Two ethyl 2-deoxy-α-D-hexo-3,7-pyranoso-3-octulosonate derivatives

In each of the two pyran­oid sugars, ethyl 2-deoxy-4,5,6,8-tetra-O-acetyl-α-D-gluco-3,7-pyran­oso-3-octulosonate, C₁₈H₂₆O₁₂, and ethyl 2-deoxy-4,5,6,8-tetra-O-benzyl-α-D-galacto-3,7-pyranoso-3-octulosonate, C₃₈H₄₂O₈, the anomeric configuration is α. The acetoxy­methyl substituent on the hexo­pyran­ose ring of the former compound and the ethoxy­carbonyl­methyl substituents in both sugars all have the gauche–trans conformation, while the benzyl­oxy­methyl substituent of the galacto­pyran­ose sugar has the trans–gauche conformation. In each structure, the anomeric hydroxy group forms an intramolecular hydrogen bond with the carbonyl O atom of the ethoxy­carbonyl­methyl substituent.

S1. Comment

C-Glycosides are now widely used as chiral templates for the synthesis of complex target molecules (Martin et al., 1991; Jiang et al., 1996), many of which have been found to show interesting and useful biological activities (Pougny et al., 1981; Martin et al., 1991; Watson et al., 1994; Bichard et al., 1995). One group of C-glycosides that have not been widely studied for their enzyme inhibition activities is that where the compounds contain an exocyclic double bond at the anomeric centre. We are presently interested in studying the synthesis and structure of this class of derivatives and now report the low-temperature crystal structures of ethyl 2-deoxy-4,5,6,8-tetra-O-acetyl-α-D-gluco-3,7-pyranoso-3-octulosonate, (I), and ethyl 2-deoxy-4,5,6,8-tetra-O-benzyl-α-D-galacto-3,7-pyranoso-3-octulosonate, (II), which are precursors used in the synthesis of their exocyclic alkenylic analogues. \sch

Figs. 1 and 2 depict the correct absolute configurations of compounds (I) and (II), which were assigned to agree with the known chirality of the precursor sugars, D-glucose and D-galactose, respectively. Both sugars are α-anomers and the pyranose ring in each compound has a slightly distorted ⁴C₁ chair conformation. The ring puckering parameters (Cremer & Pople, 1975) are Q = 0.570 (2) Å, q₂ = 0.062 (2) Å, q₃ = 0.567 (3) Å, ϕ₂ = 68.5 (18)° and θ = 6.4 (2)° for compound (I), and Q = 0.590 (3) Å, q₂ = 0.054 (2) Å, q₃ = 0.588 (3) Å, ϕ₂ = 157 (3)° and θ = 5.2 (2)° for compound (II). The bond lengths and angles exhibit normal values and generally agree with the corresponding parameters found for other α-pyranose sugars (Berman et al., 1967).

The conformation of the C5 acetoxymethyl group in (I) is gauche-trans [O5—C5—C6—O6 72.1 (2)° and C4—C5—C6—O6 - 168.41 (17)°]. In contrast, the corresponding benzyloxymethyl group in (II) has a trans-gauche conformation [O5—C5—C6—O6 - 170.90 (19)° and C4—C5—C6—O6 - 50.0 (3)°]. In D-glucopyranose, a trans-gauche conformation would be forbidden because of the resultant unfavourable steric interaction between O4 and O6, but most galactopyranoses have either the gauche-trans or trans-gauche conformation (Longchambon et al., 1975; Kanters et al. 1988), with a slight preference for the gauche-trans form (Kanters et al., 1978). The gauche-gauche conformation is not usually observed for galactopyranoses, because this results in an unfavourable 1,3-peri interaction between the synaxial atoms O4 and O6.

The conformation of the C1 ethoxycarbonylmethyl substituent in each sugar is also gauche-trans [O5—C1—C9—C10 - 66.7 (2)° and C2—C1—C9—C10 177.68 (18)° for (I), and O5—C1—C14—C15 - 62.5 (3)° and C2—C1—C14—C15 178.6 (2)° for (II)]. In each sugar, the anomeric C1 hydroxy group forms an intramolecular hydrogen bond with the ethoxycarbonyl O atom (Tables 1 and 2), thereby closing a six-membered loop with a graph-set motif of S(6) (Bernstein et al., 1995).

Related literature

For related literature, see: Berman et al. (1967); Bernstein et al. (1995); Bichard et al. (1995); Cremer & Pople (1975); Flack (1983); Flack & Bernardinelli (2000); Jiang et al. (1996); Kanters et al. (1978, 1988); Longchambon et al. (1975); Martin et al. (1991); Pougny et al. (1981); Shriner (1942); Spek (2001); Watson et al. (1994).

S2. Experimental

Compounds (I) and (II) were synthesized from the corresponding 2,3,4,6-tetra-O-benzyl glucono- or galactono- lactone using the Reformatsky reaction (Shriner, 1942). The activated zinc used in the reaction was prepared by washing zinc dust successively with 5% HCl, distilled water, acetone, absolute ethanol and anhydrous ether, and then dried at 373 K under vacuum. The Reformatsky reaction produced the benzylated analogue of compound (I) and pure compound (II), respectively. Compound (I) was then obtained by converting its benzylated analogue to the acetylated derivative as follows. A solution of ethyl 2-deoxy-4,5,6,8-tetra-O-benzyl-α-D-gluco-3,7-pyranoso-3-octulosonate (0.5 g, 0.8 mmol) in ethanol (5 ml) was hydrogenated [10% palladium-on-charcoal (80 mg) under hydrogen (50 psi)] for ca 12 h, after which thin layer chromatography (hexane/ethyl acetate, 3:1) showed that all starting material had been consumed. The solution was filtered, concentrated and acetylated with acetic anhydride (0.8 ml) in pyridine (1 ml). The reaction mixture was worked up in the usual manner and purified by flash column chromatography to give compound (I) (0.22 g, 64.2%; m.p. 383–385 K). Spectroscopic analysis: [α]_D +40.5° (c 4.38, CHCl₃); ¹H NMR (CDCl₃, δ, p.p.m.): 5.52 (t, 1H, J_3,4 = 9.5 Hz, H3), 5.09 (t, 1H, J_4,5 = 9.7 Hz, H4), 4.90 (d, 1H, J_2,3 = 9.7 Hz, H2), 4.22–4.31 (m, 1H, H5), 4.21 (q, 2H, J_12,13 = 7.1 Hz, H12a,b), 2.58, 2.64 (2 × s, 2H, H9a,b), 1.98, 2.01, 2.05, 2.09 (4 × s, 12H, 4 × CH₃CO), 1.27 (t, 3H, H13a,b,c); ¹³C NMR (CDCl₃, δ, p.p.m.): 171.98, 170.01, 169.92, 169.52, 169.55 (C═O), 96.12 (C1), 72.54 (C2), 70.92 (C3), 68.52, 68.01 (C4,5), 61.82, 61.50 (C1, C6), 61.50 (C9), 39.62 (C12), 20.53, 20.59 (CH₃CO), 13.88 (C13). Analysis calculated for C₁₈H₂₆O₁₂: C 49.79, H 9.66%; found: C 49.52, H 9.61%. Compound (II) was obtained in 85.5% yield (m.p. 389–392 K). Spectroscopic analysis: [α]_D -5.81 (c 10.69, CHCl₃); ¹H NMR (CDCl₃, δ, p.p.m.): 7.20–7.40 (m, 20H, Ar—H), 5.00, 4.95, 4.65, 4.61, 4.48, 4.42 (6 × d, 6H, J = 11.4–11.8 Hz, 3 × PhCH₂), 4.77 (s, 2H, H7a,b), 4.04–21 (m, 5H, H3, 4, 5, 17a,b), 3.81 (d, 1H, J_2,3 = 9.8 Hz, H2), 3.74 (dd, 1H, J_5,6a = 7.8 Hz, J_{6a,6 b} = 9.3 Hz, H6a), 3.48 (dd, 1H, J_{6a,6 b} = 9.3 Hz, H6b), 2.37, 2.83 (2 × s, 2H, H14a,b), 1.27 (t, 3H, H18a,b,c); ¹³C NMR (CDCl₃, δ, p.p.m.): 172.44 (C═O), 127.46, 127.58, 127.72, 128.02, 128.12, 128.28, 128.32, 128.47, 138.04, 138.38, 138.77 (Ar—C), 97.20 (C1), 80.34 (C3), 78.34 (C2), 74.77 (C4), 72.52, 73.29, 74.60, 75.15 (PhCH₂), 70.08 (C5), 68.59 (C6, C17), 40.56 (C14), 13.91 (C18). Analysis calculated for C₃₈H₄₂O₈: C 72.86, H 6.71%; found: C 72.03, H 6.80%. Suitable crystals of each compound were obtained by slow evaporation of their solutions in ethanol.

