A comparative analysis of mono- and disaccharide benzyl fucopyranosides

The syntheses and X-ray analyses of two fuco­pyran­osides, the monosaccharide benzyl 3,4-di-O-acetyl-2-hydro­xy-β-D-fuco­pyran­oside, C₁₇H₂₂O₇, and the disaccharide 1-benzyl O-(2,3-di-O-acetyl-4,6-O-benzyl­idene-β-D-gluco­pyran­osyl)-(12)-3,4-O-iso­propyl­idene-β-D-fuco­pyran­oside, C₃₃H₄₀O₁₂, are de­scribed. The different substituents induce small conformational changes on the fuco­pyran­oside ring. However, the conformation of the benzyl group varies from (+)gauche for the monosaccharide to synperiplanar for the disaccharide.

S1. Comment

Fucose is an important deoxysugar found recently as a constituent unit of glycoresins from the genus Ipomea (Bah & Pereda-Miranda, 1997). These glycoresins, called tricolorins, have attracted great interest from the biological and chemical points of view. As part of a strategy directed towards the synthesis of analogues of the mentioned glycosides, the syntheses and X-ray analyses of benzyl fucopyranoside, (I) (Fig. 1), and the closely related benzyl disaccharide, (II) (Fig. 2), have been performed and the results are presented here. \sch

In both compounds, the pyranoside rings have a ⁴C₁ chair conformation, with all substituents oriented at equatorial positions, except the substituent at position C4 of the glucopyranoside moiety, which exhibits an axial orientation. For compound (II), the equatorial orientation at position 3 in the fucopyranoside ring is frustrated by the formation of a five-membered ring. Therefore, a biaxial conformation is observed, with an angle of 53.9 (2)° between the C3—O3 bond and the Cremer-Pople plane, calculated as defined in Cremer & Pople (1975) and defined, in both compounds, by the atoms C1—C5 and O5.

The isopropylidene group also produces the significant deviation from the ideal ⁴C₁ chair conformation observed in the fucopyranoside of compound (II), as can be seen when comparing the puckering parameters (Cremer & Pople, 1975) in both fucopyranoside rings [Q = 0.572 (2)°, θ = 176.9 (2)° and ϕ = 186 (3)° for (I), and Q = 0.556 (3)°, θ = 159.9 (3)° and ϕ = 220.9 (8)° for (II)]. In compound (II), the effect of the benzylidene group on the glucopyranosil conformation is smaller, and the ring defined by atoms O10 and C17—C21 is very close to the ideal ⁴C₁ chair conformation [Q = 0.597 (3)°, θ = 170.7 (3)° and ϕ = 156.0 (16)°].

The angle between the glycosidic bond and the normals to both Cremer-Pople planes, calculated for both fucopyranoside rings, are 68.7 (1)° for (I) and 76.0 (2)° for (II). Due to the exoanomeric effect, the substituent on C1, in this case the benzyl group, should prefer a (+) gauche conformation (Jeffrey, 1990). This is the case in (I), as can be seen in the C12—C11—O1—C1 torsion angle, but not in (II), which shows a clear synperiplanar conformation, with atoms C1, O1, C10 and C11 in almost the same plane [largest deviation from the least-squares plane 0.023 (1) Å for which atom?]. It is also noticeable that, for (I), the C5—O5, C1—O5 and C1—O1 bond distances (Table 1) are closer to the standard values for an axial glycosidic bond (1.434, 1.419 and 1.398 Å, respectively) than for an equatorial one (1.426, 1.428 and 1.385 Å, respectively) (Jeffrey & Taylor, 1980; Jeffrey, 1990). In (II), these bond distances (Table 3) do not correspond clearly to equatorial or axial cases.

In the disaccharide, (II), atoms O5, C1, C2, O2, C17, C18 and C19 are almost co-planar [largest deviation from the least squares plane -0.109 (2) Å for C19]. Therefore, three atoms of each saccharide lie in the plane defined by the glycosidic linkage. For each pyranoside, the rest of the atoms lie on one side of this plane, the two rings being on opposite sides of the plane. For this reason, the O10—C17—O2—C2 torsion angle is almost equal to C3—C2—O2—C17. This conformation can be partly due to the weak hydrogen bond joining C17 in the glucopyranoside and O3 in the fucopyranoside (Table 4).

An O—H···O hydrogen bond is observed in (I) between the hydroxy group and one of the acetate O atoms (Table 2). Due to this intermolecular interaction, the molecules form chains along the b direction (Fig. 3). There are also weak C—H···O interactions involving the benzyl group as donor and the pyranoside group as acceptor, which join the chains along the a direction. For compound (II), there are no strong hydrogen-bond interactions, due to the absence of hydroxyl groups. The only significant intermolecular interaction is a weak C—H···O hydrogen bond (Table 4) joining the molecules in the a direction.

S2. Experimental

Compound (I) (Scheme) was prepared using fucose (Lerner, 1993) as the starting material, which was peracetylated with acetic anhydride. Bromination of the anomeric C atom was performed using a mixed hydrobromic acid-acetic acid solution (30%; ratio of acids?) to produce intermediate (1), which was subsequently reacted with benzyl alcohol under Koenigs-Knorr conditions to yield glycoside (2) (Igarashi, 1977). Deacetylation with sodium methoxide solution afforded a compound which was treated with two equivalents of acetic anhydride to produce (I). Spectroscopic analysis for (I): ¹H NMR (CDCl₃, 300 MHz, δ, p.p.m.): 1.3 (d, 3H), 2.0 and 2.2 (both s, 3H), 3.8 (m, 1H), 3.9 (dd, 1H), 4.4 (d, 1H), 4.6 (d, 1H), 4.95 (dd, 1H), 5.0 (d, 1H), 5.22 (dd, 1H), 7.4 (m, 5H). Compound (II) (Scheme) was prepared according to Fischer O-glycoside coupling-reaction conditions, consisting of the reaction between fucose and benzyl alcohol under a controlled stream of HCl gas to produce benzyl fucose (Searle et al., 1996). Acetonide formation was performed under standard conditions (acetone, 2,2-dimethoxypropane, P-TsOH as catalyst), to afford the intermediate glycosyl acceptor, (3), which was coupled with 2,3-di-O-acetyl-4,6-O-benzylidene glucopyranosyl trichloroacetimidate, (4) (Larson & Heathcock, 1997), under AgOTf catalysis to generate the desired disaccharide, (II), in 50% yield. Spectroscopic analysis for (II): ¹H NMR (CDCl₃, 300 MHz, δ, p.p.m.): 1.3 (s, 3H), 1.4 (d, 3H), 1.5 (s, 3H), 2.0, 2.1 (s, 6H), 3.4 (m, 1H), 3.7 (m, 4H), 3.9 (dd, 1H), 4.0 (m, 2H), 4.3 (d, 1H), 4.6 (d, 1H), 4.9 (t, 2H), 5.0 (t, 1H), 5.4 (s, 1H), 7.3 (m, 10H).

