A low-temperature structure of ginkgolide A monohydrate, (1R,3S,3aS,4R,6aR,7aR,7bR,8S,10aS,11aS)-3-(1,1-dimethylethyl)-hexahydro-4,7b-dihydroxy-8-methyl-9H-1,7a-epoxymethano-1H,6aH-cyclopenta[c]furo[2,3-b]furo[3′,2′:3,4]cyclopenta[1,2-d]furan-5,9,12(4H)-trione monohydrate, C20H24O9·H2O, obtained from Mo Kα data, is a factor of three more precise than the previous room-temperature determination. A refinement of the ginkgolide A monohydrate structure with Cu Kα data has allowed the assignment of the absolute configuration of the series of compounds. Ginkgolide C sesquihydrate, (1S,2R,3S,3aS,4R,6aR,7aR,7bR,8S,10aS,11S,11aR)-3-(1,1-dimethylethyl)-hexahydro-2,4,7b,11-tetrahydroxy-8-methyl-9H-1,7a-epoxymethano-1H,6aH-cyclopenta[c]furo[2,3-b]furo[3′,2′:3,4]cyclopenta[1,2-d]furan-5,9,12(4H)-trione sesquihydrate, C20H24O11·1.5H2O, has two independent diterpene molecules, both of which exhibit intramolecular hydrogen bonding between OH groups. Ginkgolide J dihydrate, (1S,2R,3S,3aS,4R,6aR,7aR,7bR,8S,10aS,11aS)-3-(1,1-dimethylethyl)-hexahydro-2,4,7b-trihydroxy-8-methyl-9H-1,7a-epoxymethano-1H,6aH-cyclopenta[c]furo[2,3-b]furo[3′,2′:3,4]cyclopenta[1,2-d]furan-5,9,12(4H)-trione dihydrate, C20H24O10·2H2O, has the same basic skeleton as the other ginkgolides, with its three OH groups having the same configurations as those in ginkgolide C. The conformations of the six five-membered rings are quite similar across ginkgolides A–C and J, except for the A and F rings of ginkgolide A.
Supporting information
CCDC references: 183038; 183039; 183040
Ginkgolides A, B, C and J were isolated in large scale from standardized extract
(Neutrasource Inc. San Carlos, CA) of Ginkgo biloba L. (Ginkgoaceae)
using a sodium acetate-impregnated silica-gel chromatographic technique (van
Beek & Lelyveld, 1997) with the combination of a preseparation by normal
column chromatography. Ginkgolide A, (I), was recrystallized from methanol
(MeOH) as plates [m.p. 583 K; [α]D -38 (c, 0.069, dioxane) and -56° (c,
0.06, MeOH)], Ginkgolide C, (III), was recrystallized as plates from
acetone/n-hexane [m.p. 558 K; [α]D -16° (c, 0.055, dioxane)] and
ginkgolide J, (IV), was recrystallized as needles from acetone/n-hexane [m.p.
563 K; [α]D +1.6° (c, 0.061, dioxane)]. The initial physical and NMR data
recorded at 500 (1H) and 125 (13C) MHz using a Bruker Avance DRX-500
instrument, were in agreement with those reported in the literature
(Roumestand et al., 1989; Van Beek & Lankhorst, 1996; Weinges et
al., 1987).
Population parameters of the disordered water sites in ginkgolide C
sesquihydrate were refined, with each pair (O2W/O2W' and O3W/O3W') constrained
to sum to unity. H atoms were placed in calculated positions, with C—H bond
distances in the range 0.96–1.00 Å and thereafter treated as riding. A
torsional parameter was refined for each methyl group. OH and H2O H atoms
were placed from difference maps and refined as follows: for ginkgolide A
monohydrate and ginkgolide J dihydrate, hydroxy O—H distances were
constrained to be 0.82 Å and torsional parameters were refined, while water
H-atom positions were refined individually. For ginkgolide C sesquihydrate,
hydroxy O—H distances were constrained to be 0.84 Å and torsional
parameters were refined, while water H atoms could not be unambiguously
placed. For all compounds, Uiso = 1.2Ueq of the attached
atom (1.5 for methyl groups and H atoms on O atoms).
For all compounds, data collection: COLLECT (Nonius 2000); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996). Software used to prepare material for publication: SHELXL97 for (I), (III); SHELXL97 (Sheldrick, 1997) for (IV).
(I) (1
R,3S,3aS,4
R,6aR,7aR,7bR,8
S,10aS,11aS) 3-
(1,1dimethylethyl)hexahydro-4,7 b-dihydroxy-8-methyl-9
H-1,7a-
(epoxymethano)-1H,6aH-cyclopenta[
c]furo[2,3 b]furo[3',2':3,4]
cyclopenta[1,2-
d]furan-5,9,12(4
H)-trione monohydrate
top
Crystal data top
C20H24O9·H2O | Dx = 1.446 Mg m−3 |
Mr = 426.41 | Melting point: 583 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.931 (2) Å | Cell parameters from 19931 reflections |
b = 12.338 (2) Å | θ = 2.5–33.2° |
c = 17.779 (3) Å | µ = 0.12 mm−1 |
V = 1959.2 (6) Å3 | T = 120 K |
Z = 4 | Fragment, colorless |
F(000) = 904 | 0.48 × 0.37 × 0.35 mm |
Data collection top
KappaCCD (with Oxford Cryosystems Cryostream cooler) diffractometer | 3936 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 33.2°, θmin = 2.5° |
ω scans with κ offsets | h = −13→13 |
19931 measured reflections | k = −18→18 |
4144 independent reflections | l = −27→27 |
Refinement top
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0419P)2 + 0.373P] where P = (Fo2 + 2Fc2)/3 |
4144 reflections | (Δ/σ)max < 0.001 |
283 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
Crystal data top
C20H24O9·H2O | V = 1959.2 (6) Å3 |
Mr = 426.41 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.931 (2) Å | µ = 0.12 mm−1 |
b = 12.338 (2) Å | T = 120 K |
c = 17.779 (3) Å | 0.48 × 0.37 × 0.35 mm |
Data collection top
KappaCCD (with Oxford Cryosystems Cryostream cooler) diffractometer | 3936 reflections with I > 2σ(I) |
19931 measured reflections | Rint = 0.017 |
4144 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.29 e Å−3 |
4144 reflections | Δρmin = −0.21 e Å−3 |
283 parameters | |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