S3. Refinement

Examination of the structure of (I) with PLATON (Spek, 2001) revealed that the unit-cell parameters can be transformed metrically to an orthorhombic C lattice, but that the overall structure itself is not consistent with the higher symmetry. For (I), the anisotropic displacement ellipsoids for O16 and, to a lesser extent, O18 are significantly elongated. In addition, the maximum peak of residual electron density of 0.49 e Å^-3 is 1.0 Å from O16 and the next highest peak is only 0.25 e Å^-3. This suggests that these two atoms may be disordered, particularly O16. Indeed, the position of O16 could be divided into two almost equally occupied sites that are approximately 0.5 Å apart, and the refinement of this model reduced R_F to 0.035 and the maximum peak of residual electron density to 0.25 e Å^-3. Nevertheless, the anisotropic displacement ellipsoid for one of the disordered positions became even more elongated than that of O16 in the ordered model, even when light restraints were applied, and more severe restraints upset the realism of the geometric parameters. Therefore, it was considered to be more appropriate to use the ordered model in the final refinement. For each compound, the methyl H atoms were constrained to an ideal geometry (C—H = 0.98 Å) with U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about the C—C bonds. The positions of the hydroxy H atoms were refined freely, along with individual isotropic displacement parameters. All other H atoms were placed in geometrically idealized positions (C—H = 0.95–1.00 Å) and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C). The absolute configuration could not be determined because of the absence of significant anomalous scatterers in the compound. The enantiomer used in each model was based on the known chirality of the precursor sugars, D-glucose and D-galactose, from which (I) and (II), respectively, were synthesized. Due to the absence of any significant anomalous scatterers, attempts to confirm the absolute structure by refinement of the Flack parameter (Flack, 1983) led to inconclusive values (Flack & Bernardinelli, 2000) for this parameter [-0.7 (7) for (I) and -0.3 (11) for (II)]. Therefore, Friedel equivalents [3030 for (I) and 560 for (II)] were merged before the final refinements.

Computing details

For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2001).

Figures

	Fig. 1. A view of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by circles of arbitrary size.
	Fig. 2. A view of the molecule of (II) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by circles of arbitrary size.

(I) ethyl 2-deoxy-4,5,6,8-tetra-O-acetyl-α-D-gluco-3,7-pyranoso-3-octulosonate

Crystal data

C18H26O12	F(000) = 460
Mr = 434.39	Dx = 1.328 Mg m^−3
Monoclinic, P21	Melting point = 383–385 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 9.3164 (15) Å	Cell parameters from 25 reflections
b = 13.038 (2) Å	θ = 19.0–20.0°
c = 9.3130 (15) Å	µ = 0.11 mm^−1
β = 106.224 (12)°	T = 173 K
V = 1086.2 (3) Å^3	Prism, colourless
Z = 2	0.46 × 0.33 × 0.24 mm

Data collection

Rigaku AFC-5R diffractometer	Rint = 0.024
Radiation source: Rigaku rotating anode generator	θmax = 30.0°, θmin = 2.7°
Graphite monochromator	h = 0→13
ω/2θ scans	k = −18→18
6676 measured reflections	l = −13→12
3285 independent reflections	3 standard reflections every 150 reflections
2717 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0554P)^2 + 0.1486P] where P = (Fo^2 + 2Fc^2)/3
3285 reflections	(Δ/σ)max = 0.001
280 parameters	Δρmax = 0.49 e Å^−3
1 restraint	Δρmin = −0.36 e Å^−3

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.