S3. Refinement

The absolute configurations of these two light-atom structures were not determined by the present X-ray analyses but were already known from the known configuration of the starting materials. H atoms were placed on calculated positions, with C—H = 0.93–0.98 Å Is this added text correct?, and their isotropic displacement parameters were fixed to 1.2 or 1.5 times the U_iso of the bonded atom.

Computing details

For both compounds, data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 1998); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of the molecular structure of (I), showing 50% displacement ellipsoids and the atom-numbering scheme. H atoms are drawn as small spheres of arbitrary radii.
	Fig. 2. A view of the molecular structure of (II) showing 50% displacement ellipsoids and the atom-numbering scheme. H atoms are drawn as small spheres of arbitrary radii.
	Fig. 3. A drawing of the unit cell of (I) viewed along the a axis. Dashed lines indicate hydrogen bonds. Atom O7* is at symmetry position (2 - x, y + 1/2, 1 - z) and atom O2# is at symmetry position (2 - x, y - 1/2, 1 - z).

(I) benzyl 2-hydroxo-3,4-di-O-acetyl-β-D-fucopyranoside

Crystal data

C17H22O7	F(000) = 360
Mr = 338.36	Dx = 1.273 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 15 reflections
a = 8.735 (2) Å	θ = 11.2–12.6°
b = 9.526 (2) Å	µ = 0.10 mm^−1
c = 10.605 (3) Å	T = 293 K
β = 91.00 (2)°	Prism, colourless
V = 882.4 (5) Å^3	0.85 × 0.70 × 0.32 mm
Z = 2

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.017
non–profiled ω/2θ scans	θmax = 30.4°, θmin = 2.3°
Absorption correction: ψ scan (North et al., 1968)	h = 0→12
Tmin = 0.890, Tmax = 0.965	k = −13→0
2982 measured reflections	l = −15→15
2820 independent reflections	3 standard reflections every 60 min
2457 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.040	w = 1/[σ^2(Fo^2) + (0.0964P)^2 + 0.0099P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.130	(Δ/σ)max = 0.004
S = 1.09	Δρmax = 0.23 e Å^−3
2820 reflections	Δρmin = −0.16 e Å^−3
221 parameters

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	0.93177 (18)	0.7069 (2)	0.25656 (14)	0.0433 (3)
H1	1.0371	0.6783	0.2770	0.052*
C2	0.86241 (18)	0.78169 (18)	0.36932 (14)	0.0418 (3)
H2	0.7608	0.8184	0.3465	0.05*
C3	0.85001 (17)	0.67704 (18)	0.47599 (13)	0.0394 (3)
H3	0.9531	0.6522	0.5064	0.047*
C4	0.76643 (17)	0.54421 (17)	0.43430 (14)	0.0413 (3)
H4	0.7695	0.4747	0.5024	0.05*
C5	0.8412 (2)	0.4843 (2)	0.31704 (17)	0.0487 (4)
H5	0.9467	0.4575	0.3388	0.058*
C6	0.7596 (3)	0.3583 (3)	0.2631 (2)	0.0718 (6)
H6A	0.8125	0.3257	0.1901	0.108*
H6B	0.6567	0.3838	0.2394	0.108*
H6C	0.7574	0.2851	0.3252	0.108*
C7	0.5017 (2)	0.5503 (2)	0.4878 (2)	0.0527 (4)
C8	0.3486 (2)	0.6008 (3)	0.4429 (2)	0.0643 (5)
H8A	0.3463	0.7015	0.4452	0.096*
H8B	0.2708	0.5641	0.4967	0.096*
H8C	0.3300	0.5692	0.3581	0.096*
C9	0.8020 (2)	0.7019 (2)	0.69494 (15)	0.0457 (3)