O2 | 0.58578 (10) | 0.27144 (8) | 0.31825 (5) | 0.02002 (18) | |
H2O | 0.6126 | 0.2190 | 0.3452 | 0.030* | |
O3 | 0.24970 (10) | 0.41947 (7) | 0.27989 (5) | 0.01649 (16) | |
O4 | 0.41751 (11) | 0.23326 (9) | 0.16733 (5) | 0.02142 (19) | |
O5 | −0.04901 (11) | 0.11715 (7) | 0.30436 (5) | 0.01907 (17) | |
H5O | −0.1284 | 0.1001 | 0.3268 | 0.029* | |
O6 | −0.07587 (11) | 0.27195 (9) | 0.42798 (5) | 0.02288 (19) | |
O7 | 0.03324 (10) | 0.39217 (7) | 0.35017 (5) | 0.01712 (16) | |
O8 | 0.50061 (11) | 0.40372 (9) | 0.17777 (6) | 0.0236 (2) | |
O9 | 0.27240 (10) | 0.30683 (7) | 0.44388 (5) | 0.01737 (17) | |
O10 | 0.28594 (13) | 0.47482 (8) | 0.48987 (6) | 0.0244 (2) | |
C1 | 0.26641 (14) | 0.16387 (10) | 0.34871 (7) | 0.0164 (2) | |
H1A | 0.1682 | 0.1515 | 0.3731 | 0.020* | |
H1B | 0.3152 | 0.0928 | 0.3404 | 0.020* | |
C2 | 0.36437 (13) | 0.23569 (10) | 0.39779 (6) | 0.0156 (2) | |
H2 | 0.4345 | 0.1917 | 0.4293 | 0.019* | |
C3 | 0.44985 (13) | 0.31425 (10) | 0.34594 (7) | 0.0160 (2) | |
C4 | 0.34378 (13) | 0.32591 (9) | 0.27695 (6) | 0.01434 (19) | |
C5 | 0.24565 (13) | 0.22449 (9) | 0.27271 (6) | 0.01373 (18) | |
C6 | 0.30576 (14) | 0.16278 (10) | 0.20308 (7) | 0.0175 (2) | |
H6 | 0.3491 | 0.0908 | 0.2171 | 0.021* | |
C7 | 0.17387 (15) | 0.15090 (11) | 0.15005 (7) | 0.0191 (2) | |
H7A | 0.1120 | 0.0872 | 0.1636 | 0.023* | |
H7B | 0.2080 | 0.1432 | 0.0973 | 0.023* | |
C8 | 0.08596 (14) | 0.25680 (10) | 0.16095 (6) | 0.0156 (2) | |
H8 | 0.1523 | 0.3154 | 0.1409 | 0.019* | |
C9 | 0.08828 (12) | 0.27060 (9) | 0.24849 (6) | 0.01333 (18) | |
C10 | −0.04446 (13) | 0.22997 (10) | 0.29420 (6) | 0.01510 (19) | |
H10 | −0.1383 | 0.2525 | 0.2678 | 0.018* | |
C11 | −0.03200 (13) | 0.29514 (10) | 0.36653 (7) | 0.0163 (2) | |
C12 | 0.09822 (13) | 0.38938 (9) | 0.27503 (6) | 0.01452 (19) | |
H12 | 0.0425 | 0.4385 | 0.2401 | 0.017* | |
C13 | 0.43176 (13) | 0.32779 (11) | 0.20352 (7) | 0.0180 (2) | |
C14 | 0.46471 (14) | 0.41759 (10) | 0.39373 (7) | 0.0179 (2) | |
H14 | 0.4540 | 0.4838 | 0.3617 | 0.021* | |
C15 | 0.33331 (14) | 0.40665 (10) | 0.44711 (7) | 0.0182 (2) | |
C16 | 0.61053 (16) | 0.42162 (13) | 0.43927 (9) | 0.0270 (3) | |
H16A | 0.6073 | 0.4831 | 0.4741 | 0.041* | |
H16B | 0.6956 | 0.4301 | 0.4050 | 0.041* | |
H16C | 0.6218 | 0.3542 | 0.4678 | 0.041* | |
C17 | −0.06227 (15) | 0.26571 (11) | 0.11536 (7) | 0.0189 (2) | |
C18 | −0.17177 (17) | 0.17144 (12) | 0.12845 (8) | 0.0257 (3) | |
H18A | −0.2021 | 0.1702 | 0.1814 | 0.039* | |
H18B | −0.1226 | 0.1029 | 0.1157 | 0.039* | |
H18C | −0.2603 | 0.1812 | 0.0966 | 0.039* | |
C19 | −0.01925 (18) | 0.26524 (14) | 0.03146 (7) | 0.0282 (3) | |
H19A | 0.0253 | 0.1951 | 0.0184 | 0.042* | |
H19B | 0.0533 | 0.3231 | 0.0217 | 0.042* | |
H19C | −0.1090 | 0.2771 | 0.0008 | 0.042* | |
C20 | −0.14044 (16) | 0.37442 (11) | 0.13101 (8) | 0.0227 (2) | |
H20A | −0.2285 | 0.3813 | 0.0984 | 0.034* | |
H20B | −0.0709 | 0.4340 | 0.1208 | 0.034* | |
H20C | −0.1718 | 0.3772 | 0.1838 | 0.034* | |
O1W | 0.32204 (11) | 0.57887 (8) | 0.12744 (6) | 0.02132 (18) | |
H1W | 0.372 (3) | 0.5233 (17) | 0.1416 (12) | 0.032* | |
H2W | 0.301 (2) | 0.5633 (17) | 0.0835 (12) | 0.032* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O2 | 0.0155 (4) | 0.0230 (4) | 0.0216 (4) | 0.0046 (4) | 0.0025 (3) | 0.0049 (4) |
O3 | 0.0133 (4) | 0.0133 (3) | 0.0229 (4) | 0.0006 (3) | 0.0003 (3) | 0.0021 (3) |
O4 | 0.0182 (4) | 0.0271 (5) | 0.0190 (4) | 0.0010 (4) | 0.0060 (3) | −0.0002 (4) |
O5 | 0.0197 (4) | 0.0137 (3) | 0.0238 (4) | −0.0018 (3) | 0.0045 (3) | 0.0006 (3) |
O6 | 0.0242 (4) | 0.0269 (5) | 0.0176 (4) | −0.0017 (4) | 0.0067 (3) | 0.0003 (4) |
O7 | 0.0192 (4) | 0.0154 (4) | 0.0168 (3) | −0.0002 (3) | 0.0039 (3) | −0.0022 (3) |
O8 | 0.0178 (4) | 0.0277 (5) | 0.0252 (4) | 0.0012 (4) | 0.0049 (3) | 0.0101 (4) |
O9 | 0.0179 (4) | 0.0184 (4) | 0.0158 (3) | 0.0007 (3) | 0.0015 (3) | 0.0011 (3) |
O10 | 0.0306 (5) | 0.0213 (4) | 0.0212 (4) | 0.0029 (4) | 0.0015 (4) | −0.0025 (4) |
C1 | 0.0179 (5) | 0.0143 (5) | 0.0169 (4) | 0.0005 (4) | 0.0000 (4) | 0.0028 (4) |
C2 | 0.0160 (5) | 0.0162 (5) | 0.0147 (4) | 0.0013 (4) | 0.0010 (4) | 0.0023 (4) |
C3 | 0.0138 (4) | 0.0172 (5) | 0.0171 (5) | 0.0014 (4) | 0.0002 (4) | 0.0023 (4) |
C4 | 0.0140 (4) | 0.0144 (4) | 0.0146 (4) | 0.0007 (4) | 0.0016 (4) | 0.0023 (4) |
C5 | 0.0139 (4) | 0.0133 (4) | 0.0140 (4) | 0.0010 (4) | 0.0021 (4) | 0.0008 (4) |
C6 | 0.0177 (5) | 0.0176 (5) | 0.0173 (5) | 0.0038 (4) | 0.0034 (4) | −0.0005 (4) |
C7 | 0.0215 (5) | 0.0192 (5) | 0.0165 (5) | 0.0027 (5) | 0.0012 (4) | −0.0030 (4) |
C8 | 0.0168 (5) | 0.0169 (5) | 0.0131 (4) | 0.0008 (4) | 0.0004 (4) | −0.0002 (4) |
C9 | 0.0134 (4) | 0.0130 (4) | 0.0136 (4) | 0.0011 (4) | 0.0014 (4) | 0.0005 (4) |
C10 | 0.0154 (5) | 0.0143 (4) | 0.0156 (4) | −0.0003 (4) | 0.0019 (4) | −0.0006 (4) |
C11 | 0.0142 (5) | 0.0166 (5) | 0.0181 (5) | 0.0008 (4) | 0.0023 (4) | −0.0002 (4) |
C12 | 0.0143 (4) | 0.0139 (4) | 0.0154 (4) | 0.0007 (4) | 0.0011 (4) | 0.0006 (4) |
C13 | 0.0133 (4) | 0.0230 (5) | 0.0179 (5) | 0.0033 (4) | 0.0020 (4) | 0.0049 (4) |
C14 | 0.0178 (5) | 0.0172 (5) | 0.0188 (5) | −0.0017 (4) | −0.0001 (4) | 0.0004 (4) |
C15 | 0.0187 (5) | 0.0195 (5) | 0.0165 (5) | 0.0014 (4) | −0.0024 (4) | 0.0013 (4) |
C16 | 0.0213 (6) | 0.0284 (7) | 0.0314 (7) | −0.0029 (5) | −0.0064 (5) | −0.0035 (6) |