Refinement. 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	0.18308 (19)	0.75187 (12)	0.24341 (18)	0.0297 (3)
H1	0.224 (5)	0.758 (4)	0.180 (4)	0.065 (11)*
O2	0.27787 (17)	0.77533 (12)	0.55010 (16)	0.0273 (3)
O3	−0.00010 (18)	0.77229 (12)	0.60306 (16)	0.0281 (3)
O4	−0.24324 (17)	0.74930 (12)	0.31831 (16)	0.0275 (3)
O5	0.03963 (17)	0.90181 (11)	0.21439 (16)	0.0262 (3)
O6	−0.2115 (2)	0.91846 (13)	−0.04618 (17)	0.0337 (4)
O7	−0.2811 (3)	1.08360 (14)	−0.0632 (2)	0.0452 (5)
O10	0.3332 (3)	0.85864 (14)	0.0689 (2)	0.0458 (5)
O11	0.3118 (2)	1.02873 (13)	0.09877 (18)	0.0336 (4)
O14	0.3901 (2)	0.91622 (14)	0.6718 (2)	0.0380 (4)
O16	−0.0621 (5)	0.6059 (2)	0.5835 (3)	0.0885 (11)
O18	−0.3527 (2)	0.82734 (19)	0.4755 (3)	0.0601 (7)
C1	0.1707 (2)	0.84948 (15)	0.3001 (2)	0.0242 (4)
C2	0.1550 (2)	0.83512 (15)	0.4592 (2)	0.0234 (4)
H2	0.1502	0.9033	0.5068	0.028*
C3	0.0154 (2)	0.77330 (16)	0.4528 (2)	0.0238 (4)
H3	0.0270	0.7017	0.4193	0.029*
C4	−0.1224 (2)	0.82304 (16)	0.3478 (2)	0.0240 (4)
H4	−0.1502	0.8868	0.3934	0.029*
C5	−0.0971 (2)	0.84656 (16)	0.1952 (2)	0.0262 (4)
H5	−0.0944	0.7813	0.1396	0.031*
C6	−0.2212 (3)	0.91510 (19)	0.1055 (2)	0.0322 (4)
H61	−0.3196	0.8876	0.1077	0.039*
H62	−0.2103	0.9850	0.1487	0.039*
C7	−0.2465 (3)	1.00845 (17)	−0.1200 (2)	0.0278 (4)
C8	−0.2390 (3)	0.99913 (19)	−0.2782 (2)	0.0329 (5)
H81	−0.3369	0.9782	−0.3426	0.049*
H82	−0.1641	0.9476	−0.2834	0.049*
H83	−0.2112	1.0655	−0.3120	0.049*
C9	0.2998 (2)	0.92219 (17)	0.2996 (2)	0.0286 (4)
H91	0.2799	0.9907	0.3359	0.034*
H92	0.3937	0.8957	0.3680	0.034*
C10	0.3169 (3)	0.93159 (19)	0.1436 (3)	0.0313 (4)
C12	0.3143 (3)	1.0458 (2)	−0.0562 (3)	0.0363 (5)
H121	0.3854	0.9974	−0.0817	0.044*
H122	0.3487	1.1165	−0.0670	0.044*
C13	0.1610 (3)	1.0303 (2)	−0.1613 (3)	0.0425 (6)
H131	0.1308	0.9586	−0.1569	0.064*
H132	0.1626	1.0469	−0.2635	0.064*
H133	0.0897	1.0752	−0.1320	0.064*
C14	0.3826 (2)	0.82485 (19)	0.6598 (2)	0.0291 (4)
C15	0.4827 (3)	0.7496 (2)	0.7621 (3)	0.0452 (6)
H151	0.5802	0.7814	0.8074	0.068*
H152	0.4960	0.6889	0.7050	0.068*
H153	0.4375	0.7291	0.8410	0.068*
C16	−0.0337 (3)	0.6819 (2)	0.6579 (3)	0.0434 (6)
C17	−0.0361 (4)	0.6925 (3)	0.8168 (3)	0.0499 (7)
H171	−0.0819	0.6314	0.8466	0.075*
H172	−0.0944	0.7533	0.8270	0.075*
H173	0.0664	0.6998	0.8811	0.075*
C18	−0.3478 (2)	0.75728 (19)	0.3931 (3)	0.0320 (5)
C19	−0.4523 (3)	0.6686 (2)	0.3618 (3)	0.0395 (5)
H191	−0.5253	0.6759	0.4191	0.059*
H192	−0.3958	0.6049	0.3909	0.059*
H193	−0.5045	0.6665	0.2548	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0385 (8)	0.0241 (7)	0.0289 (7)	0.0018 (6)	0.0133 (7)	−0.0028 (6)
O2	0.0271 (7)	0.0253 (7)	0.0275 (7)	0.0015 (6)	0.0042 (6)	0.0019 (6)
O3	0.0337 (8)	0.0288 (8)	0.0231 (7)	−0.0019 (6)	0.0100 (6)	0.0047 (6)
O4	0.0277 (7)	0.0264 (7)	0.0287 (7)	−0.0019 (6)	0.0082 (6)	−0.0038 (6)
O5	0.0307 (8)	0.0229 (7)	0.0244 (6)	0.0005 (6)	0.0067 (6)	0.0040 (5)
O6	0.0454 (9)	0.0291 (8)	0.0237 (7)	0.0073 (7)	0.0049 (6)	0.0039 (6)
O7	0.0691 (14)	0.0318 (9)	0.0347 (9)	0.0120 (9)	0.0143 (9)	0.0040 (7)
O10	0.0708 (13)	0.0354 (9)	0.0421 (9)	0.0052 (9)	0.0335 (10)	0.0009 (8)
O11	0.0451 (10)	0.0311 (8)	0.0291 (8)	−0.0071 (7)	0.0176 (7)	0.0000 (6)
O14	0.0384 (9)	0.0347 (9)	0.0371 (8)	−0.0038 (7)	0.0043 (7)	−0.0066 (7)
O16	0.178 (3)	0.0447 (13)	0.0454 (12)	−0.0422 (17)	0.0352 (17)	0.0026 (10)
O18	0.0420 (11)	0.0660 (14)	0.0817 (15)	−0.0202 (10)	0.0330 (11)	−0.0465 (13)
C1	0.0294 (10)	0.0214 (9)	0.0229 (8)	0.0004 (7)	0.0091 (7)	0.0011 (7)
C2	0.0269 (9)	0.0225 (9)	0.0204 (8)	0.0010 (8)	0.0060 (7)	0.0018 (7)
C3	0.0274 (9)	0.0250 (9)	0.0190 (8)	−0.0003 (7)	0.0067 (7)	0.0012 (7)
C4	0.0256 (9)	0.0217 (8)	0.0240 (9)	0.0001 (7)	0.0058 (7)	0.0000 (7)
C5	0.0305 (10)	0.0243 (9)	0.0225 (9)	0.0015 (8)	0.0052 (7)	0.0004 (7)
C6	0.0349 (11)	0.0354 (11)	0.0249 (9)	0.0088 (10)	0.0062 (8)	0.0048 (9)
C7	0.0256 (10)	0.0283 (10)	0.0259 (9)	0.0003 (8)	0.0013 (8)	0.0042 (8)
C8	0.0365 (12)	0.0324 (11)	0.0272 (10)	0.0004 (9)	0.0045 (9)	0.0031 (9)
C9	0.0331 (10)	0.0279 (10)	0.0278 (9)	−0.0057 (9)	0.0137 (8)	0.0000 (8)
C10	0.0328 (11)	0.0340 (11)	0.0313 (10)	−0.0009 (9)	0.0159 (9)	0.0006 (9)
C12	0.0439 (13)	0.0394 (12)	0.0297 (11)	−0.0073 (11)	0.0169 (10)	0.0046 (9)
C13	0.0480 (15)	0.0428 (14)	0.0371 (12)	−0.0021 (12)	0.0126 (11)	0.0053 (11)
C14	0.0276 (10)	0.0351 (11)	0.0245 (9)	−0.0012 (9)	0.0071 (8)	−0.0001 (8)
C15	0.0401 (13)	0.0480 (15)	0.0396 (12)	0.0053 (12)	−0.0021 (11)	0.0064 (12)
C16	0.0573 (16)	0.0396 (13)	0.0325 (12)	−0.0143 (12)	0.0115 (11)	0.0093 (10)
C17	0.0624 (19)	0.0578 (18)	0.0319 (12)	−0.0058 (15)	0.0173 (12)	0.0142 (12)
C18	0.0244 (10)	0.0359 (12)	0.0346 (10)	−0.0018 (9)	0.0065 (8)	−0.0079 (9)
C19	0.0302 (11)	0.0410 (13)	0.0497 (14)	−0.0089 (10)	0.0151 (10)	−0.0116 (11)

Geometric parameters (Å, º)