C10	0.6959 (3)	0.7658 (4)	0.7866 (2)	0.0757 (7)
H10A	0.7045	0.7171	0.8656	0.114*
H10B	0.5927	0.7588	0.7546	0.114*
H10C	0.7219	0.8629	0.7987	0.114*
C11	1.0074 (2)	0.7551 (3)	0.04565 (17)	0.0605 (5)
H11A	0.9953	0.8256	−0.0198	0.073*
H11B	0.9577	0.6700	0.0159	0.073*
C12	1.1764 (2)	0.7259 (2)	0.06563 (15)	0.0493 (4)
C13	1.2672 (3)	0.8160 (3)	0.1345 (2)	0.0640 (5)
H13	1.2240	0.8952	0.1708	0.077*
C14	1.4228 (3)	0.7906 (5)	0.1507 (2)	0.0859 (10)
H14	1.4821	0.8522	0.1989	0.103*
C15	1.4893 (3)	0.6779 (5)	0.0975 (3)	0.0923 (11)
H15	1.5937	0.6617	0.1082	0.111*
C16	1.3995 (5)	0.5870 (4)	0.0268 (4)	0.0987 (12)
H16	1.4440	0.5093	−0.0109	0.118*
C17	1.2414 (3)	0.6107 (3)	0.0112 (2)	0.0707 (6)
H17	1.1814	0.5485	−0.0358	0.085*
O1	0.93110 (14)	0.80326 (18)	0.15765 (12)	0.0542 (3)
O2	0.95875 (17)	0.89248 (17)	0.41208 (13)	0.0593 (4)
H2A	0.9850	0.9400	0.3517	0.089*
O3	0.76822 (14)	0.74379 (14)	0.57660 (10)	0.0447 (3)
O4	0.60999 (12)	0.57921 (15)	0.40270 (11)	0.0451 (3)
O5	0.84441 (14)	0.58883 (16)	0.21977 (11)	0.0494 (3)
O6	0.5285 (2)	0.4934 (4)	0.58677 (19)	0.0944 (8)
O7	0.90249 (19)	0.6210 (2)	0.72177 (12)	0.0636 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0386 (6)	0.0554 (9)	0.0360 (6)	0.0019 (6)	0.0041 (5)	0.0038 (6)
C2	0.0410 (6)	0.0460 (8)	0.0384 (6)	−0.0049 (6)	0.0028 (5)	0.0016 (6)
C3	0.0381 (6)	0.0463 (8)	0.0340 (6)	0.0032 (6)	0.0050 (4)	−0.0018 (5)
C4	0.0411 (6)	0.0447 (7)	0.0383 (6)	0.0020 (6)	0.0043 (5)	−0.0001 (6)
C5	0.0530 (8)	0.0490 (8)	0.0441 (7)	0.0015 (7)	0.0065 (6)	−0.0069 (7)
C6	0.0934 (17)	0.0573 (12)	0.0649 (12)	−0.0120 (12)	0.0135 (11)	−0.0174 (10)
C7	0.0491 (7)	0.0566 (10)	0.0528 (9)	−0.0065 (7)	0.0127 (6)	0.0030 (8)
C8	0.0450 (8)	0.0678 (13)	0.0805 (13)	−0.0014 (8)	0.0121 (8)	0.0020 (11)
C9	0.0529 (8)	0.0478 (8)	0.0363 (6)	0.0025 (7)	0.0030 (5)	−0.0039 (6)
C10	0.0856 (14)	0.0989 (19)	0.0431 (8)	0.0313 (15)	0.0139 (9)	−0.0047 (11)
C11	0.0567 (9)	0.0863 (15)	0.0387 (7)	0.0029 (10)	0.0044 (6)	0.0106 (9)
C12	0.0589 (9)	0.0535 (9)	0.0358 (6)	0.0015 (7)	0.0132 (6)	0.0104 (6)
C13	0.0626 (11)	0.0766 (14)	0.0531 (10)	−0.0059 (11)	0.0118 (8)	−0.0030 (10)
C14	0.0637 (12)	0.135 (3)	0.0596 (12)	−0.0153 (17)	0.0082 (9)	0.0097 (16)
C15	0.0643 (13)	0.132 (3)	0.0811 (16)	0.0172 (18)	0.0157 (12)	0.037 (2)
C16	0.112 (2)	0.086 (2)	0.100 (2)	0.046 (2)	0.0504 (19)	0.0271 (18)
C17	0.0922 (15)	0.0526 (11)	0.0680 (12)	0.0005 (11)	0.0243 (11)	0.0034 (10)
O1	0.0509 (6)	0.0688 (8)	0.0431 (6)	0.0081 (6)	0.0078 (4)	0.0133 (6)
O2	0.0680 (8)	0.0585 (8)	0.0516 (7)	−0.0243 (7)	0.0042 (6)	−0.0018 (6)
O3	0.0488 (5)	0.0498 (6)	0.0355 (5)	0.0073 (5)	0.0060 (4)	−0.0016 (4)
O4	0.0383 (4)	0.0543 (6)	0.0428 (5)	−0.0034 (5)	0.0034 (4)	0.0037 (5)
O5	0.0509 (6)	0.0602 (7)	0.0373 (5)	−0.0027 (6)	0.0033 (4)	−0.0035 (5)
O6	0.0712 (9)	0.138 (2)	0.0752 (11)	0.0016 (12)	0.0211 (8)	0.0479 (14)
O7	0.0775 (9)	0.0712 (10)	0.0419 (6)	0.0229 (8)	−0.0024 (6)	0.0011 (6)

