
H11A	1.5470	0.2819	0.5826	0.053*
H11B	1.6113	0.1770	0.5280	0.053*
H11C	1.5362	0.1870	0.6120	0.053*
C12	1.1847 (3)	−0.0930 (2)	0.30316 (17)	0.0280 (6)
H12A	1.0990	−0.0980	0.2600	0.034*
H12B	1.2802	−0.0988	0.2765	0.034*
C13	1.1444 (3)	−0.2827 (2)	0.26254 (17)	0.0317 (6)
H13A	1.1613	−0.3333	0.2879	0.038*
H13B	1.2283	−0.2801	0.2282	0.038*
C14	0.9888 (3)	−0.3226 (2)	0.20257 (17)	0.0281 (6)
C15	0.9706 (3)	−0.3175 (2)	0.12135 (17)	0.0287 (6)
C16	0.8250 (3)	−0.3495 (2)	0.06788 (17)	0.0289 (6)
C17	0.6961 (3)	−0.3873 (2)	0.09806 (17)	0.0298 (6)
H17	0.5984	−0.4089	0.0632	0.036*
C18	0.7087 (3)	−0.3939 (2)	0.17870 (17)	0.0280 (6)
C19	0.8559 (3)	−0.3616 (2)	0.22998 (17)	0.0284 (6)
H19	0.8662	−0.3660	0.2839	0.034*
C20	0.5647 (3)	−0.4312 (2)	0.21081 (18)	0.0339 (6)
H20A	0.5015	−0.3756	0.2284	0.051*
H20B	0.5966	−0.4465	0.2600	0.051*
H20C	0.5047	−0.4951	0.1644	0.051*
C21	1.1840 (4)	−0.3559 (2)	0.0412 (2)	0.0405 (7)
H21A	1.2261	−0.3907	0.0753	0.061*
H21B	1.2684	−0.3226	0.0221	0.061*
H21C	1.1138	−0.4082	−0.0091	0.061*
C22	0.8090 (3)	−0.3404 (2)	−0.01948 (18)	0.0347 (7)
H22A	0.8817	−0.2780	−0.0144	0.042*
H22B	0.8382	−0.4036	−0.0638	0.042*
C23	0.6166 (3)	−0.2272 (2)	0.00261 (18)	0.0315 (6)
H23A	0.6447	−0.2094	0.0645	0.038*
H23B	0.5039	−0.2307	−0.0083	0.038*
C24	0.6983 (3)	−0.1383 (2)	−0.01740 (16)	0.0256 (6)
C25	0.7411 (3)	−0.0338 (2)	0.04815 (16)	0.0257 (6)
C26	0.8068 (3)	0.0508 (2)	0.02899 (16)	0.0264 (6)
C27	0.8336 (3)	0.0287 (2)	−0.05658 (17)	0.0279 (6)
H27	0.8764	0.0848	−0.0698	0.033*
C28	0.7982 (3)	−0.0750 (2)	−0.12275 (16)	0.0260 (6)
C29	0.7298 (3)	−0.1569 (2)	−0.10173 (17)	0.0273 (6)
H29	0.7041	−0.2265	−0.1456	0.033*
C30	0.8354 (3)	−0.0977 (2)	−0.21405 (17)	0.0338 (6)
H30A	0.8427	−0.1725	−0.2440	0.051*
H30B	0.9336	−0.0543	−0.2103	0.051*
H30C	0.7535	−0.0809	−0.2459	0.051*
C31	0.8543 (3)	0.1632 (2)	0.09953 (17)	0.0286 (6)
H31A	0.8702	0.1610	0.1566	0.034*
H31B	0.9522	0.1969	0.0903	0.034*
C32	0.7742 (4)	0.3341 (2)	0.16010 (17)	0.0347 (7)
H32A	0.7027	0.3762	0.1467	0.042*
H32B	0.8795	0.3628	0.1555	0.042*
C33	0.7682 (3)	0.3460 (2)	0.25276 (17)	0.0303 (6)
C34	0.9009 (3)	0.3538 (2)	0.30889 (17)	0.0291 (6)
C35	0.8907 (3)	0.3572 (2)	0.39237 (17)	0.0281 (6)
C36	0.7432 (3)	0.3549 (2)	0.41930 (17)	0.0305 (6)
H36	0.7349	0.3573	0.4749	0.037*
C37	0.6076 (3)	0.3491 (2)	0.36598 (18)	0.0310 (6)
C38	0.6236 (3)	0.3439 (2)	0.28330 (18)	0.0326 (6)