O1—C1	1.395 (2)	C5—H5	1.0000
O1—H1	0.79 (4)	C6—H61	0.9900
O2—C14	1.362 (3)	C6—H62	0.9900
O2—C2	1.447 (2)	C7—C8	1.500 (3)
O3—C16	1.356 (3)	C8—H81	0.9800
O3—C3	1.446 (2)	C8—H82	0.9800
O4—C18	1.351 (3)	C8—H83	0.9800
O4—C4	1.447 (3)	C9—C10	1.511 (3)
O5—C5	1.431 (3)	C9—H91	0.9900
O5—C1	1.431 (3)	C9—H92	0.9900
O6—C7	1.353 (3)	C12—C13	1.502 (4)
O6—C6	1.441 (3)	C12—H121	0.9900
O7—C7	1.199 (3)	C12—H122	0.9900
O10—C10	1.213 (3)	C13—H131	0.9800
O11—C10	1.330 (3)	C13—H132	0.9800
O11—C12	1.467 (3)	C13—H133	0.9800
O14—C14	1.197 (3)	C14—C15	1.498 (3)
O16—C16	1.195 (4)	C15—H151	0.9800
O18—C18	1.202 (3)	C15—H152	0.9800
C1—C9	1.532 (3)	C15—H153	0.9800
C1—C2	1.541 (3)	C16—C17	1.493 (4)
C2—C3	1.517 (3)	C17—H171	0.9800
C2—H2	1.0000	C17—H172	0.9800
C3—C4	1.524 (3)	C17—H173	0.9800
C3—H3	1.0000	C18—C19	1.487 (3)
C4—C5	1.535 (3)	C19—H191	0.9800
C4—H4	1.0000	C19—H192	0.9800
C5—C6	1.514 (3)	C19—H193	0.9800
C1—O1—H1	108 (3)	H81—C8—H83	109.5
C14—O2—C2	117.86 (17)	H82—C8—H83	109.5
C16—O3—C3	117.91 (18)	C10—C9—C1	110.28 (18)
C18—O4—C4	119.07 (17)	C10—C9—H91	109.6
C5—O5—C1	114.89 (15)	C1—C9—H91	109.6
C7—O6—C6	116.88 (18)	C10—C9—H92	109.6
C10—O11—C12	116.36 (18)	C1—C9—H92	109.6
O1—C1—O5	111.83 (16)	H91—C9—H92	108.1
O1—C1—C9	114.57 (17)	O10—C10—O11	124.5 (2)
O5—C1—C9	104.56 (16)	O10—C10—C9	123.5 (2)
O1—C1—C2	107.04 (15)	O11—C10—C9	112.02 (19)
O5—C1—C2	107.38 (15)	O11—C12—C13	110.30 (19)
C9—C1—C2	111.30 (16)	O11—C12—H121	109.6
O2—C2—C3	105.44 (16)	C13—C12—H121	109.6
O2—C2—C1	110.86 (15)	O11—C12—H122	109.6
C3—C2—C1	109.72 (15)	C13—C12—H122	109.6
O2—C2—H2	110.2	H121—C12—H122	108.1
C3—C2—H2	110.2	C12—C13—H131	109.5
C1—C2—H2	110.2	C12—C13—H132	109.5
O3—C3—C2	106.43 (15)	H131—C13—H132	109.5
O3—C3—C4	109.31 (16)	C12—C13—H133	109.5
C2—C3—C4	111.01 (16)	H131—C13—H133	109.5
O3—C3—H3	110.0	H132—C13—H133	109.5
C2—C3—H3	110.0	O14—C14—O2	123.5 (2)
C4—C3—H3	110.0	O14—C14—C15	125.7 (2)
O4—C4—C3	108.07 (16)	O2—C14—C15	110.8 (2)
O4—C4—C5	105.65 (15)	C14—C15—H151	109.5
C3—C4—C5	111.06 (16)	C14—C15—H152	109.5
O4—C4—H4	110.6	H151—C15—H152	109.5
C3—C4—H4	110.6	C14—C15—H153	109.5
C5—C4—H4	110.6	H151—C15—H153	109.5
O5—C5—C6	106.71 (18)	H152—C15—H153	109.5
O5—C5—C4	110.29 (16)	O16—C16—O3	122.7 (2)
C6—C5—C4	109.73 (17)	O16—C16—C17	126.1 (3)
O5—C5—H5	110.0	O3—C16—C17	111.2 (2)
C6—C5—H5	110.0	C16—C17—H171	109.5
C4—C5—H5	110.0	C16—C17—H172	109.5
O6—C6—C5	108.16 (18)	H171—C17—H172	109.5
O6—C6—H61	110.1	C16—C17—H173	109.5
C5—C6—H61	110.1	H171—C17—H173	109.5
O6—C6—H62	110.1	H172—C17—H173	109.5
C5—C6—H62	110.1	O18—C18—O4	123.3 (2)
H61—C6—H62	108.4	O18—C18—C19	125.2 (2)
O7—C7—O6	122.8 (2)	O4—C18—C19	111.5 (2)
O7—C7—C8	126.2 (2)	C18—C19—H191	109.5
O6—C7—C8	110.98 (19)	C18—C19—H192	109.5
C7—C8—H81	109.5	H191—C19—H192	109.5
C7—C8—H82	109.5	C18—C19—H193	109.5
H81—C8—H82	109.5	H191—C19—H193	109.5
C7—C8—H83	109.5	H192—C19—H193	109.5
C5—O5—C1—O1	53.7 (2)	C1—O5—C5—C4	59.7 (2)
C5—O5—C1—C9	178.25 (15)	O4—C4—C5—O5	−167.87 (15)
C5—O5—C1—C2	−63.4 (2)	C3—C4—C5—O5	−50.9 (2)
C14—O2—C2—C3	−133.23 (18)	O4—C4—C5—C6	74.8 (2)
C14—O2—C2—C1	108.10 (19)	C3—C4—C5—C6	−168.22 (18)
O1—C1—C2—O2	55.2 (2)	C7—O6—C6—C5	−144.5 (2)
O5—C1—C2—O2	175.40 (15)	O5—C5—C6—O6	72.1 (2)
C9—C1—C2—O2	−70.7 (2)	C4—C5—C6—O6	−168.41 (17)
O1—C1—C2—C3	−60.9 (2)	C6—O6—C7—O7	1.6 (3)
O5—C1—C2—C3	59.34 (19)	C6—O6—C7—C8	−177.1 (2)
C9—C1—C2—C3	173.22 (17)	O1—C1—C9—C10	56.1 (2)
C16—O3—C3—C2	−135.1 (2)	O5—C1—C9—C10	−66.7 (2)
C16—O3—C3—C4	104.9 (2)	C2—C1—C9—C10	177.68 (18)
O2—C2—C3—O3	66.42 (18)	C12—O11—C10—O10	5.1 (4)
C1—C2—C3—O3	−174.14 (15)	C12—O11—C10—C9	−174.87 (19)
O2—C2—C3—C4	−174.72 (15)	C1—C9—C10—O10	−54.8 (3)
C1—C2—C3—C4	−55.3 (2)	C1—C9—C10—O11	125.2 (2)
C18—O4—C4—C3	100.4 (2)	C10—O11—C12—C13	80.8 (3)
C18—O4—C4—C5	−140.62 (19)	C2—O2—C14—O14	−10.6 (3)
O3—C3—C4—O4	−76.62 (19)	C2—O2—C14—C15	168.34 (19)
C2—C3—C4—O4	166.28 (15)	C3—O3—C16—O16	−5.9 (5)
O3—C3—C4—C5	167.94 (16)	C3—O3—C16—C17	176.4 (2)
C2—C3—C4—C5	50.8 (2)	C4—O4—C18—O18	5.8 (4)
C1—O5—C5—C6	178.81 (16)	C4—O4—C18—C19	−173.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O10	0.79 (4)	2.11 (4)	2.794 (3)	146 (4)