Geometric parameters (Å, º)

C1—O1	1.394 (2)	C8—H8C	0.96
C1—O5	1.411 (2)	C9—O7	1.199 (2)
C1—C2	1.527 (2)	C9—O3	1.3445 (19)
C1—H1	0.98	C9—C10	1.485 (3)
C2—O2	1.419 (2)	C10—H10A	0.96
C2—C3	1.513 (2)	C10—H10B	0.96
C2—H2	0.98	C10—H10C	0.96
C3—O3	1.4419 (17)	C11—O1	1.447 (2)
C3—C4	1.523 (2)	C11—C12	1.513 (3)
C3—H3	0.98	C11—H11A	0.97
C4—O4	1.4403 (18)	C11—H11B	0.97
C4—C5	1.526 (2)	C12—C17	1.368 (3)
C4—H4	0.98	C12—C13	1.371 (3)
C5—O5	1.434 (2)	C13—C14	1.389 (4)
C5—C6	1.503 (3)	C13—H13	0.93
C5—H5	0.98	C14—C15	1.349 (6)
C6—H6A	0.96	C14—H14	0.93
C6—H6B	0.96	C15—C16	1.381 (6)
C6—H6C	0.96	C15—H15	0.93
C7—O6	1.202 (3)	C16—C17	1.406 (5)
C7—O4	1.346 (2)	C16—H16	0.93
C7—C8	1.492 (3)	C17—H17	0.93
C8—H8A	0.96	O2—H2A	0.82
C8—H8B	0.96
O1—C1—O5	108.78 (13)	C7—C8—H8C	109.5
O1—C1—C2	106.60 (14)	H8A—C8—H8C	109.5
O5—C1—C2	111.65 (12)	H8B—C8—H8C	109.5
O1—C1—H1	109.9	O7—C9—O3	124.04 (15)
O5—C1—H1	109.9	O7—C9—C10	124.83 (17)
C2—C1—H1	109.9	O3—C9—C10	111.11 (17)
O2—C2—C3	107.50 (13)	C9—C10—H10A	109.5
O2—C2—C1	110.87 (13)	C9—C10—H10B	109.5
C3—C2—C1	108.22 (14)	H10A—C10—H10B	109.5
O2—C2—H2	110.1	C9—C10—H10C	109.5
C3—C2—H2	110.1	H10A—C10—H10C	109.5
C1—C2—H2	110.1	H10B—C10—H10C	109.5
O3—C3—C2	107.82 (13)	O1—C11—C12	113.94 (15)
O3—C3—C4	109.86 (12)	O1—C11—H11A	108.8
C2—C3—C4	111.76 (12)	C12—C11—H11A	108.8
O3—C3—H3	109.1	O1—C11—H11B	108.8
C2—C3—H3	109.1	C12—C11—H11B	108.8
C4—C3—H3	109.1	H11A—C11—H11B	107.7
O4—C4—C3	108.88 (13)	C17—C12—C13	119.1 (2)
O4—C4—C5	108.35 (13)	C17—C12—C11	120.0 (2)
C3—C4—C5	109.75 (13)	C13—C12—C11	120.9 (2)
O4—C4—H4	109.9	C12—C13—C14	120.9 (3)
C3—C4—H4	109.9	C12—C13—H13	119.6
C5—C4—H4	109.9	C14—C13—H13	119.6
O5—C5—C6	107.17 (16)	C15—C14—C13	121.0 (3)
O5—C5—C4	109.90 (14)	C15—C14—H14	119.5
C6—C5—C4	113.70 (16)	C13—C14—H14	119.5
O5—C5—H5	108.6	C14—C15—C16	118.8 (3)
C6—C5—H5	108.6	C14—C15—H15	120.6
C4—C5—H5	108.6	C16—C15—H15	120.6
C5—C6—H6A	109.5	C15—C16—C17	120.7 (3)
C5—C6—H6B	109.5	C15—C16—H16	119.6
H6A—C6—H6B	109.5	C17—C16—H16	119.6
C5—C6—H6C	109.5	C12—C17—C16	119.5 (3)
H6A—C6—H6C	109.5	C12—C17—H17	120.2
H6B—C6—H6C	109.5	C16—C17—H17	120.2
O6—C7—O4	123.3 (2)	C1—O1—C11	114.44 (16)
O6—C7—C8	125.73 (19)	C2—O2—H2A	109.5
O4—C7—C8	110.94 (18)	C9—O3—C3	117.19 (13)
C7—C8—H8A	109.5	C7—O4—C4	118.14 (14)
C7—C8—H8B	109.5	C1—O5—C5	111.84 (12)
H8A—C8—H8B	109.5
O1—C1—C2—O2	−66.54 (17)	C13—C14—C15—C16	−0.4 (5)
O5—C1—C2—O2	174.80 (13)	C14—C15—C16—C17	−0.5 (5)
O1—C1—C2—C3	175.78 (12)	C13—C12—C17—C16	0.0 (3)
O5—C1—C2—C3	57.13 (16)	C11—C12—C17—C16	177.9 (2)
O2—C2—C3—O3	66.81 (16)	C15—C16—C17—C12	0.7 (4)
C1—C2—C3—O3	−173.38 (12)	O5—C1—O1—C11	−65.48 (18)
O2—C2—C3—C4	−172.35 (13)	C2—C1—O1—C11	174.01 (14)
C1—C2—C3—C4	−52.54 (16)	C12—C11—O1—C1	−62.4 (3)
O3—C3—C4—O4	54.24 (15)	O7—C9—O3—C3	5.6 (3)
C2—C3—C4—O4	−65.38 (15)	C10—C9—O3—C3	−172.74 (19)
O3—C3—C4—C5	172.68 (13)	C2—C3—O3—C9	−150.35 (14)
C2—C3—C4—C5	53.06 (17)	C4—C3—O3—C9	87.64 (16)
O4—C4—C5—O5	63.03 (18)	O6—C7—O4—C4	−2.2 (4)
C3—C4—C5—O5	−55.72 (17)	C8—C7—O4—C4	176.70 (17)
O4—C4—C5—C6	−57.1 (2)	C3—C4—O4—C7	−101.17 (18)
C3—C4—C5—C6	−175.85 (17)	C5—C4—O4—C7	139.52 (17)
O1—C11—C12—C17	139.1 (2)	O1—C1—O5—C5	179.48 (13)
O1—C11—C12—C13	−43.0 (3)	C2—C1—O5—C5	−63.19 (17)
C17—C12—C13—C14	−0.9 (3)	C6—C5—O5—C1	−174.24 (15)
C11—C12—C13—C14	−178.7 (2)	C4—C5—O5—C1	61.74 (17)
C12—C13—C14—C15	1.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O7^i	0.82	2.14	2.878 (2)	150
C15—H15···O5^ii	0.93	2.57	3.447 (3)	158

Symmetry codes: (i) −x+2, y+1/2, −z+1; (ii) x+1, y, z.

(II) O-(2,3-di-O-acetyl-4,6-O-benzylidene-β-D-glucopyranosyl)- (1→ 2)–3,4-O-isopropylidene-β-D-fucopyranoside

Crystal data

C33H40O12	F(000) = 1336
Mr = 628.65	Dx = 1.286 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 8.901 (1) Å	θ = 11.9–20.9°
b = 14.261 (1) Å	µ = 0.10 mm^−1
c = 25.583 (1) Å	T = 293 K
V = 3247.4 (4) Å^3	Prism, colourless
Z = 4	0.65 × 0.50 × 0.32 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0
non–profiled ω/2θ scans	θmax = 30.4°, θmin = 2.4°
Absorption correction: ψ scan (North et al., 1968)	h = −12→0
Tmin = 0.905, Tmax = 0.965	k = −20→0
5471 measured reflections	l = 0→36
5471 independent reflections	3 standard reflections every 60 min
2832 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.041	w = 1/[σ^2(Fo^2) + (0.0882P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.138	(Δ/σ)max = 0.022
S = 0.89	Δρmax = 0.21 e Å^−3
5471 reflections	Δρmin = −0.19 e Å^−3
411 parameters