C17 | 0.0205 (5) | 0.0198 (5) | 0.0164 (5) | 0.0001 (5) | −0.0026 (4) | 0.0007 (4) |
C18 | 0.0268 (6) | 0.0251 (6) | 0.0253 (6) | −0.0063 (5) | −0.0068 (5) | −0.0002 (5) |
C19 | 0.0327 (7) | 0.0359 (7) | 0.0159 (5) | 0.0036 (7) | −0.0035 (5) | 0.0004 (5) |
C20 | 0.0209 (6) | 0.0221 (6) | 0.0252 (6) | 0.0034 (5) | −0.0056 (5) | 0.0007 (5) |
O1W | 0.0223 (4) | 0.0192 (4) | 0.0224 (4) | 0.0011 (4) | −0.0016 (4) | −0.0011 (4) |
Geometric parameters (Å, º) top
O2—C3 | 1.413 (2) | C7—H7A | 0.9900 |
O2—H2O | 0.8400 | C7—H7B | 0.9900 |
O3—C12 | 1.406 (2) | C8—C17 | 1.556 (2) |
O3—C4 | 1.429 (2) | C8—C9 | 1.566 (2) |
O4—C13 | 1.338 (2) | C8—H8 | 1.0000 |
O4—C6 | 1.469 (2) | C9—C10 | 1.522 (2) |
O5—C10 | 1.404 (2) | C9—C12 | 1.542 (2) |
O5—H5O | 0.8400 | C10—C11 | 1.521 (2) |
O6—C11 | 1.196 (2) | C10—H10 | 1.0000 |
O7—C11 | 1.363 (2) | C12—H12 | 1.0000 |
O7—C12 | 1.457 (2) | C14—C15 | 1.515 (2) |
O8—C13 | 1.210 (2) | C14—C16 | 1.534 (2) |
O9—C15 | 1.348 (2) | C14—H14 | 1.0000 |
O9—C2 | 1.455 (2) | C16—H16A | 0.9800 |
O10—C15 | 1.210 (2) | C16—H16B | 0.9800 |
C1—C2 | 1.521 (2) | C16—H16C | 0.9800 |
C1—C5 | 1.555 (2) | C17—C18 | 1.537 (2) |
C1—H1A | 0.9900 | C17—C20 | 1.538 (2) |
C1—H1B | 0.9900 | C17—C19 | 1.540 (2) |
C2—C3 | 1.540 (2) | C18—H18A | 0.9800 |
C2—H2 | 1.0000 | C18—H18B | 0.9800 |
C3—C14 | 1.538 (2) | C18—H18C | 0.9800 |
C3—C4 | 1.556 (2) | C19—H19A | 0.9800 |
C4—C13 | 1.524 (2) | C19—H19B | 0.9800 |
C4—C5 | 1.530 (2) | C19—H19C | 0.9800 |
C5—C6 | 1.549 (2) | C20—H20A | 0.9800 |
C5—C9 | 1.576 (2) | C20—H20B | 0.9800 |
C6—C7 | 1.516 (2) | C20—H20C | 0.9800 |
C6—H6 | 1.0000 | O1W—H1W | 0.86 (2) |
C7—C8 | 1.537 (2) | O1W—H2W | 0.83 (2) |
| | | |
C3—O2—H2O | 109.5 | C8—C9—C5 | 104.13 (9) |
C12—O3—C4 | 110.52 (9) | O5—C10—C11 | 114.68 (10) |
C13—O4—C6 | 111.89 (9) | O5—C10—C9 | 114.69 (10) |
C10—O5—H5O | 109.5 | C11—C10—C9 | 102.73 (9) |
C11—O7—C12 | 110.20 (9) | O5—C10—H10 | 108.1 |
C15—O9—C2 | 110.34 (9) | C11—C10—H10 | 108.1 |
C2—C1—C5 | 106.67 (9) | C9—C10—H10 | 108.1 |
C2—C1—H1A | 110.4 | O6—C11—O7 | 123.06 (11) |
C5—C1—H1A | 110.4 | O6—C11—C10 | 128.49 (11) |
C2—C1—H1B | 110.4 | O7—C11—C10 | 108.38 (10) |
C5—C1—H1B | 110.4 | O3—C12—O7 | 108.71 (9) |
H1A—C1—H1B | 108.6 | O3—C12—C9 | 108.98 (9) |
O9—C2—C1 | 110.49 (10) | O7—C12—C9 | 106.26 (9) |
O9—C2—C3 | 103.72 (9) | O3—C12—H12 | 110.9 |
C1—C2—C3 | 107.97 (9) | O7—C12—H12 | 110.9 |
O9—C2—H2 | 111.5 | C9—C12—H12 | 110.9 |
C1—C2—H2 | 111.5 | O8—C13—O4 | 122.76 (12) |
C3—C2—H2 | 111.5 | O8—C13—C4 | 126.71 (12) |
O2—C3—C14 | 115.37 (10) | O4—C13—C4 | 110.46 (10) |
O2—C3—C2 | 113.54 (10) | C15—C14—C16 | 109.25 (10) |
C14—C3—C2 | 103.53 (9) | C15—C14—C3 | 101.85 (10) |
O2—C3—C4 | 106.43 (9) | C16—C14—C3 | 113.06 (11) |
C14—C3—C4 | 114.28 (10) | C15—C14—H14 | 110.8 |
C2—C3—C4 | 103.18 (9) | C16—C14—H14 | 110.8 |
O3—C4—C13 | 108.80 (9) | C3—C14—H14 | 110.8 |
O3—C4—C5 | 109.01 (9) | O10—C15—O9 | 121.40 (12) |
C13—C4—C5 | 105.41 (9) | O10—C15—C14 | 127.04 (12) |
O3—C4—C3 | 113.81 (9) | O9—C15—C14 | 111.54 (10) |
C13—C4—C3 | 111.26 (9) | C14—C16—H16A | 109.5 |
C5—C4—C3 | 108.18 (9) | C14—C16—H16B | 109.5 |
C4—C5—C6 | 104.05 (9) | H16A—C16—H16B | 109.5 |
C4—C5—C1 | 106.40 (9) | C14—C16—H16C | 109.5 |
C6—C5—C1 | 114.61 (9) | H16A—C16—H16C | 109.5 |
C4—C5—C9 | 103.25 (9) | H16B—C16—H16C | 109.5 |
C6—C5—C9 | 105.55 (9) | C18—C17—C20 | 110.10 (11) |
C1—C5—C9 | 121.14 (9) | C18—C17—C19 | 107.61 (11) |
O4—C6—C7 | 108.43 (10) | C20—C17—C19 | 106.97 (11) |
O4—C6—C5 | 106.87 (10) | C18—C17—C8 | 114.14 (10) |
C7—C6—C5 | 105.98 (9) | C20—C17—C8 | 110.71 (10) |
O4—C6—H6 | 111.8 | C19—C17—C8 | 106.97 (11) |
C7—C6—H6 | 111.8 | C17—C18—H18A | 109.5 |
C5—C6—H6 | 111.8 | C17—C18—H18B | 109.5 |
C6—C7—C8 | 103.68 (10) | H18A—C18—H18B | 109.5 |
C6—C7—H7A | 111.0 | C17—C18—H18C | 109.5 |
C8—C7—H7A | 111.0 | H18A—C18—H18C | 109.5 |
C6—C7—H7B | 111.0 | H18B—C18—H18C | 109.5 |
C8—C7—H7B | 111.0 | C17—C19—H19A | 109.5 |
H7A—C7—H7B | 109.0 | C17—C19—H19B | 109.5 |
C7—C8—C17 | 115.41 (10) | H19A—C19—H19B | 109.5 |
C7—C8—C9 | 102.18 (9) | C17—C19—H19C | 109.5 |
C17—C8—C9 | 121.42 (10) | H19A—C19—H19C | 109.5 |
C7—C8—H8 | 105.5 | H19B—C19—H19C | 109.5 |
C17—C8—H8 | 105.5 | C17—C20—H20A | 109.5 |
C9—C8—H8 | 105.5 | C17—C20—H20B | 109.5 |
C10—C9—C12 | 101.22 (9) | H20A—C20—H20B | 109.5 |
C10—C9—C8 | 118.98 (10) | C17—C20—H20C | 109.5 |
C12—C9—C8 | 114.09 (9) | H20A—C20—H20C | 109.5 |
C10—C9—C5 | 115.45 (9) | H20B—C20—H20C | 109.5 |
C12—C9—C5 | 102.01 (9) | H1W—O1W—H2W | 102.1 (19) |
| | | |
C15—O9—C2—C1 | −139.48 (10) | C4—C5—C9—C12 | −23.49 (10) |
C15—O9—C2—C3 | −23.99 (12) | C6—C5—C9—C12 | −132.43 (9) |
C5—C1—C2—O9 | 92.01 (11) | C1—C5—C9—C12 | 95.26 (11) |
C5—C1—C2—C3 | −20.79 (12) | C4—C5—C9—C8 | 95.44 (10) |
O9—C2—C3—O2 | 155.81 (9) | C6—C5—C9—C8 | −13.49 (11) |
C1—C2—C3—O2 | −86.93 (12) | C1—C5—C9—C8 | −145.80 (10) |
O9—C2—C3—C14 | 29.98 (11) | C12—C9—C10—O5 | −157.45 (10) |
C1—C2—C3—C14 | 147.23 (10) | C8—C9—C10—O5 | 76.71 (13) |
O9—C2—C3—C4 | −89.42 (10) | C5—C9—C10—O5 | −48.22 (14) |
C1—C2—C3—C4 | 27.84 (12) | C12—C9—C10—C11 | −32.36 (11) |
C12—O3—C4—C13 | 112.18 (10) | C8—C9—C10—C11 | −158.20 (10) |
C12—O3—C4—C5 | −2.29 (12) | C5—C9—C10—C11 | 76.87 (12) |
C12—O3—C4—C3 | −123.14 (10) | C12—O7—C11—O6 | 169.98 (12) |
O2—C3—C4—O3 | −143.58 (9) | C12—O7—C11—C10 | −13.07 (13) |