(II) ethyl 2-deoxy-4,5,6,8-tetra-O-benzyl-α-D-galacto-3,7-pyranoso-3-octulosonate

Crystal data

C38H42O8	Dx = 1.237 Mg m^−3
Mr = 626.72	Melting point = 389–392 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 14.977 (2) Å	θ = 11.0–17.5°
b = 19.832 (7) Å	µ = 0.09 mm^−1
c = 11.326 (2) Å	T = 173 K
V = 3364.0 (14) Å^3	Prism, colourless
Z = 4	0.50 × 0.33 × 0.30 mm
F(000) = 1336

Data collection

Rigaku AFC-5R diffractometer	Rint = 0.020
Radiation source: Rigaku rotating anode generator	θmax = 27.5°, θmin = 2.7°
Graphite monochromator	h = 0→19
ω/2θ scans	k = −1→25
4998 measured reflections	l = −1→14
4302 independent reflections	3 standard reflections every 150 reflections
3230 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.103	w = 1/[σ^2(Fo^2) + (0.0379P)^2 + 0.5383P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
4302 reflections	Δρmax = 0.21 e Å^−3
421 parameters	Δρmin = −0.22 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0024 (5)

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.

Refinement. 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	0.11666 (13)	0.88411 (10)	0.17495 (18)	0.0311 (4)
H1	0.128 (2)	0.9179 (16)	0.204 (3)	0.042 (10)*
O2	0.18985 (12)	0.78947 (9)	0.02511 (16)	0.0284 (4)
O3	0.07256 (12)	0.68303 (9)	0.09457 (16)	0.0286 (4)
O4	0.13430 (12)	0.68082 (9)	0.33400 (17)	0.0304 (4)
O5	0.16670 (11)	0.82437 (9)	0.34059 (16)	0.0275 (4)
O6	0.00418 (13)	0.74225 (11)	0.52414 (16)	0.0380 (5)
O15	0.23209 (14)	0.97999 (9)	0.2649 (2)	0.0418 (5)
O16	0.34622 (13)	0.93177 (9)	0.36090 (17)	0.0344 (5)
C1	0.18097 (17)	0.83825 (13)	0.2180 (2)	0.0262 (5)
C2	0.17310 (16)	0.77284 (12)	0.1457 (2)	0.0245 (5)
H2	0.2191	0.7399	0.1735	0.029*
C3	0.08033 (17)	0.74291 (13)	0.1641 (2)	0.0262 (5)
H3	0.0342	0.7763	0.1381	0.031*
C4	0.06895 (17)	0.72879 (13)	0.2959 (2)	0.0276 (6)
H4	0.0078	0.7104	0.3108	0.033*
C5	0.08127 (18)	0.79388 (13)	0.3659 (2)	0.0274 (6)
H5	0.0325	0.8262	0.3450	0.033*
C6	0.08105 (19)	0.78191 (14)	0.4989 (2)	0.0317 (6)
H61	0.1359	0.7578	0.5232	0.038*
H62	0.0783	0.8254	0.5417	0.038*
C7	−0.0008 (2)	0.72263 (15)	0.6454 (2)	0.0390 (7)
H71	0.0589	0.7073	0.6716	0.047*
H72	−0.0424	0.6841	0.6528	0.047*
C8	−0.03198 (18)	0.77880 (14)	0.7259 (2)	0.0309 (6)
C9	0.0174 (2)	0.79671 (14)	0.8242 (3)	0.0367 (7)
H9	0.0711	0.7732	0.8414	0.044*
C10	−0.0103 (2)	0.84867 (15)	0.8985 (3)	0.0404 (7)
H10	0.0240	0.8601	0.9661	0.048*
C11	−0.0878 (2)	0.88333 (15)	0.8732 (3)	0.0439 (8)
H11	−0.1068	0.9191	0.9229	0.053*
C12	−0.1378 (2)	0.86580 (17)	0.7751 (3)	0.0480 (8)
H12	−0.1912	0.8897	0.7576	0.058*
C13	−0.1104 (2)	0.81370 (16)	0.7025 (3)	0.0399 (7)
H13	−0.1456	0.8017	0.6360	0.048*
C14	0.27535 (18)	0.86729 (13)	0.2119 (2)	0.0307 (6)
H141	0.3182	0.8342	0.2446	0.037*
H142	0.2915	0.8757	0.1284	0.037*
C15	0.28148 (18)	0.93245 (13)	0.2808 (3)	0.0320 (6)
C17	0.3588 (2)	0.99449 (14)	0.4270 (3)	0.0413 (7)
H171	0.3041	1.0061	0.4715	0.050*
H172	0.3733	1.0321	0.3729	0.050*
C18	0.4353 (2)	0.98141 (16)	0.5103 (3)	0.0430 (7)
H181	0.4181	0.9465	0.5673	0.064*
H182	0.4502	1.0231	0.5526	0.064*
H183	0.4874	0.9661	0.4654	0.064*
C19	0.24533 (19)	0.74144 (13)	−0.0324 (2)	0.0346 (7)
H191	0.2144	0.6974	−0.0360	0.042*
H192	0.3013	0.7355	0.0129	0.042*
C20	0.26677 (17)	0.76529 (13)	−0.1562 (2)	0.0289 (6)
C21	0.30681 (19)	0.72078 (14)	−0.2350 (3)	0.0366 (7)
H21	0.3185	0.6757	−0.2111	0.044*
C22	0.32974 (19)	0.74127 (15)	−0.3473 (3)	0.0399 (7)
H22	0.3574	0.7104	−0.4000	0.048*
C23	0.3125 (2)	0.80706 (15)	−0.3841 (3)	0.0404 (7)
H23	0.3279	0.8212	−0.4616	0.048*
C24	0.27282 (19)	0.85136 (15)	−0.3062 (3)	0.0380 (7)
H24	0.2607	0.8963	−0.3306	0.046*
C25	0.25028 (18)	0.83111 (14)	−0.1927 (2)	0.0327 (6)
H25	0.2235	0.8623	−0.1397	0.039*
C26	−0.01932 (18)	0.66693 (14)	0.0706 (3)	0.0342 (6)
H261	−0.0466	0.7032	0.0225	0.041*
H262	−0.0528	0.6635	0.1457	0.041*
C27	−0.02433 (17)	0.60121 (13)	0.0053 (2)	0.0302 (6)
C28	−0.0721 (2)	0.54710 (15)	0.0507 (3)	0.0431 (7)
H28	−0.1016	0.5516	0.1245	0.052*
C29	−0.0772 (2)	0.48660 (16)	−0.0103 (3)	0.0554 (9)
H29	−0.1103	0.4500	0.0218	0.067*
C30	−0.0341 (2)	0.47938 (17)	−0.1182 (3)	0.0518 (9)
H30	−0.0370	0.4378	−0.1598	0.062*
C31	0.0126 (2)	0.53280 (16)	−0.1641 (3)	0.0464 (8)
H31	0.0420	0.5282	−0.2380	0.056*