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	0.1685 (3)	0.68255 (18)	0.51999 (9)	0.0470 (6)
H1	0.0669	0.7052	0.5124	0.056*
C2	0.1662 (3)	0.61609 (18)	0.56627 (9)	0.0444 (6)
H2	0.2686	0.5949	0.5739	0.053*
C3	0.1024 (3)	0.66820 (18)	0.61399 (9)	0.0469 (6)
H3	−0.0072	0.6717	0.6113	0.056*
C4	0.1670 (3)	0.76676 (18)	0.62111 (10)	0.0496 (6)
H4	0.0995	0.8040	0.6431	0.06*
C5	0.1974 (4)	0.81875 (18)	0.57041 (11)	0.0548 (7)
H5	0.1012	0.8408	0.5565	0.066*
C6	0.2994 (5)	0.9027 (2)	0.57687 (13)	0.0773 (10)
H6A	0.3904	0.8837	0.5940	0.116*
H6B	0.2496	0.9494	0.5976	0.116*
H6C	0.3228	0.9282	0.5431	0.116*
C7	0.2672 (4)	0.6736 (2)	0.68490 (11)	0.0590 (8)
C8	0.4014 (5)	0.6097 (3)	0.68855 (17)	0.0974 (13)
H8A	0.4348	0.5935	0.6540	0.146*
H8B	0.3741	0.5536	0.7071	0.146*
H8C	0.4810	0.6410	0.7069	0.146*
C9	0.2161 (6)	0.7123 (3)	0.73726 (12)	0.0899 (13)
H9A	0.2994	0.7418	0.7545	0.135*
H9B	0.1787	0.6621	0.7586	0.135*
H9C	0.1378	0.7576	0.7318	0.135*
C10	0.2136 (4)	0.6927 (2)	0.43067 (10)	0.0569 (7)
H10A	0.2709	0.7501	0.4346	0.068*
H10B	0.1090	0.7094	0.4255	0.068*
C11	0.2699 (3)	0.63912 (19)	0.38400 (10)	0.0492 (6)
C12	0.3568 (4)	0.5600 (2)	0.38771 (12)	0.0614 (7)
H12	0.3800	0.5360	0.4205	0.074*
C13	0.4111 (4)	0.5149 (2)	0.34319 (15)	0.0754 (9)
H13	0.4704	0.4615	0.3462	0.091*
C14	0.3764 (5)	0.5501 (3)	0.29519 (15)	0.0822 (11)
H14	0.4119	0.5206	0.2652	0.099*
C15	0.2899 (6)	0.6281 (3)	0.29106 (12)	0.0882 (12)
H15	0.2664	0.6515	0.2581	0.106*
C16	0.2365 (4)	0.6731 (3)	0.33477 (12)	0.0724 (9)
H16	0.1777	0.7267	0.3312	0.087*
C17	0.0720 (3)	0.46527 (17)	0.58895 (10)	0.0431 (5)
H17	0.0382	0.4894	0.6228	0.052*
C18	−0.0343 (3)	0.39002 (19)	0.56967 (10)	0.0451 (6)
H18	−0.0075	0.3724	0.5338	0.054*
C19	−0.0314 (3)	0.30273 (17)	0.60481 (9)	0.0436 (6)
H19	−0.0814	0.3164	0.6381	0.052*
C20	0.1281 (3)	0.27292 (17)	0.61463 (10)	0.0423 (5)
H20	0.1720	0.2489	0.5821	0.051*
C21	0.2185 (3)	0.35700 (18)	0.63348 (9)	0.0440 (6)
H21	0.1720	0.3826	0.6651	0.053*
C23	0.2839 (3)	0.17493 (19)	0.66415 (11)	0.0483 (6)
H23	0.3308	0.1512	0.6321	0.058*
C22	0.3760 (3)	0.3259 (2)	0.64573 (13)	0.0605 (8)
H22A	0.4253	0.3037	0.6143	0.073*
H22B	0.4337	0.3779	0.6597	0.073*
C24	0.2842 (3)	0.09979 (18)	0.70513 (10)	0.0465 (6)
C25	0.3745 (4)	0.0221 (2)	0.69959 (12)	0.0568 (7)
H25	0.4353	0.0164	0.6702	0.068*
C26	0.3761 (4)	−0.0474 (2)	0.73705 (14)	0.0682 (9)
H26	0.4365	−0.1000	0.7325	0.082*
C27	0.2896 (4)	−0.0392 (2)	0.78065 (15)	0.0722 (9)
H27	0.2890	−0.0866	0.8056	0.087*
C28	0.2025 (4)	0.0402 (2)	0.78763 (14)	0.0726 (9)
H28	0.1463	0.0470	0.8180	0.087*
C29	0.1983 (3)	0.1090 (2)	0.75006 (12)	0.0600 (7)
H29	0.1380	0.1616	0.7548	0.072*
C30	−0.2503 (3)	0.2075 (3)	0.59460 (14)	0.0634 (8)
C31	−0.3233 (4)	0.1410 (3)	0.55849 (17)	0.0901 (12)
H31A	−0.3663	0.0903	0.5781	0.135*
H31B	−0.2502	0.1168	0.5344	0.135*
H31C	−0.4011	0.1728	0.5394	0.135*
C32	−0.2699 (4)	0.4179 (3)	0.52700 (19)	0.0807 (12)
C33	−0.4168 (4)	0.4691 (4)	0.5345 (2)	0.137 (2)
H33A	−0.4063	0.5327	0.5227	0.206*
H33B	−0.4435	0.4686	0.5708	0.206*
H33C	−0.4940	0.4385	0.5146	0.206*
O1	0.2281 (2)	0.63696 (13)	0.47667 (7)	0.0540 (5)
O2	0.0753 (2)	0.53732 (12)	0.55201 (6)	0.0496 (4)
O3	0.1431 (2)	0.62353 (13)	0.66183 (7)	0.0536 (5)
O4	0.3019 (2)	0.74719 (13)	0.64901 (7)	0.0560 (5)
O5	0.2644 (2)	0.75863 (13)	0.53258 (7)	0.0545 (5)
O6	−0.1837 (2)	0.42944 (15)	0.57032 (8)	0.0602 (5)
O7	−0.1095 (2)	0.22851 (13)	0.57805 (7)	0.0546 (5)
O8	0.1324 (2)	0.20144 (13)	0.65362 (7)	0.0486 (4)
O9	0.3666 (2)	0.25224 (14)	0.68334 (8)	0.0564 (5)