H38	0.5339	0.3387	0.2464	0.039*
C39	0.4496 (3)	0.3473 (3)	0.3975 (2)	0.0422 (7)
H39A	0.3737	0.3574	0.3578	0.063*
H39B	0.4574	0.4042	0.4551	0.063*
H39C	0.4171	0.2793	0.3997	0.063*
C40	1.1261 (3)	0.4600 (2)	0.2962 (2)	0.0389 (7)
H40A	1.0671	0.4875	0.2614	0.058*
H40B	1.2297	0.4563	0.2803	0.058*
H40C	1.1333	0.5071	0.3573	0.058*
C41	1.0377 (3)	0.3623 (2)	0.45033 (17)	0.0308 (6)
H41A	1.0989	0.3105	0.4156	0.037*
H41B	1.1010	0.4334	0.4713	0.037*
C42	0.9611 (3)	0.2275 (2)	0.49944 (17)	0.0307 (6)
H42A	0.8782	0.1977	0.4494	0.037*
H42B	0.9197	0.2166	0.5477	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0239 (9)	0.0333 (11)	0.0303 (10)	−0.0023 (8)	−0.0006 (8)	0.0177 (8)
O2	0.0250 (10)	0.0432 (12)	0.0393 (11)	0.0064 (8)	0.0069 (8)	0.0233 (9)
O3	0.0250 (9)	0.0369 (11)	0.0264 (10)	0.0097 (8)	0.0068 (8)	0.0153 (8)
O4	0.0335 (10)	0.0261 (10)	0.0301 (10)	0.0013 (8)	0.0017 (8)	0.0152 (8)
O5	0.0320 (10)	0.0320 (11)	0.0411 (11)	0.0026 (8)	0.0075 (9)	0.0179 (9)
O6	0.0350 (11)	0.0282 (11)	0.0325 (10)	−0.0007 (8)	−0.0038 (8)	0.0127 (8)
O7	0.0344 (10)	0.0271 (10)	0.0307 (10)	0.0115 (8)	0.0015 (8)	0.0099 (8)
O8	0.0322 (10)	0.0297 (11)	0.0380 (11)	0.0071 (8)	0.0121 (8)	0.0164 (8)
O9	0.0340 (10)	0.0306 (11)	0.0256 (10)	0.0069 (8)	0.0051 (8)	0.0083 (8)
C1	0.0256 (14)	0.0318 (15)	0.0305 (14)	0.0007 (11)	0.0059 (11)	0.0168 (12)
C2	0.0274 (14)	0.0287 (15)	0.0322 (15)	0.0037 (11)	0.0057 (11)	0.0137 (12)
C3	0.0277 (14)	0.0326 (16)	0.0308 (15)	0.0101 (12)	0.0067 (12)	0.0117 (12)
C4	0.0238 (14)	0.0394 (17)	0.0335 (15)	0.0109 (12)	0.0095 (12)	0.0169 (13)
C5	0.0262 (14)	0.0313 (15)	0.0270 (14)	0.0042 (11)	0.0074 (11)	0.0168 (12)
C6	0.0247 (13)	0.0299 (15)	0.0265 (14)	0.0002 (11)	0.0035 (11)	0.0160 (11)
C7	0.0261 (13)	0.0260 (14)	0.0258 (14)	0.0034 (11)	0.0054 (11)	0.0153 (11)
C8	0.0274 (14)	0.0300 (15)	0.0293 (14)	0.0064 (11)	0.0077 (11)	0.0176 (12)
C9	0.0280 (14)	0.0301 (15)	0.0264 (14)	0.0027 (11)	0.0040 (11)	0.0157 (11)
C10	0.0269 (14)	0.0291 (15)	0.0240 (14)	0.0023 (11)	0.0048 (11)	0.0118 (11)
C11	0.0285 (15)	0.0395 (17)	0.0329 (15)	0.0044 (12)	0.0024 (12)	0.0113 (13)
C12	0.0273 (14)	0.0297 (15)	0.0298 (14)	0.0015 (11)	0.0038 (11)	0.0161 (12)
C13	0.0332 (15)	0.0262 (15)	0.0354 (15)	0.0061 (12)	0.0026 (12)	0.0128 (12)
C14	0.0293 (14)	0.0213 (14)	0.0327 (15)	0.0035 (11)	0.0023 (11)	0.0109 (11)
C15	0.0273 (14)	0.0228 (14)	0.0365 (15)	0.0041 (11)	0.0078 (12)	0.0123 (12)