C14—C3—C4—O3 | −15.03 (14) | O5—C10—C11—O6 | −28.67 (19) |
C2—C3—C4—O3 | 96.64 (11) | C9—C10—C11—O6 | −153.76 (13) |
O2—C3—C4—C13 | −20.23 (13) | O5—C10—C11—O7 | 154.60 (10) |
C14—C3—C4—C13 | 108.32 (11) | C9—C10—C11—O7 | 29.50 (12) |
C2—C3—C4—C13 | −140.01 (10) | C4—O3—C12—O7 | 101.34 (10) |
O2—C3—C4—C5 | 95.11 (11) | C4—O3—C12—C9 | −14.06 (12) |
C14—C3—C4—C5 | −136.35 (10) | C11—O7—C12—O3 | −125.77 (10) |
C2—C3—C4—C5 | −24.67 (12) | C11—O7—C12—C9 | −8.61 (12) |
O3—C4—C5—C6 | 126.92 (9) | C10—C9—C12—O3 | 142.97 (9) |
C13—C4—C5—C6 | 10.27 (11) | C8—C9—C12—O3 | −88.00 (12) |
C3—C4—C5—C6 | −108.84 (10) | C5—C9—C12—O3 | 23.62 (11) |
O3—C4—C5—C1 | −111.67 (10) | C10—C9—C12—O7 | 25.99 (11) |
C13—C4—C5—C1 | 131.68 (9) | C8—C9—C12—O7 | 155.02 (9) |
C3—C4—C5—C1 | 12.57 (12) | C5—C9—C12—O7 | −93.36 (10) |
O3—C4—C5—C9 | 16.88 (11) | C6—O4—C13—O8 | −168.83 (11) |
C13—C4—C5—C9 | −99.78 (10) | C6—O4—C13—C4 | 8.17 (13) |
C3—C4—C5—C9 | 141.11 (9) | O3—C4—C13—O8 | 48.26 (16) |
C2—C1—C5—C4 | 4.88 (12) | C5—C4—C13—O8 | 165.05 (12) |
C2—C1—C5—C6 | 119.29 (11) | C3—C4—C13—O8 | −77.91 (15) |
C2—C1—C5—C9 | −112.30 (11) | O3—C4—C13—O4 | −128.59 (10) |
C13—O4—C6—C7 | 112.67 (11) | C5—C4—C13—O4 | −11.80 (13) |
C13—O4—C6—C5 | −1.17 (13) | C3—C4—C13—O4 | 105.24 (11) |
C4—C5—C6—O4 | −6.06 (12) | O2—C3—C14—C15 | −149.59 (10) |
C1—C5—C6—O4 | −121.83 (10) | C2—C3—C14—C15 | −24.93 (11) |
C9—C5—C6—O4 | 102.29 (10) | C4—C3—C14—C15 | 86.53 (11) |
C4—C5—C6—C7 | −121.56 (10) | O2—C3—C14—C16 | −32.50 (15) |
C1—C5—C6—C7 | 122.67 (11) | C2—C3—C14—C16 | 92.16 (12) |
C9—C5—C6—C7 | −13.21 (12) | C4—C3—C14—C16 | −156.38 (11) |
O4—C6—C7—C8 | −78.97 (11) | C2—O9—C15—O10 | −170.55 (12) |
C5—C6—C7—C8 | 35.47 (12) | C2—O9—C15—C14 | 7.87 (13) |
C6—C7—C8—C17 | −177.37 (10) | C16—C14—C15—O10 | 70.15 (17) |
C6—C7—C8—C9 | −43.50 (12) | C3—C14—C15—O10 | −170.04 (13) |
C7—C8—C9—C10 | −95.57 (12) | C16—C14—C15—O9 | −108.16 (12) |
C17—C8—C9—C10 | 34.69 (16) | C3—C14—C15—O9 | 11.65 (13) |
C7—C8—C9—C12 | 145.01 (10) | C7—C8—C17—C18 | 54.85 (14) |
C17—C8—C9—C12 | −84.73 (14) | C9—C8—C17—C18 | −69.48 (15) |
C7—C8—C9—C5 | 34.67 (11) | C7—C8—C17—C20 | 179.74 (10) |
C17—C8—C9—C5 | 164.93 (10) | C9—C8—C17—C20 | 55.41 (15) |
C4—C5—C9—C10 | −132.25 (10) | C7—C8—C17—C19 | −64.05 (14) |
C6—C5—C9—C10 | 118.82 (11) | C9—C8—C17—C19 | 171.62 (11) |
C1—C5—C9—C10 | −13.49 (15) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O1Wi | 0.84 | 1.89 | 2.694 (2) | 160 |
O5—H5O···O1Wii | 0.84 | 1.93 | 2.764 (2) | 172 |
O1W—H1W···O8 | 0.86 (2) | 1.98 (2) | 2.831 (2) | 175 (2) |
O1W—H2W···O10iii | 0.83 (2) | 1.90 (2) | 2.711 (2) | 169 (2) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) −x+1/2, −y+1, z−1/2. |
(III) (1
S,2
R,3
S,3aS,4
R,6aR,7aR,7bR,8
S,10aS,11
S,11aR) 3-(1,1-dimethylethyl) hexahydro-2,4,7 b,11-tetrahydroxy-8-methyl-9
H-1,7a-(epoxymethano)-1H,6aH–
cyclopenta[
c]furo[2,3 b]furo[3',2':3,4]cyclopenta[1,2-
d]furan-5,9,12 (4
H)-trione
sesquihydrate
top
Crystal data top
C20H24O11·1.5H2O | Dx = 1.526 Mg m−3 |
Mr = 467.42 | Melting point: 558 K |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.4945 (15) Å | Cell parameters from 5587 reflections |
b = 12.973 (3) Å | θ = 2.5–29.6° |
c = 20.934 (4) Å | µ = 0.13 mm−1 |
β = 91.00 (2)° | T = 120 K |
V = 2035.0 (7) Å3 | Prism, colorless |
Z = 4 | 0.47 × 0.27 × 0.25 mm |
F(000) = 988 | |
Data collection top
KappaCCD (with Oxford Cryosystems Cryostream cooler) diffractometer | 5752 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 29.6°, θmin = 2.7° |
ω scans with κ offsets | h = −10→10 |
22429 measured reflections | k = −18→13 |
5921 independent reflections | l = −29→29 |
Refinement top
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0549P)2 + 0.4304P] where P = (Fo2 + 2Fc2)/3 |
5921 reflections | (Δ/σ)max = 0.001 |
622 parameters | Δρmax = 0.37 e Å−3 |
1 restraint | Δρmin = −0.18 e Å−3 |
Crystal data top
C20H24O11·1.5H2O | V = 2035.0 (7) Å3 |
Mr = 467.42 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.4945 (15) Å | µ = 0.13 mm−1 |
b = 12.973 (3) Å | T = 120 K |
c = 20.934 (4) Å | 0.47 × 0.27 × 0.25 mm |
β = 91.00 (2)° | |
Data collection top
KappaCCD (with Oxford Cryosystems Cryostream cooler) diffractometer | 5752 reflections with I > 2σ(I) |
22429 measured reflections | Rint = 0.019 |
5921 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | 1 restraint |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.37 e Å−3 |
5921 reflections | Δρmin = −0.18 e Å−3 |
622 parameters | |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
O1A | −0.10445 (15) | 0.32753 (11) | 0.53160 (6) | 0.0182 (2) | |
H1HA | −0.0863 | 0.3537 | 0.4956 | 0.027* | |
O2A | 0.18859 (17) | 0.13714 (10) | 0.69354 (6) | 0.0183 (2) | |
H2HA | 0.2881 | 0.1164 | 0.7075 | 0.027* | |
O3A | 0.47719 (15) | 0.21528 (10) | 0.57649 (6) | 0.0149 (2) | |
O4A | 0.15237 (17) | 0.04164 (10) | 0.53658 (6) | 0.0174 (2) | |
O5A | 0.11116 (16) | 0.38425 (10) | 0.43266 (6) | 0.0179 (2) | |
H5HA | 0.1080 | 0.4312 | 0.4051 | 0.027* | |
O6A | 0.33504 (18) | 0.52395 (10) | 0.50839 (6) | 0.0204 (3) | |
O7A | 0.48890 (16) | 0.38203 (10) | 0.53639 (6) | 0.0164 (2) | |
O8A | 0.37947 (19) | 0.00138 (10) | 0.60183 (6) | 0.0211 (3) | |
O9A | −0.01476 (17) | 0.33786 (10) | 0.67684 (6) | 0.0193 (2) | |
O10A | 0.1254 (2) | 0.42475 (12) | 0.75432 (7) | 0.0286 (3) | |