O10	0.2186 (2)	0.42692 (13)	0.59347 (7)	0.0485 (4)
O11	−0.2303 (4)	0.3766 (3)	0.48987 (13)	0.1122 (11)
O12	−0.3056 (3)	0.2422 (3)	0.63190 (11)	0.1018 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0541 (15)	0.0464 (14)	0.0405 (13)	0.0003 (13)	0.0022 (11)	0.0039 (11)
C2	0.0482 (14)	0.0428 (12)	0.0422 (12)	−0.0004 (12)	−0.0027 (11)	0.0062 (11)
C3	0.0511 (15)	0.0487 (14)	0.0410 (12)	0.0036 (12)	−0.0002 (12)	0.0058 (11)
C4	0.0570 (16)	0.0433 (13)	0.0486 (14)	0.0069 (13)	−0.0021 (12)	0.0016 (11)
C5	0.0713 (19)	0.0421 (13)	0.0511 (14)	0.0071 (14)	−0.0062 (14)	0.0070 (12)
C6	0.112 (3)	0.0471 (16)	0.073 (2)	−0.008 (2)	−0.002 (2)	0.0100 (15)
C7	0.073 (2)	0.0507 (15)	0.0530 (15)	−0.0087 (15)	−0.0156 (15)	0.0126 (13)
C8	0.092 (3)	0.079 (2)	0.121 (3)	−0.001 (2)	−0.037 (3)	0.031 (3)
C9	0.143 (4)	0.077 (2)	0.0504 (17)	−0.035 (3)	−0.008 (2)	0.0035 (16)
C10	0.0728 (19)	0.0505 (15)	0.0473 (14)	0.0054 (16)	0.0066 (14)	0.0079 (12)
C11	0.0518 (15)	0.0495 (14)	0.0462 (13)	−0.0041 (13)	0.0032 (12)	0.0048 (12)
C12	0.0698 (19)	0.0556 (17)	0.0588 (16)	0.0005 (16)	−0.0022 (16)	0.0076 (14)
C13	0.080 (2)	0.0600 (19)	0.086 (2)	0.0064 (18)	0.0084 (19)	−0.0096 (18)
C14	0.103 (3)	0.076 (2)	0.068 (2)	0.001 (2)	0.016 (2)	−0.0156 (19)
C15	0.124 (3)	0.096 (3)	0.0455 (16)	0.012 (3)	0.001 (2)	0.0007 (18)
C16	0.089 (2)	0.075 (2)	0.0537 (16)	0.017 (2)	0.0007 (17)	0.0081 (16)
C17	0.0461 (13)	0.0439 (13)	0.0393 (12)	0.0019 (12)	0.0003 (11)	0.0015 (11)
C18	0.0429 (13)	0.0475 (13)	0.0450 (12)	0.0009 (12)	0.0007 (11)	0.0025 (11)
C19	0.0432 (13)	0.0442 (13)	0.0435 (13)	−0.0053 (12)	−0.0014 (11)	−0.0023 (11)
C20	0.0439 (13)	0.0414 (13)	0.0415 (12)	−0.0009 (11)	−0.0013 (11)	−0.0005 (11)
C21	0.0446 (13)	0.0440 (14)	0.0434 (12)	−0.0022 (12)	−0.0031 (11)	0.0064 (10)
C23	0.0455 (14)	0.0496 (14)	0.0499 (14)	0.0046 (13)	−0.0003 (12)	0.0021 (12)
C22	0.0443 (14)	0.0550 (16)	0.0820 (19)	−0.0085 (14)	−0.0093 (15)	0.0199 (15)
C24	0.0450 (13)	0.0456 (14)	0.0489 (14)	−0.0008 (12)	−0.0045 (12)	0.0010 (11)
C25	0.0595 (17)	0.0504 (15)	0.0604 (16)	0.0046 (15)	−0.0028 (14)	−0.0059 (13)
C26	0.0681 (19)	0.0479 (16)	0.089 (2)	0.0034 (16)	−0.0100 (19)	0.0049 (16)
C27	0.0637 (19)	0.0608 (19)	0.092 (2)	−0.0101 (18)	−0.0055 (19)	0.0273 (18)
C28	0.0621 (18)	0.079 (2)	0.076 (2)	−0.002 (2)	0.0120 (17)	0.0218 (18)
C29	0.0518 (16)	0.0623 (17)	0.0659 (17)	0.0072 (15)	0.0066 (14)	0.0090 (15)
C30	0.0440 (16)	0.0705 (19)	0.076 (2)	−0.0038 (15)	−0.0117 (15)	0.0110 (17)
C31	0.070 (2)	0.082 (2)	0.119 (3)	−0.012 (2)	−0.032 (2)	−0.008 (2)
C32	0.057 (2)	0.090 (3)	0.095 (3)	−0.015 (2)	−0.026 (2)	0.048 (2)
C33	0.059 (2)	0.189 (6)	0.164 (5)	0.017 (3)	−0.006 (3)	0.099 (4)
O1	0.0688 (12)	0.0501 (10)	0.0430 (9)	0.0037 (10)	0.0072 (9)	0.0079 (8)
O2	0.0608 (11)	0.0455 (9)	0.0424 (9)	−0.0051 (10)	−0.0035 (8)	0.0069 (8)
O3	0.0681 (12)	0.0521 (10)	0.0407 (9)	−0.0100 (10)	−0.0057 (9)	0.0065 (8)
O4	0.0629 (11)	0.0503 (10)	0.0548 (10)	−0.0080 (10)	−0.0116 (9)	0.0126 (9)
O5	0.0645 (11)	0.0469 (10)	0.0521 (10)	−0.0051 (10)	0.0048 (9)	0.0065 (8)
O6	0.0461 (10)	0.0659 (12)	0.0686 (13)	0.0081 (10)	−0.0013 (9)	0.0167 (11)
O7	0.0524 (11)	0.0519 (11)	0.0593 (11)	−0.0050 (9)	−0.0038 (9)	−0.0056 (9)
O8	0.0452 (9)	0.0461 (9)	0.0544 (10)	−0.0027 (9)	−0.0065 (8)	0.0086 (8)
O9	0.0467 (10)	0.0543 (11)	0.0681 (12)	−0.0057 (10)	−0.0115 (9)	0.0150 (9)
O10	0.0446 (9)	0.0483 (9)	0.0525 (10)	−0.0025 (9)	0.0019 (8)	0.0109 (8)
O11	0.118 (3)	0.128 (3)	0.0902 (19)	−0.015 (2)	−0.054 (2)	0.0065 (19)
O12	0.0602 (14)	0.145 (3)	0.1005 (19)	−0.0225 (18)	0.0204 (14)	−0.0256 (19)