C16	0.0325 (15)	0.0217 (14)	0.0317 (15)	0.0033 (11)	0.0044 (12)	0.0109 (11)
C17	0.0291 (14)	0.0248 (14)	0.0330 (15)	0.0048 (11)	0.0017 (12)	0.0100 (11)
C18	0.0287 (14)	0.0221 (14)	0.0329 (15)	0.0074 (11)	0.0075 (12)	0.0098 (11)
C19	0.0312 (14)	0.0247 (14)	0.0305 (14)	0.0073 (11)	0.0035 (12)	0.0123 (11)
C20	0.0342 (15)	0.0278 (15)	0.0408 (16)	0.0049 (12)	0.0085 (13)	0.0149 (12)
C21	0.0406 (17)	0.0426 (18)	0.0467 (18)	0.0115 (14)	0.0171 (14)	0.0241 (15)
C22	0.0354 (16)	0.0342 (16)	0.0378 (16)	0.0067 (13)	0.0054 (13)	0.0182 (13)
C23	0.0285 (14)	0.0317 (16)	0.0366 (16)	0.0044 (12)	0.0022 (12)	0.0172 (12)
C24	0.0218 (13)	0.0281 (15)	0.0291 (14)	0.0060 (11)	0.0001 (11)	0.0143 (11)
C25	0.0226 (13)	0.0300 (15)	0.0273 (14)	0.0075 (11)	0.0041 (11)	0.0139 (11)
C26	0.0225 (13)	0.0275 (14)	0.0305 (14)	0.0076 (11)	0.0016 (11)	0.0129 (11)
C27	0.0243 (13)	0.0292 (15)	0.0359 (15)	0.0071 (11)	0.0044 (11)	0.0185 (12)
C28	0.0247 (13)	0.0312 (15)	0.0244 (14)	0.0081 (11)	0.0018 (11)	0.0135 (11)
C29	0.0262 (14)	0.0253 (14)	0.0293 (14)	0.0034 (11)	−0.0022 (11)	0.0118 (11)
C30	0.0389 (16)	0.0351 (16)	0.0288 (15)	0.0081 (13)	0.0050 (12)	0.0143 (12)
C31	0.0255 (14)	0.0305 (15)	0.0316 (15)	0.0089 (11)	0.0048 (11)	0.0136 (12)
C32	0.0440 (17)	0.0252 (15)	0.0346 (16)	0.0095 (13)	0.0053 (13)	0.0111 (12)
C33	0.0372 (16)	0.0216 (14)	0.0322 (15)	0.0085 (12)	0.0042 (12)	0.0104 (11)
C34	0.0303 (15)	0.0207 (14)	0.0341 (15)	0.0067 (11)	0.0094 (12)	0.0078 (11)
C35	0.0299 (14)	0.0230 (14)	0.0306 (15)	0.0040 (11)	0.0048 (11)	0.0103 (11)
C36	0.0334 (15)	0.0270 (15)	0.0310 (15)	0.0038 (12)	0.0061 (12)	0.0120 (12)
C37	0.0289 (15)	0.0271 (15)	0.0353 (15)	0.0034 (12)	0.0033 (12)	0.0119 (12)
C38	0.0307 (15)	0.0282 (15)	0.0357 (16)	0.0041 (12)	−0.0014 (12)	0.0116 (12)
C39	0.0340 (16)	0.047 (2)	0.0469 (18)	0.0054 (14)	0.0058 (14)	0.0219 (15)
C40	0.0388 (17)	0.0320 (17)	0.0485 (18)	0.0027 (13)	0.0108 (14)	0.0196 (14)
C41	0.0284 (14)	0.0286 (15)	0.0360 (16)	0.0035 (12)	0.0051 (12)	0.0145 (12)
C42	0.0305 (15)	0.0351 (16)	0.0302 (15)	0.0051 (12)	0.0068 (12)	0.0172 (12)

Geometric parameters (Å, º)

O1—C6	1.394 (3)	C9—C11	1.504 (3)
O1—C1	1.441 (3)	C13—C14	1.512 (3)
O2—C2	1.429 (3)	C14—C15	1.392 (4)
O2—C3	1.431 (3)	C14—C19	1.400 (4)
O3—C25	1.389 (3)	C15—C16	1.397 (4)
O3—C4	1.444 (3)	C16—C17	1.392 (4)
O4—C13	1.435 (3)	C16—C22	1.519 (4)