O11A | 0.07426 (19) | 0.03387 (11) | 0.40540 (6) | 0.0219 (3) | |
H11A | 0.1357 | −0.0136 | 0.4219 | 0.033* | |
C1A | 0.0605 (2) | 0.30858 (13) | 0.56292 (8) | 0.0136 (3) | |
H1A | 0.1285 | 0.3746 | 0.5674 | 0.016* | |
C2A | 0.0309 (2) | 0.26188 (13) | 0.62915 (8) | 0.0154 (3) | |
H2A | −0.0606 | 0.2058 | 0.6270 | 0.018* | |
C3A | 0.2144 (2) | 0.21871 (13) | 0.64991 (8) | 0.0141 (3) | |
C4A | 0.2974 (2) | 0.18345 (13) | 0.58571 (8) | 0.0129 (3) | |
C5A | 0.1790 (2) | 0.22646 (12) | 0.53140 (7) | 0.0116 (3) | |
C6A | 0.0753 (2) | 0.13291 (13) | 0.50537 (8) | 0.0147 (3) | |
H6A | −0.0559 | 0.1390 | 0.5124 | 0.018* | |
C7A | 0.1199 (2) | 0.12857 (13) | 0.43446 (8) | 0.0153 (3) | |
H7A | 0.0491 | 0.1837 | 0.4123 | 0.018* | |
C8A | 0.3188 (2) | 0.16099 (13) | 0.43317 (7) | 0.0134 (3) | |
H8A | 0.3870 | 0.1058 | 0.4563 | 0.016* | |
C9A | 0.3177 (2) | 0.25622 (12) | 0.47859 (7) | 0.0116 (3) | |
C10A | 0.2891 (2) | 0.36256 (13) | 0.44944 (8) | 0.0139 (3) | |
H10A | 0.3628 | 0.3679 | 0.4102 | 0.017* | |
C11A | 0.3674 (2) | 0.43433 (14) | 0.49988 (8) | 0.0151 (3) | |
C12A | 0.4887 (2) | 0.27250 (13) | 0.51990 (7) | 0.0131 (3) | |
H12A | 0.5978 | 0.2536 | 0.4957 | 0.016* | |
C13A | 0.2857 (2) | 0.06556 (13) | 0.57760 (8) | 0.0155 (3) | |
C14A | 0.2983 (2) | 0.31438 (13) | 0.68223 (8) | 0.0166 (3) | |
H14A | 0.3454 | 0.3600 | 0.6479 | 0.020* | |
C15A | 0.1343 (3) | 0.36608 (14) | 0.70958 (9) | 0.0204 (3) | |
C16A | 0.4481 (3) | 0.29640 (16) | 0.73098 (9) | 0.0252 (4) | |
H16A | 0.4875 | 0.3627 | 0.7487 | 0.038* | |
H16B | 0.5484 | 0.2625 | 0.7102 | 0.038* | |
H16C | 0.4047 | 0.2524 | 0.7655 | 0.038* | |
C17A | 0.4033 (2) | 0.17030 (14) | 0.36585 (8) | 0.0171 (3) | |
C18A | 0.2843 (3) | 0.23041 (17) | 0.31799 (8) | 0.0226 (4) | |
H18A | 0.3395 | 0.2300 | 0.2759 | 0.034* | |
H18B | 0.2712 | 0.3017 | 0.3327 | 0.034* | |
H18C | 0.1665 | 0.1977 | 0.3150 | 0.034* | |
C19A | 0.4275 (3) | 0.06132 (16) | 0.33818 (9) | 0.0270 (4) | |
H19A | 0.3101 | 0.0305 | 0.3296 | 0.040* | |
H19B | 0.4939 | 0.0186 | 0.3690 | 0.040* | |
H19C | 0.4938 | 0.0656 | 0.2983 | 0.040* | |
C20A | 0.5922 (2) | 0.21718 (16) | 0.37150 (8) | 0.0206 (3) | |
H20A | 0.6641 | 0.1770 | 0.4021 | 0.031* | |
H20B | 0.5839 | 0.2886 | 0.3864 | 0.031* | |
H20C | 0.6487 | 0.2157 | 0.3296 | 0.031* | |
O1B | 0.37642 (16) | 0.23496 (10) | 0.00320 (6) | 0.0178 (2) | |
H1HB | 0.3920 | 0.2776 | −0.0264 | 0.027* | |
O2B | 0.61554 (18) | 0.04031 (11) | 0.16805 (6) | 0.0207 (3) | |
H2HB | 0.7072 | 0.0121 | 0.1837 | 0.031* | |
O3B | 0.94462 (16) | 0.10996 (10) | 0.06296 (6) | 0.0166 (2) | |
O4B | 0.62239 (17) | −0.04148 (9) | 0.00060 (6) | 0.0170 (2) | |
O5B | 0.64412 (17) | 0.31774 (10) | −0.08190 (6) | 0.0180 (2) | |
H5HB | 0.6562 | 0.3666 | −0.1078 | 0.027* | |
O6B | 0.84724 (19) | 0.43445 (11) | 0.01391 (7) | 0.0235 (3) | |
O7B | 0.97973 (16) | 0.28380 (10) | 0.03741 (6) | 0.0182 (2) | |
O8B | 0.80101 (19) | −0.09892 (11) | 0.07933 (6) | 0.0225 (3) | |
O9B | 0.45961 (19) | 0.25553 (11) | 0.15083 (6) | 0.0220 (3) | |
O10B | 0.6126 (2) | 0.33470 (12) | 0.22943 (7) | 0.0292 (3) | |
O11B | 0.57728 (19) | −0.02014 (11) | −0.13452 (6) | 0.0222 (3) | |
H11B | 0.6226 | −0.0747 | −0.1200 | 0.033* | |
C1B | 0.5365 (2) | 0.22233 (13) | 0.03826 (8) | 0.0133 (3) | |
H1B | 0.5987 | 0.2901 | 0.0433 | 0.016* | |
C2B | 0.4957 (2) | 0.17680 (13) | 0.10383 (8) | 0.0165 (3) | |
H2B | 0.3939 | 0.1271 | 0.1005 | 0.020* | |
C3B | 0.6665 (2) | 0.12164 (13) | 0.12719 (8) | 0.0159 (3) | |
C4B | 0.7584 (2) | 0.08721 (13) | 0.06466 (8) | 0.0139 (3) | |
C5B | 0.6639 (2) | 0.14185 (12) | 0.00859 (7) | 0.0118 (3) | |
C6B | 0.5623 (2) | 0.05577 (12) | −0.02715 (8) | 0.0141 (3) | |
H6B | 0.4300 | 0.0644 | −0.0248 | 0.017* | |
C7B | 0.6286 (2) | 0.06384 (13) | −0.09516 (8) | 0.0146 (3) | |
H7B | 0.5730 | 0.1270 | −0.1143 | 0.018* | |
C8B | 0.8299 (2) | 0.08659 (13) | −0.08607 (7) | 0.0130 (3) | |
H8B | 0.8817 | 0.0256 | −0.0632 | 0.016* | |
C9B | 0.82132 (19) | 0.17495 (13) | −0.03565 (7) | 0.0119 (3) | |
C10B | 0.8125 (2) | 0.28688 (13) | −0.05862 (8) | 0.0143 (3) | |
H10B | 0.9011 | 0.2963 | −0.0933 | 0.017* | |
C11B | 0.8768 (2) | 0.34667 (14) | 0.00000 (8) | 0.0171 (3) | |
C12B | 0.9781 (2) | 0.17819 (13) | 0.01261 (8) | 0.0151 (3) | |
H12B | 1.0932 | 0.1613 | −0.0084 | 0.018* | |
C13B | 0.7335 (2) | −0.02818 (14) | 0.05136 (8) | 0.0162 (3) | |
C14B | 0.7643 (2) | 0.20958 (14) | 0.16239 (8) | 0.0187 (3) | |
H14B | 0.8269 | 0.2514 | 0.1295 | 0.022* | |
C15B | 0.6111 (3) | 0.27390 (15) | 0.18651 (8) | 0.0215 (3) | |
C16B | 0.9015 (3) | 0.18147 (17) | 0.21383 (9) | 0.0277 (4) | |
H16D | 0.9386 | 0.2439 | 0.2369 | 0.042* | |
H16E | 1.0055 | 0.1499 | 0.1940 | 0.042* | |
H16F | 0.8487 | 0.1326 | 0.2438 | 0.042* | |
C17B | 0.9404 (2) | 0.09985 (14) | −0.14806 (8) | 0.0162 (3) | |
C18B | 0.8508 (2) | 0.17222 (15) | −0.19726 (8) | 0.0196 (3) | |
H18D | 0.8451 | 0.2421 | −0.1796 | 0.029* | |
H18E | 0.7298 | 0.1476 | −0.2071 | 0.029* | |
H18F | 0.9206 | 0.1730 | −0.2364 | 0.029* | |
C19B | 0.9631 (3) | −0.00728 (15) | −0.17895 (9) | 0.0232 (4) | |
H19D | 0.8470 | −0.0319 | −0.1950 | 0.035* | |
H19E | 1.0105 | −0.0558 | −0.1470 | 0.035* | |
H19F | 1.0461 | −0.0022 | −0.2145 | 0.035* | |
C20B | 1.1300 (2) | 0.13842 (16) | −0.13184 (9) | 0.0205 (3) | |
H20D | 1.2022 | 0.1371 | −0.1704 | 0.031* | |
H20E | 1.1846 | 0.0936 | −0.0993 | 0.031* | |