Geometric parameters (Å, º)

C1—O1	1.390 (3)	C17—O10	1.419 (3)
C1—O5	1.418 (3)	C17—C18	1.513 (4)
C1—C2	1.517 (3)	C17—H17	0.98
C1—H1	0.98	C18—O6	1.444 (3)
C2—O2	1.432 (3)	C18—C19	1.536 (3)
C2—C3	1.538 (4)	C18—H18	0.98
C2—H2	0.98	C19—O7	1.439 (3)
C3—O3	1.426 (3)	C19—C20	1.504 (4)
C3—C4	1.529 (4)	C19—H19	0.98
C3—H3	0.98	C20—O8	1.426 (3)
C4—O4	1.424 (3)	C20—C21	1.522 (3)
C4—C5	1.519 (4)	C20—H20	0.98
C4—H4	0.98	C21—O10	1.429 (3)
C5—O5	1.424 (3)	C21—C22	1.504 (4)
C5—C6	1.511 (5)	C21—H21	0.98
C5—H5	0.98	C23—O9	1.414 (3)
C6—H6A	0.96	C23—O8	1.426 (3)
C6—H6B	0.96	C23—C24	1.499 (4)
C6—H6C	0.96	C23—H23	0.98
C7—O4	1.428 (3)	C22—O9	1.427 (3)
C7—O3	1.442 (4)	C22—H22A	0.97
C7—C8	1.506 (5)	C22—H22B	0.97
C7—C9	1.519 (5)	C24—C25	1.376 (4)
C8—H8A	0.96	C24—C29	1.387 (4)
C8—H8B	0.96	C25—C26	1.379 (4)
C8—H8C	0.96	C25—H25	0.93
C9—H9A	0.96	C26—C27	1.361 (5)
C9—H9B	0.96	C26—H26	0.93
C9—H9C	0.96	C27—C28	1.383 (5)
C10—O1	1.426 (3)	C27—H27	0.93
C10—C11	1.503 (4)	C28—C29	1.374 (4)
C10—H10A	0.97	C28—H28	0.93
C10—H10B	0.97	C29—H29	0.93
C11—C12	1.371 (4)	C30—O12	1.182 (4)
C11—C16	1.382 (4)	C30—O7	1.357 (4)
C12—C13	1.395 (4)	C30—C31	1.475 (5)
C12—H12	0.93	C31—H31A	0.96
C13—C14	1.362 (5)	C31—H31B	0.96
C13—H13	0.93	C31—H31C	0.96
C14—C15	1.357 (5)	C32—O11	1.172 (5)
C14—H14	0.93	C32—O6	1.358 (4)
C15—C16	1.374 (5)	C32—C33	1.510 (6)
C15—H15	0.93	C33—H33A	0.96
C16—H16	0.93	C33—H33B	0.96
C17—O2	1.396 (3)	C33—H33C	0.96
O1—C1—O5	108.0 (2)	C18—C17—H17	110.2
O1—C1—C2	109.6 (2)	O6—C18—C17	107.2 (2)
O5—C1—C2	108.0 (2)	O6—C18—C19	108.9 (2)
O1—C1—H1	110.4	C17—C18—C19	111.9 (2)
O5—C1—H1	110.4	O6—C18—H18	109.6
C2—C1—H1	110.4	C17—C18—H18	109.6
O2—C2—C1	107.41 (19)	C19—C18—H18	109.6
O2—C2—C3	111.9 (2)	O7—C19—C20	109.1 (2)
C1—C2—C3	108.8 (2)	O7—C19—C18	108.05 (19)
O2—C2—H2	109.5	C20—C19—C18	110.0 (2)
C1—C2—H2	109.5	O7—C19—H19	109.9
C3—C2—H2	109.5	C20—C19—H19	109.9
O3—C3—C4	102.29 (19)	C18—C19—H19	109.9
O3—C3—C2	111.8 (2)	O8—C20—C19	110.1 (2)
C4—C3—C2	113.6 (2)	O8—C20—C21	109.11 (19)
O3—C3—H3	109.6	C19—C20—C21	109.2 (2)
C4—C3—H3	109.6	O8—C20—H20	109.5
C2—C3—H3	109.6	C19—C20—H20	109.5
O4—C4—C5	111.9 (2)	C21—C20—H20	109.5
O4—C4—C3	101.33 (19)	O10—C21—C22	110.8 (2)
C5—C4—C3	114.5 (2)	O10—C21—C20	108.84 (19)
O4—C4—H4	109.6	C22—C21—C20	109.1 (2)
C5—C4—H4	109.6	O10—C21—H21	109.4
C3—C4—H4	109.6	C22—C21—H21	109.4
O5—C5—C6	107.5 (3)	C20—C21—H21	109.4
O5—C5—C4	111.2 (2)	O9—C23—O8	110.6 (2)
C6—C5—C4	113.6 (2)	O9—C23—C24	108.3 (2)
O5—C5—H5	108.1	O8—C23—C24	108.9 (2)
C6—C5—H5	108.1	O9—C23—H23	109.7
C4—C5—H5	108.1	O8—C23—H23	109.7
C5—C6—H6A	109.5	C24—C23—H23	109.7
C5—C6—H6B	109.5	O9—C22—C21	107.6 (2)
H6A—C6—H6B	109.5	O9—C22—H22A	110.2
C5—C6—H6C	109.5	C21—C22—H22A	110.2
H6A—C6—H6C	109.5	O9—C22—H22B	110.2
H6B—C6—H6C	109.5	C21—C22—H22B	110.2
O4—C7—O3	105.4 (2)	H22A—C22—H22B	108.5
O4—C7—C8	108.3 (3)	C25—C24—C29	118.9 (3)
O3—C7—C8	109.5 (3)	C25—C24—C23	120.3 (2)
O4—C7—C9	111.4 (2)	C29—C24—C23	120.7 (2)
O3—C7—C9	108.2 (3)	C24—C25—C26	120.9 (3)
C8—C7—C9	113.8 (3)	C24—C25—H25	119.6
C7—C8—H8A	109.5	C26—C25—H25	119.6
C7—C8—H8B	109.5	C27—C26—C25	120.1 (3)
H8A—C8—H8B	109.5	C27—C26—H26	119.9
C7—C8—H8C	109.5	C25—C26—H26	119.9
H8A—C8—H8C	109.5	C26—C27—C28	119.6 (3)
H8B—C8—H8C	109.5	C26—C27—H27	120.2
C7—C9—H9A	109.5	C28—C27—H27	120.2
C7—C9—H9B	109.5	C29—C28—C27	120.6 (3)
H9A—C9—H9B	109.5	C29—C28—H28	119.7
C7—C9—H9C	109.5	C27—C28—H28	119.7
H9A—C9—H9C	109.5	C28—C29—C24	119.8 (3)
H9B—C9—H9C	109.5	C28—C29—H29	120.1
O1—C10—C11	110.0 (2)	C24—C29—H29	120.1
O1—C10—H10A	109.7	O12—C30—O7	122.9 (3)
C11—C10—H10A	109.7	O12—C30—C31	126.3 (3)