O4—C12	1.441 (3)	C17—C18	1.391 (4)
O5—C15	1.398 (3)	C18—C19	1.392 (3)
O5—C21	1.433 (3)	C18—C20	1.512 (4)
O6—C22	1.429 (3)	C23—C24	1.505 (4)
O6—C23	1.430 (3)	C24—C29	1.392 (3)
O7—C32	1.434 (3)	C24—C25	1.396 (4)
O7—C31	1.435 (3)	C25—C26	1.398 (4)
O8—C34	1.398 (3)	C26—C27	1.391 (4)
O8—C40	1.439 (3)	C26—C31	1.502 (4)
O9—C41	1.426 (3)	C27—C28	1.389 (4)
O9—C42	1.432 (3)	C28—C29	1.391 (4)
C1—C2	1.504 (3)	C28—C30	1.509 (3)
C3—C4	1.505 (3)	C32—C33	1.505 (4)
C5—C10	1.394 (3)	C33—C34	1.390 (4)
C5—C6	1.394 (4)	C33—C38	1.394 (4)
C5—C42	1.511 (4)	C34—C35	1.396 (4)
C6—C7	1.397 (4)	C35—C36	1.392 (4)
C7—C8	1.388 (3)	C35—C41	1.515 (4)
C7—C12	1.505 (3)	C36—C37	1.391 (4)
C8—C9	1.390 (4)	C37—C38	1.382 (4)
C9—C10	1.393 (4)	C37—C39	1.510 (4)
C6—O1—C1	114.92 (18)	C17—C18—C19	118.2 (2)
C2—O2—C3	117.04 (19)	C17—C18—C20	120.5 (2)
C25—O3—C4	115.48 (18)	C19—C18—C20	121.2 (2)
C13—O4—C12	112.4 (2)	C18—C19—C14	121.8 (2)
C15—O5—C21	113.4 (2)	O6—C22—C16	113.1 (2)
C22—O6—C23	112.2 (2)	O6—C23—C24	114.1 (2)
C32—O7—C31	111.9 (2)	C29—C24—C25	118.1 (2)
C34—O8—C40	113.1 (2)	C29—C24—C23	121.3 (2)
C41—O9—C42	111.52 (19)	C25—C24—C23	120.6 (2)
O1—C1—C2	108.7 (2)	O3—C25—C24	118.8 (2)
O2—C2—C1	115.1 (2)	O3—C25—C26	119.9 (2)
O2—C3—C4	114.3 (2)	C24—C25—C26	121.0 (2)
O3—C4—C3	107.4 (2)	C27—C26—C25	118.7 (2)
C10—C5—C6	118.4 (2)	C27—C26—C31	120.0 (2)
C10—C5—C42	120.6 (2)	C25—C26—C31	121.2 (2)
C6—C5—C42	121.0 (2)	C28—C27—C26	121.7 (2)
O1—C6—C5	118.8 (2)	C27—C28—C29	117.9 (2)
O1—C6—C7	119.6 (2)	C27—C28—C30	120.7 (2)
C5—C6—C7	121.4 (2)	C29—C28—C30	121.4 (2)
C8—C7—C6	118.3 (2)	C28—C29—C24	122.4 (2)
C8—C7—C12	120.4 (2)	O7—C31—C26	109.1 (2)
C6—C7—C12	121.4 (2)	O7—C32—C33	112.6 (2)
C7—C8—C9	122.1 (2)	C34—C33—C38	117.7 (2)
C8—C9—C10	118.1 (2)	C34—C33—C32	122.7 (3)
C8—C9—C11	121.1 (2)	C38—C33—C32	119.5 (2)
C10—C9—C11	120.7 (2)	C33—C34—C35	121.6 (2)
C9—C10—C5	121.7 (2)	C33—C34—O8	119.9 (2)
O4—C12—C7	107.7 (2)	C35—C34—O8	118.4 (2)
O4—C13—C14	112.5 (2)	C36—C35—C34	118.0 (2)
C15—C14—C19	118.1 (2)	C36—C35—C41	122.1 (2)
C15—C14—C13	121.9 (2)	C34—C35—C41	119.9 (2)
C19—C14—C13	119.9 (2)	C37—C36—C35	122.3 (2)
C14—C15—O5	119.2 (2)	C38—C37—C36	117.4 (3)
C14—C15—C16	121.9 (2)	C38—C37—C39	121.7 (2)
O5—C15—C16	118.8 (2)	C36—C37—C39	120.9 (2)
C17—C16—C15	118.0 (2)	C37—C38—C33	122.9 (2)
C17—C16—C22	121.6 (2)	O9—C41—C35	113.0 (2)
C15—C16—C22	120.4 (2)	O9—C42—C5	112.6 (2)
C18—C17—C16	122.1 (2)