H20F | 1.1240 | 0.2091 | −0.1155 | 0.031* | |
O1W | 0.5019 (2) | 0.53009 (13) | 0.26802 (8) | 0.0334 (3) | |
O2W | 0.2407 (13) | −0.0403 (4) | 0.1721 (4) | 0.0346 (16) | 0.72 (3) |
O2W' | 0.181 (3) | −0.0269 (7) | 0.1514 (11) | 0.032 (3) | 0.28 (3) |
O3W | 0.2362 (6) | 0.5574 (3) | 0.36358 (18) | 0.0241 (11) | 0.494 (10) |
O3W' | 0.1490 (7) | 0.5294 (3) | 0.34387 (18) | 0.0307 (14) | 0.506 (10) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1A | 0.0114 (5) | 0.0213 (6) | 0.0219 (6) | 0.0031 (4) | −0.0002 (4) | 0.0012 (5) |
O2A | 0.0233 (6) | 0.0159 (6) | 0.0158 (5) | 0.0005 (5) | 0.0049 (5) | 0.0039 (5) |
O3A | 0.0113 (5) | 0.0201 (6) | 0.0133 (5) | 0.0004 (4) | 0.0003 (4) | 0.0039 (4) |
O4A | 0.0214 (6) | 0.0121 (5) | 0.0186 (5) | −0.0019 (4) | 0.0004 (5) | 0.0007 (4) |
O5A | 0.0142 (5) | 0.0172 (6) | 0.0219 (6) | 0.0033 (4) | −0.0042 (4) | 0.0038 (5) |
O6A | 0.0229 (6) | 0.0132 (6) | 0.0252 (6) | −0.0018 (5) | 0.0001 (5) | −0.0016 (5) |
O7A | 0.0156 (5) | 0.0152 (6) | 0.0182 (5) | −0.0021 (4) | −0.0034 (4) | −0.0006 (4) |
O8A | 0.0283 (7) | 0.0165 (6) | 0.0185 (6) | 0.0067 (5) | 0.0021 (5) | 0.0021 (5) |
O9A | 0.0240 (6) | 0.0169 (6) | 0.0171 (6) | 0.0029 (5) | 0.0070 (5) | −0.0025 (5) |
O10A | 0.0425 (8) | 0.0221 (7) | 0.0213 (6) | 0.0017 (6) | 0.0048 (6) | −0.0078 (5) |
O11A | 0.0278 (7) | 0.0159 (6) | 0.0220 (6) | −0.0058 (5) | −0.0020 (5) | −0.0050 (5) |
C1A | 0.0111 (6) | 0.0134 (7) | 0.0164 (7) | 0.0004 (5) | 0.0008 (5) | −0.0011 (6) |
C2A | 0.0161 (7) | 0.0127 (7) | 0.0175 (7) | 0.0004 (6) | 0.0056 (6) | −0.0019 (6) |
C3A | 0.0178 (7) | 0.0117 (6) | 0.0130 (7) | −0.0004 (5) | 0.0034 (5) | −0.0001 (5) |
C4A | 0.0129 (6) | 0.0129 (7) | 0.0130 (7) | 0.0002 (5) | 0.0015 (5) | 0.0005 (5) |
C5A | 0.0105 (6) | 0.0121 (6) | 0.0122 (6) | 0.0000 (5) | 0.0008 (5) | 0.0003 (5) |
C6A | 0.0145 (7) | 0.0111 (6) | 0.0185 (7) | −0.0012 (5) | 0.0007 (5) | 0.0006 (6) |
C7A | 0.0170 (7) | 0.0136 (7) | 0.0152 (7) | −0.0022 (6) | −0.0004 (6) | −0.0028 (6) |
C8A | 0.0148 (7) | 0.0130 (7) | 0.0126 (7) | 0.0004 (5) | 0.0014 (5) | −0.0003 (5) |
C9A | 0.0108 (6) | 0.0129 (6) | 0.0111 (6) | −0.0006 (5) | 0.0000 (5) | −0.0001 (5) |
C10A | 0.0131 (7) | 0.0133 (7) | 0.0154 (7) | 0.0004 (5) | −0.0005 (5) | 0.0011 (6) |
C11A | 0.0146 (7) | 0.0152 (7) | 0.0155 (7) | −0.0015 (6) | 0.0012 (6) | 0.0013 (6) |
C12A | 0.0115 (6) | 0.0147 (7) | 0.0132 (6) | −0.0004 (5) | −0.0002 (5) | 0.0008 (6) |
C13A | 0.0186 (7) | 0.0140 (7) | 0.0140 (7) | 0.0008 (6) | 0.0053 (6) | −0.0005 (6) |
C14A | 0.0210 (7) | 0.0144 (7) | 0.0144 (7) | −0.0025 (6) | 0.0011 (6) | −0.0010 (6) |
C15A | 0.0298 (9) | 0.0144 (7) | 0.0170 (7) | −0.0001 (6) | 0.0039 (6) | −0.0003 (6) |
C16A | 0.0286 (9) | 0.0267 (9) | 0.0201 (8) | −0.0026 (7) | −0.0060 (7) | −0.0021 (7) |
C17A | 0.0197 (7) | 0.0182 (8) | 0.0136 (7) | 0.0015 (6) | 0.0023 (6) | −0.0008 (6) |
C18A | 0.0241 (8) | 0.0298 (9) | 0.0137 (7) | 0.0017 (7) | −0.0020 (6) | 0.0009 (7) |
C19A | 0.0405 (11) | 0.0212 (9) | 0.0196 (8) | 0.0026 (8) | 0.0096 (8) | −0.0040 (7) |
C20A | 0.0180 (7) | 0.0280 (9) | 0.0159 (7) | 0.0024 (7) | 0.0049 (6) | 0.0030 (7) |
O1B | 0.0120 (5) | 0.0169 (6) | 0.0243 (6) | 0.0014 (4) | −0.0005 (4) | 0.0046 (5) |
O2B | 0.0267 (6) | 0.0183 (6) | 0.0173 (5) | 0.0028 (5) | 0.0045 (5) | 0.0066 (5) |
O3B | 0.0114 (5) | 0.0216 (6) | 0.0169 (5) | 0.0020 (4) | −0.0013 (4) | 0.0017 (5) |
O4B | 0.0192 (6) | 0.0120 (5) | 0.0198 (6) | −0.0018 (4) | −0.0004 (5) | 0.0013 (4) |
O5B | 0.0166 (5) | 0.0156 (6) | 0.0218 (6) | 0.0004 (5) | −0.0008 (4) | 0.0038 (5) |
O6B | 0.0246 (6) | 0.0163 (6) | 0.0298 (7) | −0.0043 (5) | 0.0037 (5) | −0.0054 (5) |
O7B | 0.0164 (5) | 0.0199 (6) | 0.0183 (5) | −0.0045 (5) | −0.0014 (4) | −0.0033 (5) |
O8B | 0.0293 (7) | 0.0165 (6) | 0.0218 (6) | 0.0071 (5) | 0.0010 (5) | 0.0052 (5) |
O9B | 0.0280 (7) | 0.0205 (6) | 0.0176 (6) | 0.0070 (5) | 0.0067 (5) | −0.0007 (5) |
O10B | 0.0503 (9) | 0.0204 (7) | 0.0170 (6) | 0.0047 (6) | 0.0058 (6) | −0.0024 (5) |
O11B | 0.0271 (7) | 0.0181 (6) | 0.0214 (6) | −0.0053 (5) | −0.0026 (5) | −0.0067 (5) |
C1B | 0.0105 (6) | 0.0133 (7) | 0.0161 (7) | 0.0006 (5) | 0.0022 (5) | 0.0018 (6) |
C2B | 0.0177 (7) | 0.0144 (7) | 0.0177 (7) | 0.0026 (6) | 0.0061 (6) | 0.0011 (6) |
C3B | 0.0199 (7) | 0.0141 (7) | 0.0137 (7) | 0.0016 (6) | 0.0028 (6) | 0.0028 (6) |
C4B | 0.0140 (7) | 0.0144 (7) | 0.0132 (7) | 0.0010 (5) | −0.0001 (5) | 0.0009 (5) |
C5B | 0.0104 (6) | 0.0117 (6) | 0.0133 (6) | −0.0007 (5) | 0.0006 (5) | 0.0018 (5) |
C6B | 0.0128 (6) | 0.0116 (7) | 0.0179 (7) | −0.0011 (5) | −0.0007 (5) | 0.0002 (6) |
C7B | 0.0149 (7) | 0.0141 (7) | 0.0147 (7) | −0.0023 (5) | −0.0018 (5) | −0.0020 (6) |
C8B | 0.0132 (7) | 0.0126 (7) | 0.0132 (6) | 0.0002 (5) | 0.0003 (5) | 0.0001 (5) |
C9B | 0.0080 (6) | 0.0143 (7) | 0.0136 (6) | −0.0012 (5) | 0.0019 (5) | 0.0003 (5) |
C10B | 0.0138 (7) | 0.0131 (7) | 0.0160 (7) | −0.0012 (5) | 0.0022 (5) | −0.0001 (6) |
C11B | 0.0141 (7) | 0.0182 (7) | 0.0192 (7) | −0.0061 (6) | 0.0036 (6) | −0.0014 (6) |
C12B | 0.0122 (7) | 0.0168 (7) | 0.0161 (7) | −0.0007 (6) | 0.0001 (5) | −0.0011 (6) |
C13B | 0.0168 (7) | 0.0158 (7) | 0.0162 (7) | 0.0025 (6) | 0.0042 (6) | 0.0002 (6) |
C14B | 0.0247 (8) | 0.0181 (8) | 0.0134 (7) | 0.0003 (6) | −0.0006 (6) | −0.0010 (6) |
C15B | 0.0321 (9) | 0.0173 (8) | 0.0152 (7) | 0.0027 (7) | 0.0045 (7) | 0.0029 (6) |
