Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101014974/gg1083sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101014974/gg1083Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101014974/gg1083IIsup3.hkl |
CCDC references: 179267; 179268
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).
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, J3,4 = 9.5 Hz, H3), 5.09 (t, 1H, J4,5 = 9.7 Hz, H4), 4.90 (d, 1H, J2,3 = 9.7 Hz, H2), 4.22–4.31 (m, 1H, H5), 4.21 (q, 2H, J12,13 = 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, J2,3 = 9.8 Hz, H2), 3.74 (dd, 1H, J5,6a = 7.8 Hz, J6a,6 b = 9.3 Hz, H6a), 3.48 (dd, 1H, J6a,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.
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 RF 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 Uiso(H) = 1.5Ueq(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 Uiso(H) = 1.2Ueq(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.
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).
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) Å3 | Prism, colourless |
Z = 2 | 0.46 × 0.33 × 0.24 mm |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0554P)2 + 0.1486P] where P = (Fo2 + 2Fc2)/3 |
3285 reflections | (Δ/σ)max = 0.001 |
280 parameters | Δρmax = 0.49 e Å−3 |
1 restraint | Δρmin = −0.36 e Å−3 |
C18H26O12 | V = 1086.2 (3) Å3 |
Mr = 434.39 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.3164 (15) Å | µ = 0.11 mm−1 |
b = 13.038 (2) Å | T = 173 K |
c = 9.3130 (15) Å | 0.46 × 0.33 × 0.24 mm |
β = 106.224 (12)° |
Rigaku AFC-5R diffractometer | Rint = 0.024 |
6676 measured reflections | 3 standard reflections every 150 reflections |
3285 independent reflections | intensity decay: none |
2717 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.038 | 1 restraint |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.49 e Å−3 |
3285 reflections | Δρmin = −0.36 e Å−3 |
280 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
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) |
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) Å3 | Prism, colourless |
Z = 4 | 0.50 × 0.33 × 0.30 mm |
F(000) = 1336 |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0379P)2 + 0.5383P] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0024 (5) |
C38H42O8 | V = 3364.0 (14) Å3 |
Mr = 626.72 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 14.977 (2) Å | µ = 0.09 mm−1 |
b = 19.832 (7) Å | T = 173 K |
c = 11.326 (2) Å | 0.50 × 0.33 × 0.30 mm |
Rigaku AFC-5R diffractometer | Rint = 0.020 |
4998 measured reflections | 3 standard reflections every 150 reflections |
4302 independent reflections | intensity decay: none |
3230 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.103 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.21 e Å−3 |
4302 reflections | Δρmin = −0.22 e Å−3 |
421 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
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) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C18H26O12 | C38H42O8 |
Mr | 434.39 | 626.72 |
Crystal system, space group | Monoclinic, P21 | Orthorhombic, P212121 |
Temperature (K) | 173 | 173 |
a, b, c (Å) | 9.3164 (15), 13.038 (2), 9.3130 (15) | 14.977 (2), 19.832 (7), 11.326 (2) |
α, β, γ (°) | 90, 106.224 (12), 90 | 90, 90, 90 |
V (Å3) | 1086.2 (3) | 3364.0 (14) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.09 |
Crystal size (mm) | 0.46 × 0.33 × 0.24 | 0.50 × 0.33 × 0.30 |
Data collection | ||
Diffractometer | Rigaku AFC-5R diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6676, 3285, 2717 | 4998, 4302, 3230 |
Rint | 0.024 | 0.020 |
(sin θ/λ)max (Å−1) | 0.703 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.106, 1.03 | 0.042, 0.103, 1.03 |
No. of reflections | 3285 | 4302 |
No. of parameters | 280 | 421 |
No. of restraints | 1 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.49, −0.36 | 0.21, −0.22 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97 and PLATON (Spek, 2001).
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) |
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) |
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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).