C32	0.0174 (2)	0.59370 (15)	−0.1033 (3)	0.0397 (7)
H32	0.0495	0.6304	−0.1364	0.048*
C33	0.0989 (2)	0.61537 (15)	0.3519 (4)	0.0569 (10)
H331	0.0830	0.5949	0.2750	0.068*
H332	0.0442	0.6181	0.4007	0.068*
C34	0.1680 (2)	0.57251 (14)	0.4135 (3)	0.0378 (7)
C35	0.2121 (3)	0.59589 (18)	0.5103 (3)	0.0686 (12)
H35	0.1983	0.6394	0.5403	0.082*
C36	0.2770 (4)	0.5570 (2)	0.5657 (4)	0.0873 (16)
H36	0.3088	0.5746	0.6315	0.105*
C37	0.2951 (3)	0.49315 (18)	0.5250 (4)	0.0641 (11)
H37	0.3379	0.4658	0.5643	0.077*
C38	0.2522 (3)	0.46964 (16)	0.4300 (4)	0.0566 (9)
H38	0.2655	0.4259	0.4008	0.068*
C39	0.1882 (3)	0.50885 (16)	0.3736 (3)	0.0530 (9)
H39	0.1579	0.4914	0.3065	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0312 (10)	0.0298 (10)	0.0323 (11)	0.0038 (8)	−0.0019 (9)	0.0011 (9)
O2	0.0306 (9)	0.0310 (9)	0.0236 (9)	0.0039 (8)	0.0036 (8)	0.0006 (8)
O3	0.0239 (9)	0.0332 (9)	0.0287 (9)	0.0010 (8)	−0.0005 (8)	−0.0052 (9)
O4	0.0311 (9)	0.0276 (9)	0.0325 (10)	−0.0007 (8)	0.0005 (9)	0.0059 (9)
O5	0.0266 (9)	0.0308 (9)	0.0250 (9)	−0.0024 (8)	0.0020 (8)	0.0011 (8)
O6	0.0384 (11)	0.0504 (12)	0.0253 (10)	−0.0139 (10)	0.0052 (9)	−0.0017 (10)
O15	0.0406 (11)	0.0291 (10)	0.0559 (14)	0.0044 (9)	−0.0075 (11)	0.0020 (10)
O16	0.0364 (10)	0.0270 (9)	0.0398 (11)	0.0001 (8)	−0.0043 (9)	−0.0034 (9)
C1	0.0258 (13)	0.0281 (13)	0.0247 (12)	0.0022 (11)	0.0006 (11)	0.0031 (11)
C2	0.0246 (12)	0.0277 (12)	0.0212 (12)	−0.0004 (10)	0.0017 (11)	0.0027 (11)
C3	0.0262 (12)	0.0269 (12)	0.0254 (12)	0.0022 (11)	0.0013 (11)	0.0002 (11)
C4	0.0234 (12)	0.0322 (13)	0.0271 (13)	−0.0010 (11)	0.0002 (11)	0.0020 (12)
C5	0.0272 (13)	0.0308 (13)	0.0243 (13)	0.0006 (11)	0.0033 (11)	0.0013 (11)
C6	0.0349 (14)	0.0348 (14)	0.0253 (13)	−0.0074 (13)	0.0015 (12)	−0.0013 (12)
C7	0.0477 (17)	0.0392 (15)	0.0301 (15)	−0.0071 (14)	0.0087 (14)	0.0029 (14)
C8	0.0323 (13)	0.0350 (14)	0.0255 (13)	−0.0042 (12)	0.0032 (12)	0.0083 (13)
C9	0.0326 (14)	0.0398 (15)	0.0377 (16)	−0.0003 (12)	−0.0044 (13)	0.0080 (14)
C10	0.0489 (18)	0.0394 (16)	0.0328 (15)	−0.0083 (14)	−0.0092 (15)	0.0012 (14)
C11	0.0522 (19)	0.0400 (16)	0.0395 (17)	−0.0001 (15)	0.0091 (16)	−0.0008 (15)
C12	0.0353 (16)	0.056 (2)	0.052 (2)	0.0078 (15)	−0.0009 (16)	0.0061 (18)
C13	0.0403 (16)	0.0488 (17)	0.0306 (15)	−0.0002 (14)	−0.0071 (13)	0.0030 (14)
C14	0.0288 (13)	0.0315 (13)	0.0320 (14)	−0.0009 (11)	0.0025 (12)	0.0016 (12)
C15	0.0289 (13)	0.0283 (13)	0.0388 (15)	−0.0039 (11)	0.0047 (13)	0.0043 (13)
C17	0.0437 (17)	0.0315 (15)	0.0486 (18)	0.0024 (13)	−0.0041 (16)	−0.0084 (14)
C18	0.0467 (17)	0.0397 (16)	0.0425 (18)	0.0010 (14)	−0.0023 (16)	−0.0090 (15)
C19	0.0379 (15)	0.0300 (14)	0.0358 (15)	0.0070 (12)	0.0106 (13)	0.0005 (13)
C20	0.0235 (12)	0.0333 (13)	0.0300 (14)	−0.0036 (11)	0.0041 (12)	−0.0005 (12)
C21	0.0367 (15)	0.0338 (14)	0.0393 (16)	−0.0013 (13)	0.0087 (14)	−0.0050 (14)
C22	0.0399 (16)	0.0474 (17)	0.0324 (15)	−0.0050 (14)	0.0105 (14)	−0.0110 (15)
C23	0.0389 (17)	0.0530 (18)	0.0293 (15)	−0.0066 (14)	0.0060 (13)	0.0036 (14)
C24	0.0362 (15)	0.0393 (15)	0.0386 (17)	−0.0016 (13)	0.0036 (14)	0.0079 (14)
C25	0.0307 (14)	0.0344 (14)	0.0329 (15)	0.0005 (12)	0.0041 (12)	−0.0045 (13)
C26	0.0272 (13)	0.0345 (15)	0.0409 (16)	0.0010 (12)	−0.0017 (13)	−0.0036 (13)
C27	0.0238 (12)	0.0319 (13)	0.0350 (15)	0.0008 (11)	−0.0059 (12)	−0.0010 (12)
C28	0.0435 (17)	0.0420 (16)	0.0437 (18)	−0.0054 (15)	0.0085 (16)	−0.0035 (15)
C29	0.061 (2)	0.0369 (17)	0.069 (2)	−0.0117 (17)	0.012 (2)	−0.0084 (18)
C30	0.058 (2)	0.0432 (18)	0.054 (2)	−0.0017 (17)	−0.0040 (18)	−0.0149 (17)
C31	0.0555 (19)	0.0556 (19)	0.0281 (15)	0.0019 (17)	−0.0024 (16)	−0.0100 (15)
C32	0.0456 (17)	0.0397 (16)	0.0337 (16)	−0.0018 (14)	−0.0012 (14)	0.0023 (14)
C33	0.053 (2)	0.0376 (17)	0.080 (3)	−0.0132 (15)	−0.018 (2)	0.0167 (19)
C34	0.0404 (16)	0.0314 (14)	0.0415 (17)	−0.0063 (13)	0.0045 (15)	0.0075 (14)
C35	0.107 (3)	0.0437 (18)	0.055 (2)	0.033 (2)	−0.024 (2)	−0.0107 (18)
C36	0.135 (4)	0.061 (2)	0.066 (3)	0.036 (3)	−0.048 (3)	−0.014 (2)
C37	0.076 (3)	0.047 (2)	0.070 (3)	0.0233 (19)	−0.019 (2)	0.006 (2)
C38	0.066 (2)	0.0356 (16)	0.068 (2)	0.0091 (17)	0.011 (2)	−0.0027 (18)
C39	0.068 (2)	0.0364 (16)	0.055 (2)	−0.0025 (17)	−0.0033 (19)	−0.0032 (16)