C16B | 0.0341 (10) | 0.0276 (10) | 0.0212 (9) | 0.0033 (8) | −0.0090 (8) | −0.0028 (8) |
C17B | 0.0159 (7) | 0.0183 (7) | 0.0145 (7) | 0.0012 (6) | 0.0028 (5) | 0.0003 (6) |
C18B | 0.0227 (8) | 0.0220 (8) | 0.0141 (7) | 0.0016 (7) | 0.0015 (6) | 0.0010 (6) |
C19B | 0.0284 (9) | 0.0202 (8) | 0.0212 (8) | 0.0040 (7) | 0.0059 (7) | −0.0037 (7) |
C20B | 0.0157 (7) | 0.0259 (9) | 0.0199 (8) | 0.0001 (6) | 0.0039 (6) | 0.0006 (7) |
O1W | 0.0482 (9) | 0.0226 (7) | 0.0288 (7) | 0.0042 (7) | −0.0135 (7) | −0.0040 (6) |
O2W | 0.036 (3) | 0.0330 (14) | 0.035 (2) | 0.0011 (15) | −0.001 (2) | −0.0102 (15) |
O2W' | 0.035 (6) | 0.024 (3) | 0.037 (6) | 0.006 (3) | −0.007 (5) | −0.011 (3) |
O3W | 0.024 (2) | 0.0230 (15) | 0.0255 (16) | 0.0037 (13) | 0.0003 (14) | 0.0079 (12) |
O3W' | 0.036 (3) | 0.0327 (18) | 0.0235 (17) | 0.0104 (18) | 0.0065 (17) | 0.0123 (14) |
Geometric parameters (Å, º) top
O1A—C1A | 1.411 (2) | O1B—H1HB | 0.8400 |
O1A—H1HA | 0.8400 | O2B—C3B | 1.415 (2) |
O2A—C3A | 1.413 (2) | O2B—H2HB | 0.8400 |
O2A—H2HA | 0.8400 | O3B—C12B | 1.402 (2) |
O3A—C12A | 1.402 (2) | O3B—C4B | 1.427 (2) |
O3A—C4A | 1.426 (2) | O4B—C13B | 1.350 (2) |
O4A—C13A | 1.342 (2) | O4B—C6B | 1.457 (2) |
O4A—C6A | 1.466 (2) | O5B—C10B | 1.403 (2) |
O5A—C10A | 1.402 (2) | O5B—H5HB | 0.8400 |
O5A—H5HA | 0.8400 | O6B—C11B | 1.197 (2) |
O6A—C11A | 1.202 (2) | O7B—C11B | 1.361 (2) |
O7A—C11A | 1.360 (2) | O7B—C12B | 1.465 (2) |
O7A—C12A | 1.462 (2) | O8B—C13B | 1.196 (2) |
O8A—C13A | 1.197 (2) | O9B—C15B | 1.369 (2) |
O9A—C15A | 1.351 (2) | O9B—C2B | 1.447 (2) |
O9A—C2A | 1.448 (2) | O10B—C15B | 1.196 (2) |
O10A—C15A | 1.210 (2) | O11B—C7B | 1.415 (2) |
O11A—C7A | 1.410 (2) | O11B—H11B | 0.8400 |
O11A—H11A | 0.8400 | C1B—C2B | 1.530 (2) |
C1A—C2A | 1.533 (2) | C1B—C5B | 1.552 (2) |
C1A—C5A | 1.543 (2) | C1B—H1B | 1.0000 |
C1A—H1A | 1.0000 | C2B—C3B | 1.539 (2) |
C2A—C3A | 1.540 (2) | C2B—H2B | 1.0000 |
C2A—H2A | 1.0000 | C3B—C14B | 1.537 (2) |
C3A—C14A | 1.542 (2) | C3B—C4B | 1.555 (2) |
C3A—C4A | 1.559 (2) | C4B—C13B | 1.533 (2) |
C4A—C5A | 1.535 (2) | C4B—C5B | 1.534 (2) |
C4A—C13A | 1.541 (2) | C5B—C6B | 1.538 (2) |
C5A—C6A | 1.536 (2) | C5B—C9B | 1.572 (2) |
C5A—C9A | 1.578 (2) | C6B—C7B | 1.520 (2) |
C6A—C7A | 1.528 (2) | C6B—H6B | 1.0000 |
C6A—H6A | 1.0000 | C7B—C8B | 1.546 (2) |
C7A—C8A | 1.550 (2) | C7B—H7B | 1.0000 |
C7A—H7A | 1.0000 | C8B—C9B | 1.560 (2) |
C8A—C9A | 1.559 (2) | C8B—C17B | 1.561 (2) |
C8A—C17A | 1.560 (2) | C8B—H8B | 1.0000 |
C8A—H8A | 1.0000 | C9B—C10B | 1.531 (2) |
C9A—C10A | 1.522 (2) | C9B—C12B | 1.537 (2) |
C9A—C12A | 1.548 (2) | C10B—C11B | 1.523 (2) |
C10A—C11A | 1.518 (2) | C10B—H10B | 1.0000 |
C10A—H10A | 1.0000 | C12B—H12B | 1.0000 |
C12A—H12A | 1.0000 | C14B—C15B | 1.513 (3) |
C14A—C15A | 1.521 (3) | C14B—C16B | 1.520 (3) |
C14A—C16A | 1.522 (2) | C14B—H14B | 1.0000 |
C14A—H14A | 1.0000 | C16B—H16D | 0.9800 |
C16A—H16A | 0.9800 | C16B—H16E | 0.9800 |
C16A—H16B | 0.9800 | C16B—H16F | 0.9800 |
C16A—H16C | 0.9800 | C17B—C20B | 1.539 (2) |
C17A—C19A | 1.540 (3) | C17B—C18B | 1.539 (2) |
C17A—C18A | 1.542 (2) | C17B—C19B | 1.543 (3) |
C17A—C20A | 1.544 (2) | C18B—H18D | 0.9800 |
C18A—H18A | 0.9800 | C18B—H18E | 0.9800 |
C18A—H18B | 0.9800 | C18B—H18F | 0.9800 |
C18A—H18C | 0.9800 | C19B—H19D | 0.9800 |
C19A—H19A | 0.9800 | C19B—H19E | 0.9800 |
C19A—H19B | 0.9800 | C19B—H19F | 0.9800 |
C19A—H19C | 0.9800 | C20B—H20D | 0.9800 |
C20A—H20A | 0.9800 | C20B—H20E | 0.9800 |
C20A—H20B | 0.9800 | C20B—H20F | 0.9800 |
C20A—H20C | 0.9800 | O2W—O2W' | 0.641 (17) |
O1B—C1B | 1.405 (2) | O3W—O3W' | 0.849 (4) |
| | | |
C1A—O1A—H1HA | 109.5 | C1B—O1B—H1HB | 109.5 |
C3A—O2A—H2HA | 109.5 | C3B—O2B—H2HB | 109.5 |
C12A—O3A—C4A | 109.87 (12) | C12B—O3B—C4B | 109.70 (12) |
C13A—O4A—C6A | 112.43 (13) | C13B—O4B—C6B | 112.67 (13) |
C10A—O5A—H5HA | 109.5 | C10B—O5B—H5HB | 109.5 |
C11A—O7A—C12A | 110.74 (13) | C11B—O7B—C12B | 110.82 (13) |
C15A—O9A—C2A | 109.33 (13) | C15B—O9B—C2B | 109.33 (14) |
C7A—O11A—H11A | 109.5 | C7B—O11B—H11B | 109.5 |
O1A—C1A—C2A | 110.46 (13) | O1B—C1B—C2B | 109.35 (13) |
O1A—C1A—C5A | 115.33 (13) | O1B—C1B—C5B | 113.27 (13) |
C2A—C1A—C5A | 101.98 (13) | C2B—C1B—C5B | 103.50 (13) |
O1A—C1A—H1A | 109.6 | O1B—C1B—H1B | 110.2 |
C2A—C1A—H1A | 109.6 | C2B—C1B—H1B | 110.2 |
C5A—C1A—H1A | 109.6 | C5B—C1B—H1B | 110.2 |
O9A—C2A—C1A | 113.22 (14) | O9B—C2B—C1B | 112.34 (14) |
O9A—C2A—C3A | 105.87 (13) | O9B—C2B—C3B | 106.04 (14) |
C1A—C2A—C3A | 104.84 (13) | C1B—C2B—C3B | 106.63 (13) |
O9A—C2A—H2A | 110.9 | O9B—C2B—H2B | 110.6 |
C1A—C2A—H2A | 110.9 | C1B—C2B—H2B | 110.6 |
C3A—C2A—H2A | 110.9 | C3B—C2B—H2B | 110.6 |
O2A—C3A—C2A | 108.85 (13) | O2B—C3B—C14B | 113.27 (13) |
O2A—C3A—C14A | 112.22 (13) | O2B—C3B—C2B | 107.87 (13) |
C2A—C3A—C14A | 100.75 (13) | C14B—C3B—C2B | 101.21 (14) |
O2A—C3A—C4A | 113.48 (13) | O2B—C3B—C4B | 115.01 (14) |
C2A—C3A—C4A | 103.36 (13) | C14B—C3B—C4B | 113.70 (14) |
C14A—C3A—C4A | 116.64 (13) | C2B—C3B—C4B | 104.15 (13) |
O3A—C4A—C5A | 109.25 (12) | O3B—C4B—C13B | 108.28 (13) |
O3A—C4A—C13A | 108.94 (13) | O3B—C4B—C5B | 108.92 (13) |
C5A—C4A—C13A | 104.36 (13) | C13B—C4B—C5B | 105.00 (13) |
O3A—C4A—C3A | 115.08 (13) | O3B—C4B—C3B | 114.15 (13) |
C5A—C4A—C3A | 107.33 (13) | C13B—C4B—C3B | 112.25 (13) |
C13A—C4A—C3A | 111.31 (13) | C5B—C4B—C3B | 107.81 (13) |