O1—C10—H10B	109.7	O7—C30—C31	110.7 (3)
C11—C10—H10B	109.7	C30—C31—H31A	109.5
H10A—C10—H10B	108.2	C30—C31—H31B	109.5
C12—C11—C16	118.2 (3)	H31A—C31—H31B	109.5
C12—C11—C10	123.4 (2)	C30—C31—H31C	109.5
C16—C11—C10	118.3 (3)	H31A—C31—H31C	109.5
C11—C12—C13	121.2 (3)	H31B—C31—H31C	109.5
C11—C12—H12	119.4	O11—C32—O6	123.5 (4)
C13—C12—H12	119.4	O11—C32—C33	127.3 (4)
C14—C13—C12	119.2 (3)	O6—C32—C33	109.1 (4)
C14—C13—H13	120.4	C32—C33—H33A	109.5
C12—C13—H13	120.4	C32—C33—H33B	109.5
C15—C14—C13	120.0 (3)	H33A—C33—H33B	109.5
C15—C14—H14	120	C32—C33—H33C	109.5
C13—C14—H14	120	H33A—C33—H33C	109.5
C14—C15—C16	121.0 (3)	H33B—C33—H33C	109.5
C14—C15—H15	119.5	C1—O1—C10	111.29 (19)
C16—C15—H15	119.5	C17—O2—C2	114.62 (18)
C15—C16—C11	120.2 (3)	C3—O3—C7	108.94 (19)
C15—C16—H16	119.9	C4—O4—C7	106.5 (2)
C11—C16—H16	119.9	C1—O5—C5	111.3 (2)
O2—C17—O10	108.6 (2)	C32—O6—C18	117.6 (3)
O2—C17—C18	108.3 (2)	C30—O7—C19	117.4 (2)
O10—C17—C18	109.1 (2)	C23—O8—C20	110.27 (19)
O2—C17—H17	110.2	C23—O9—C22	111.8 (2)
O10—C17—H17	110.2	C17—O10—C21	109.07 (19)
O1—C1—C2—O2	−59.6 (3)	C29—C24—C25—C26	2.3 (4)
O5—C1—C2—O2	−177.07 (19)	C23—C24—C25—C26	179.8 (3)
O1—C1—C2—C3	179.1 (2)	C24—C25—C26—C27	−1.0 (5)
O5—C1—C2—C3	61.6 (3)	C25—C26—C27—C28	−1.3 (5)
O2—C2—C3—O3	81.5 (2)	C26—C27—C28—C29	2.5 (5)
C1—C2—C3—O3	−159.9 (2)	C27—C28—C29—C24	−1.2 (5)
O2—C2—C3—C4	−163.3 (2)	C25—C24—C29—C28	−1.2 (4)
C1—C2—C3—C4	−44.8 (3)	C23—C24—C29—C28	−178.7 (3)
O3—C3—C4—O4	36.2 (2)	O5—C1—O1—C10	−70.4 (3)
C2—C3—C4—O4	−84.5 (2)	C2—C1—O1—C10	172.1 (2)
O3—C3—C4—C5	156.8 (2)	C11—C10—O1—C1	−176.4 (2)
C2—C3—C4—C5	36.2 (3)	O10—C17—O2—C2	−64.5 (3)
O4—C4—C5—O5	72.1 (3)	C18—C17—O2—C2	177.1 (2)
C3—C4—C5—O5	−42.4 (3)	C1—C2—O2—C17	174.7 (2)
O4—C4—C5—C6	−49.2 (3)	C3—C2—O2—C17	−65.9 (3)
C3—C4—C5—C6	−163.8 (3)	C4—C3—O3—C7	−21.3 (3)
O1—C10—C11—C12	−15.6 (4)	C2—C3—O3—C7	100.6 (3)
O1—C10—C11—C16	166.7 (3)	O4—C7—O3—C3	−1.6 (3)
C16—C11—C12—C13	0.3 (5)	C8—C7—O3—C3	−117.9 (3)
C10—C11—C12—C13	−177.5 (3)	C9—C7—O3—C3	117.6 (2)
C11—C12—C13—C14	−0.3 (5)	C5—C4—O4—C7	−160.9 (2)
C12—C13—C14—C15	0.0 (6)	C3—C4—O4—C7	−38.5 (3)
C13—C14—C15—C16	0.2 (7)	O3—C7—O4—C4	26.1 (3)
C14—C15—C16—C11	−0.2 (7)	C8—C7—O4—C4	143.2 (3)
C12—C11—C16—C15	0.0 (5)	C9—C7—O4—C4	−90.9 (3)
C10—C11—C16—C15	177.8 (4)	O1—C1—O5—C5	169.4 (2)
O2—C17—C18—O6	−67.1 (3)	C2—C1—O5—C5	−72.1 (3)
O10—C17—C18—O6	174.77 (19)	C6—C5—O5—C1	−173.9 (2)
O2—C17—C18—C19	173.5 (2)	C4—C5—O5—C1	61.2 (3)
O10—C17—C18—C19	55.4 (3)	O11—C32—O6—C18	1.3 (5)
O6—C18—C19—O7	73.6 (2)	C33—C32—O6—C18	−176.5 (3)
C17—C18—C19—O7	−168.0 (2)	C17—C18—O6—C32	132.1 (3)
O6—C18—C19—C20	−167.3 (2)	C19—C18—O6—C32	−106.5 (3)
C17—C18—C19—C20	−48.9 (3)	O12—C30—O7—C19	−5.9 (4)
O7—C19—C20—O8	−70.7 (2)	C31—C30—O7—C19	171.2 (3)
C18—C19—C20—O8	170.88 (19)	C20—C19—O7—C30	136.4 (2)
O7—C19—C20—C21	169.5 (2)	C18—C19—O7—C30	−104.0 (3)
C18—C19—C20—C21	51.1 (3)	O9—C23—O8—C20	61.2 (3)
O8—C20—C21—O10	177.83 (19)	C24—C23—O8—C20	−179.91 (19)
C19—C20—C21—O10	−61.8 (3)	C19—C20—O8—C23	−178.3 (2)
O8—C20—C21—C22	56.9 (3)	C21—C20—O8—C23	−58.4 (3)
C19—C20—C21—C22	177.3 (2)	O8—C23—O9—C22	−62.8 (3)
O10—C21—C22—O9	−176.3 (2)	C24—C23—O9—C22	178.0 (2)
C20—C21—C22—O9	−56.6 (3)	C21—C22—O9—C23	60.1 (3)
O9—C23—C24—C25	−104.2 (3)	O2—C17—O10—C21	176.49 (18)
O8—C23—C24—C25	135.5 (3)	C18—C17—O10—C21	−65.6 (3)
O9—C23—C24—C29	73.3 (3)	C22—C21—O10—C17	−170.6 (2)
O8—C23—C24—C29	−47.0 (3)	C20—C21—O10—C17	69.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···O3	0.98	2.35	2.995 (3)	123
C22—H22A···O12^i	0.97	2.59	3.095 (4)	113

Symmetry code: (i) x+1, y, z.