Geometric parameters (Å, º)

O1—C1	1.412 (3)	C17—H172	0.9900
O1—H1	0.77 (3)	C18—H181	0.9800
O2—C19	1.422 (3)	C18—H182	0.9800
O2—C2	1.428 (3)	C18—H183	0.9800
O3—C3	1.430 (3)	C19—C20	1.514 (4)
O3—C26	1.438 (3)	C19—H191	0.9900
O4—C33	1.417 (3)	C19—H192	0.9900
O4—C4	1.431 (3)	C20—C25	1.391 (4)
O5—C1	1.431 (3)	C20—C21	1.391 (4)
O5—C5	1.444 (3)	C21—C22	1.379 (4)
O6—C6	1.423 (3)	C21—H21	0.9500
O6—C7	1.430 (3)	C22—C23	1.394 (4)
O15—C15	1.212 (3)	C22—H22	0.9500
O16—C15	1.328 (3)	C23—C24	1.379 (4)
O16—C17	1.464 (3)	C23—H23	0.9500
C1—C14	1.528 (4)	C24—C25	1.389 (4)
C1—C2	1.539 (3)	C24—H24	0.9500
C2—C3	1.525 (3)	C25—H25	0.9500
C2—H2	1.0000	C26—C27	1.501 (4)
C3—C4	1.529 (4)	C26—H261	0.9900
C3—H3	1.0000	C26—H262	0.9900
C4—C5	1.526 (4)	C27—C32	1.387 (4)
C4—H4	1.0000	C27—C28	1.388 (4)
C5—C6	1.525 (4)	C28—C29	1.386 (4)
C5—H5	1.0000	C28—H28	0.9500
C6—H61	0.9900	C29—C30	1.390 (5)
C6—H62	0.9900	C29—H29	0.9500
C7—C8	1.513 (4)	C30—C31	1.372 (5)
C7—H71	0.9900	C30—H30	0.9500
C7—H72	0.9900	C31—C32	1.393 (4)
C8—C9	1.383 (4)	C31—H31	0.9500
C8—C13	1.389 (4)	C32—H32	0.9500
C9—C10	1.393 (4)	C33—C34	1.510 (4)
C9—H9	0.9500	C33—H331	0.9900
C10—C11	1.379 (4)	C33—H332	0.9900
C10—H10	0.9500	C34—C35	1.361 (5)
C11—C12	1.384 (4)	C34—C39	1.375 (4)
C11—H11	0.9500	C35—C36	1.391 (5)
C12—C13	1.383 (4)	C35—H35	0.9500
C12—H12	0.9500	C36—C37	1.375 (5)
C13—H13	0.9500	C36—H36	0.9500
C14—C15	1.513 (4)	C37—C38	1.338 (5)
C14—H141	0.9900	C37—H37	0.9500
C14—H142	0.9900	C38—C39	1.390 (5)
C17—C18	1.506 (4)	C38—H38	0.9500
C17—H171	0.9900	C39—H39	0.9500
C1—O1—H1	105 (2)	C18—C17—H172	110.6
C19—O2—C2	112.7 (2)	H171—C17—H172	108.7
C3—O3—C26	111.48 (19)	C17—C18—H181	109.5
C33—O4—C4	113.3 (2)	C17—C18—H182	109.5
C1—O5—C5	113.90 (19)	H181—C18—H182	109.5
C6—O6—C7	112.7 (2)	C17—C18—H183	109.5
C15—O16—C17	115.8 (2)	H181—C18—H183	109.5
O1—C1—O5	110.9 (2)	H182—C18—H183	109.5
O1—C1—C14	111.9 (2)	O2—C19—C20	109.8 (2)
O5—C1—C14	104.8 (2)	O2—C19—H191	109.7
O1—C1—C2	107.9 (2)	C20—C19—H191	109.7
O5—C1—C2	110.0 (2)	O2—C19—H192	109.7
C14—C1—C2	111.4 (2)	C20—C19—H192	109.7
O2—C2—C3	112.4 (2)	H191—C19—H192	108.2
O2—C2—C1	107.52 (19)	C25—C20—C21	118.8 (3)
C3—C2—C1	109.0 (2)	C25—C20—C19	122.0 (2)
O2—C2—H2	109.3	C21—C20—C19	119.2 (2)
C3—C2—H2	109.3	C22—C21—C20	120.8 (3)
C1—C2—H2	109.3	C22—C21—H21	119.6
O3—C3—C2	108.8 (2)	C20—C21—H21	119.6
O3—C3—C4	112.1 (2)	C21—C22—C23	120.4 (3)
C2—C3—C4	107.8 (2)	C21—C22—H22	119.8
O3—C3—H3	109.4	C23—C22—H22	119.8
C2—C3—H3	109.4	C24—C23—C22	119.0 (3)
C4—C3—H3	109.4	C24—C23—H23	120.5
O4—C4—C5	108.9 (2)	C22—C23—H23	120.5
O4—C4—C3	109.9 (2)	C23—C24—C25	120.8 (3)
C5—C4—C3	109.8 (2)	C23—C24—H24	119.6
O4—C4—H4	109.4	C25—C24—H24	119.6
C5—C4—H4	109.4	C24—C25—C20	120.2 (3)
C3—C4—H4	109.4	C24—C25—H25	119.9
O5—C5—C6	105.2 (2)	C20—C25—H25	119.9
O5—C5—C4	111.0 (2)	O3—C26—C27	109.5 (2)
C6—C5—C4	112.4 (2)	O3—C26—H261	109.8
O5—C5—H5	109.4	C27—C26—H261	109.8
C6—C5—H5	109.4	O3—C26—H262	109.8
C4—C5—H5	109.4	C27—C26—H262	109.8
O6—C6—C5	106.6 (2)	H261—C26—H262	108.2
O6—C6—H61	110.4	C32—C27—C28	118.5 (3)
C5—C6—H61	110.4	C32—C27—C26	120.5 (3)
O6—C6—H62	110.4	C28—C27—C26	121.0 (3)
C5—C6—H62	110.4	C29—C28—C27	120.9 (3)
H61—C6—H62	108.6	C29—C28—H28	119.5
O6—C7—C8	113.2 (2)	C27—C28—H28	119.5
O6—C7—H71	108.9	C28—C29—C30	120.0 (3)
C8—C7—H71	108.9	C28—C29—H29	120.0
O6—C7—H72	108.9	C30—C29—H29	120.0
C8—C7—H72	108.9	C31—C30—C29	119.4 (3)
H71—C7—H72	107.7	C31—C30—H30	120.3
C9—C8—C13	118.5 (3)	C29—C30—H30	120.3
C9—C8—C7	120.6 (3)	C30—C31—C32	120.5 (3)
C13—C8—C7	120.9 (3)	C30—C31—H31	119.7
C8—C9—C10	121.1 (3)	C32—C31—H31	119.7
C8—C9—H9	119.4	C27—C32—C31	120.6 (3)
C10—C9—H9	119.4	C27—C32—H32	119.7
C11—C10—C9	119.6 (3)	C31—C32—H32	119.7
C11—C10—H10	120.2	O4—C33—C34	109.0 (3)
C9—C10—H10	120.2	O4—C33—H331	109.9
C10—C11—C12	119.8 (3)	C34—C33—H331	109.9
C10—C11—H11	120.1	O4—C33—H332	109.9
C12—C11—H11	120.1	C34—C33—H332	109.9
C13—C12—C11	120.3 (3)	H331—C33—H332	108.3
C13—C12—H12	119.8	C35—C34—C39	118.1 (3)
C11—C12—H12	119.8	C35—C34—C33	120.8 (3)
C12—C13—C8	120.6 (3)	C39—C34—C33	121.0 (3)
C12—C13—H13	119.7	C34—C35—C36	121.0 (3)
C8—C13—H13	119.7	C34—C35—H35	119.5
C15—C14—C1	110.8 (2)	C36—C35—H35	119.5
C15—C14—H141	109.5	C37—C36—C35	119.8 (4)
C1—C14—H141	109.5	C37—C36—H36	120.1
C15—C14—H142	109.5	C35—C36—H36	120.1
C1—C14—H142	109.5	C38—C37—C36	119.8 (4)
H141—C14—H142	108.1	C38—C37—H37	120.1
O15—C15—O16	123.7 (3)	C36—C37—H37	120.1
O15—C15—C14	123.4 (3)	C37—C38—C39	120.4 (3)
O16—C15—C14	112.8 (2)	C37—C38—H38	119.8
O16—C17—C18	105.8 (2)	C39—C38—H38	119.8
O16—C17—H171	110.6	C34—C39—C38	120.9 (3)
C18—C17—H171	110.6	C34—C39—H39	119.5
O16—C17—H172	110.6	C38—C39—H39	119.5
C5—O5—C1—O1	61.2 (3)	C7—C8—C13—C12	−178.8 (3)
C5—O5—C1—C14	−177.89 (19)	O1—C1—C14—C15	57.8 (3)
C5—O5—C1—C2	−58.1 (3)	O5—C1—C14—C15	−62.5 (3)
C19—O2—C2—C3	−102.7 (2)	C2—C1—C14—C15	178.6 (2)
C19—O2—C2—C1	137.4 (2)	C17—O16—C15—O15	−3.3 (4)
O1—C1—C2—O2	60.1 (2)	C17—O16—C15—C14	177.1 (2)
O5—C1—C2—O2	−178.73 (19)	C1—C14—C15—O15	−53.9 (4)
C14—C1—C2—O2	−63.0 (3)	C1—C14—C15—O16	125.7 (2)
O1—C1—C2—C3	−61.9 (3)	C15—O16—C17—C18	−179.6 (2)
O5—C1—C2—C3	59.2 (3)	C2—O2—C19—C20	−175.1 (2)
C14—C1—C2—C3	174.9 (2)	O2—C19—C20—C25	13.4 (4)
C26—O3—C3—C2	−157.5 (2)	O2—C19—C20—C21	−168.7 (2)
C26—O3—C3—C4	83.3 (3)	C25—C20—C21—C22	−0.1 (4)
O2—C2—C3—O3	59.6 (3)	C19—C20—C21—C22	−178.1 (3)
C1—C2—C3—O3	178.64 (19)	C20—C21—C22—C23	−0.4 (4)
O2—C2—C3—C4	−178.6 (2)	C21—C22—C23—C24	0.4 (4)
C1—C2—C3—C4	−59.5 (3)	C22—C23—C24—C25	0.1 (4)
C33—O4—C4—C5	135.3 (3)	C23—C24—C25—C20	−0.6 (4)
C33—O4—C4—C3	−104.4 (3)	C21—C20—C25—C24	0.6 (4)
O3—C3—C4—O4	58.2 (3)	C19—C20—C25—C24	178.5 (3)
C2—C3—C4—O4	−61.5 (3)	C3—O3—C26—C27	−175.9 (2)
O3—C3—C4—C5	177.9 (2)	O3—C26—C27—C32	−59.7 (3)
C2—C3—C4—C5	58.2 (3)	O3—C26—C27—C28	121.5 (3)
C1—O5—C5—C6	178.6 (2)	C32—C27—C28—C29	0.7 (5)
C1—O5—C5—C4	56.8 (3)	C26—C27—C28—C29	179.5 (3)
O4—C4—C5—O5	64.2 (3)	C27—C28—C29—C30	0.2 (5)
C3—C4—C5—O5	−56.1 (3)	C28—C29—C30—C31	−0.7 (5)
O4—C4—C5—C6	−53.3 (3)	C29—C30—C31—C32	0.3 (5)
C3—C4—C5—C6	−173.6 (2)	C28—C27—C32—C31	−1.1 (4)
C7—O6—C6—C5	175.4 (2)	C26—C27—C32—C31	−179.9 (3)
O5—C5—C6—O6	−170.90 (19)	C30—C31—C32—C27	0.6 (5)
C4—C5—C6—O6	−50.0 (3)	C4—O4—C33—C34	−169.3 (3)
C6—O6—C7—C8	77.1 (3)	O4—C33—C34—C35	47.8 (5)
O6—C7—C8—C9	−126.9 (3)	O4—C33—C34—C39	−132.2 (3)
O6—C7—C8—C13	52.8 (4)	C39—C34—C35—C36	1.3 (6)
C13—C8—C9—C10	−0.2 (4)	C33—C34—C35—C36	−178.7 (4)
C7—C8—C9—C10	179.5 (3)	C34—C35—C36—C37	−2.2 (7)
C8—C9—C10—C11	−0.6 (4)	C35—C36—C37—C38	2.2 (7)
C9—C10—C11—C12	0.6 (4)	C36—C37—C38—C39	−1.3 (7)
C10—C11—C12—C13	0.0 (5)	C35—C34—C39—C38	−0.4 (5)
C11—C12—C13—C8	−0.8 (5)	C33—C34—C39—C38	179.6 (3)
C9—C8—C13—C12	0.9 (4)	C37—C38—C39—C34	0.4 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O15	0.77 (3)	2.10 (3)	2.765 (3)	145 (3)