C4A—C5A—C6A | 104.95 (13) | C4B—C5B—C6B | 104.77 (13) |
C4A—C5A—C1A | 105.29 (13) | C4B—C5B—C1B | 106.49 (13) |
C6A—C5A—C1A | 113.94 (13) | C6B—C5B—C1B | 112.36 (13) |
C4A—C5A—C9A | 103.23 (12) | C4B—C5B—C9B | 103.63 (12) |
C6A—C5A—C9A | 106.26 (12) | C6B—C5B—C9B | 106.37 (12) |
C1A—C5A—C9A | 121.45 (13) | C1B—C5B—C9B | 121.68 (13) |
O4A—C6A—C7A | 108.19 (13) | O4B—C6B—C7B | 109.24 (13) |
O4A—C6A—C5A | 106.67 (13) | O4B—C6B—C5B | 106.73 (12) |
C7A—C6A—C5A | 104.83 (13) | C7B—C6B—C5B | 103.81 (12) |
O4A—C6A—H6A | 112.2 | O4B—C6B—H6B | 112.2 |
C7A—C6A—H6A | 112.2 | C7B—C6B—H6B | 112.2 |
C5A—C6A—H6A | 112.2 | C5B—C6B—H6B | 112.2 |
O11A—C7A—C6A | 113.31 (14) | O11B—C7B—C6B | 113.75 (14) |
O11A—C7A—C8A | 117.05 (14) | O11B—C7B—C8B | 118.25 (14) |
C6A—C7A—C8A | 103.51 (13) | C6B—C7B—C8B | 103.41 (12) |
O11A—C7A—H7A | 107.5 | O11B—C7B—H7B | 106.9 |
C6A—C7A—H7A | 107.5 | C6B—C7B—H7B | 106.9 |
C8A—C7A—H7A | 107.5 | C8B—C7B—H7B | 106.9 |
C7A—C8A—C9A | 100.88 (12) | C7B—C8B—C9B | 99.89 (12) |
C7A—C8A—C17A | 116.27 (13) | C7B—C8B—C17B | 116.72 (13) |
C9A—C8A—C17A | 119.77 (13) | C9B—C8B—C17B | 120.67 (13) |
C7A—C8A—H8A | 106.3 | C7B—C8B—H8B | 106.1 |
C9A—C8A—H8A | 106.3 | C9B—C8B—H8B | 106.1 |
C17A—C8A—H8A | 106.3 | C17B—C8B—H8B | 106.1 |
C10A—C9A—C12A | 102.09 (12) | C10B—C9B—C12B | 102.06 (13) |
C10A—C9A—C8A | 118.41 (12) | C10B—C9B—C8B | 119.11 (13) |
C12A—C9A—C8A | 115.82 (13) | C12B—C9B—C8B | 115.13 (13) |
C10A—C9A—C5A | 114.39 (13) | C10B—C9B—C5B | 114.54 (13) |
C12A—C9A—C5A | 101.00 (12) | C12B—C9B—C5B | 101.14 (12) |
C8A—C9A—C5A | 104.13 (12) | C8B—C9B—C5B | 103.77 (12) |
O5A—C10A—C11A | 113.93 (14) | O5B—C10B—C11B | 113.89 (14) |
O5A—C10A—C9A | 114.13 (13) | O5B—C10B—C9B | 114.43 (13) |
C11A—C10A—C9A | 103.12 (13) | C11B—C10B—C9B | 102.63 (13) |
O5A—C10A—H10A | 108.5 | O5B—C10B—H10B | 108.5 |
C11A—C10A—H10A | 108.5 | C11B—C10B—H10B | 108.5 |
C9A—C10A—H10A | 108.5 | C9B—C10B—H10B | 108.5 |
O6A—C11A—O7A | 122.30 (16) | O6B—C11B—O7B | 122.39 (17) |
O6A—C11A—C10A | 128.32 (16) | O6B—C11B—C10B | 128.53 (17) |
O7A—C11A—C10A | 109.38 (14) | O7B—C11B—C10B | 109.08 (15) |
O3A—C12A—O7A | 108.35 (13) | O3B—C12B—O7B | 108.93 (13) |
O3A—C12A—C9A | 109.72 (12) | O3B—C12B—C9B | 109.39 (13) |
O7A—C12A—C9A | 105.19 (13) | O7B—C12B—C9B | 105.07 (13) |
O3A—C12A—H12A | 111.1 | O3B—C12B—H12B | 111.1 |
O7A—C12A—H12A | 111.1 | O7B—C12B—H12B | 111.1 |
C9A—C12A—H12A | 111.1 | C9B—C12B—H12B | 111.1 |
O8A—C13A—O4A | 122.38 (16) | O8B—C13B—O4B | 122.50 (17) |
O8A—C13A—C4A | 127.71 (16) | O8B—C13B—C4B | 127.64 (16) |
O4A—C13A—C4A | 109.89 (14) | O4B—C13B—C4B | 109.84 (14) |
C15A—C14A—C16A | 114.00 (15) | C15B—C14B—C16B | 113.80 (15) |
C15A—C14A—C3A | 101.17 (14) | C15B—C14B—C3B | 102.16 (15) |
C16A—C14A—C3A | 117.47 (15) | C16B—C14B—C3B | 118.20 (16) |
C15A—C14A—H14A | 107.9 | C15B—C14B—H14B | 107.4 |
C16A—C14A—H14A | 107.9 | C16B—C14B—H14B | 107.4 |
C3A—C14A—H14A | 107.9 | C3B—C14B—H14B | 107.4 |
O10A—C15A—O9A | 120.49 (18) | O10B—C15B—O9B | 121.46 (18) |
O10A—C15A—C14A | 128.64 (19) | O10B—C15B—C14B | 128.11 (19) |
O9A—C15A—C14A | 110.87 (14) | O9B—C15B—C14B | 110.42 (15) |
C14A—C16A—H16A | 109.5 | C14B—C16B—H16D | 109.5 |
C14A—C16A—H16B | 109.5 | C14B—C16B—H16E | 109.5 |
H16A—C16A—H16B | 109.5 | H16D—C16B—H16E | 109.5 |
C14A—C16A—H16C | 109.5 | C14B—C16B—H16F | 109.5 |
H16A—C16A—H16C | 109.5 | H16D—C16B—H16F | 109.5 |
H16B—C16A—H16C | 109.5 | H16E—C16B—H16F | 109.5 |
C19A—C17A—C18A | 106.88 (15) | C20B—C17B—C18B | 109.87 (15) |
C19A—C17A—C20A | 106.08 (15) | C20B—C17B—C19B | 106.12 (15) |
C18A—C17A—C20A | 111.73 (15) | C18B—C17B—C19B | 108.58 (14) |
C19A—C17A—C8A | 108.73 (14) | C20B—C17B—C8B | 110.70 (13) |
C18A—C17A—C8A | 112.76 (14) | C18B—C17B—C8B | 113.07 (14) |
C20A—C17A—C8A | 110.34 (13) | C19B—C17B—C8B | 108.23 (14) |
C17A—C18A—H18A | 109.5 | C17B—C18B—H18D | 109.5 |
C17A—C18A—H18B | 109.5 | C17B—C18B—H18E | 109.5 |
H18A—C18A—H18B | 109.5 | H18D—C18B—H18E | 109.5 |
C17A—C18A—H18C | 109.5 | C17B—C18B—H18F | 109.5 |
H18A—C18A—H18C | 109.5 | H18D—C18B—H18F | 109.5 |
H18B—C18A—H18C | 109.5 | H18E—C18B—H18F | 109.5 |
C17A—C19A—H19A | 109.5 | C17B—C19B—H19D | 109.5 |
C17A—C19A—H19B | 109.5 | C17B—C19B—H19E | 109.5 |
H19A—C19A—H19B | 109.5 | H19D—C19B—H19E | 109.5 |
C17A—C19A—H19C | 109.5 | C17B—C19B—H19F | 109.5 |
H19A—C19A—H19C | 109.5 | H19D—C19B—H19F | 109.5 |
H19B—C19A—H19C | 109.5 | H19E—C19B—H19F | 109.5 |
C17A—C20A—H20A | 109.5 | C17B—C20B—H20D | 109.5 |
C17A—C20A—H20B | 109.5 | C17B—C20B—H20E | 109.5 |
H20A—C20A—H20B | 109.5 | H20D—C20B—H20E | 109.5 |
C17A—C20A—H20C | 109.5 | C17B—C20B—H20F | 109.5 |
H20A—C20A—H20C | 109.5 | H20D—C20B—H20F | 109.5 |
H20B—C20A—H20C | 109.5 | H20E—C20B—H20F | 109.5 |
| | | |
C15A—O9A—C2A—C1A | −95.94 (16) | C15B—O9B—C2B—C1B | −97.88 (16) |
C15A—O9A—C2A—C3A | 18.37 (17) | C15B—O9B—C2B—C3B | 18.23 (17) |
O1A—C1A—C2A—O9A | −79.85 (17) | O1B—C1B—C2B—O9B | −88.63 (17) |
C5A—C1A—C2A—O9A | 157.05 (13) | C5B—C1B—C2B—O9B | 150.38 (13) |
O1A—C1A—C2A—C3A | 165.21 (13) | O1B—C1B—C2B—C3B | 155.62 (13) |
C5A—C1A—C2A—C3A | 42.12 (15) | C5B—C1B—C2B—C3B | 34.63 (17) |
O9A—C2A—C3A—O2A | 86.17 (15) | O9B—C2B—C3B—O2B | 88.43 (15) |
C1A—C2A—C3A—O2A | −153.87 (13) | C1B—C2B—C3B—O2B | −151.66 (13) |
O9A—C2A—C3A—C14A | −31.97 (15) | O9B—C2B—C3B—C14B | −30.72 (16) |
C1A—C2A—C3A—C14A | 87.99 (14) | C1B—C2B—C3B—C14B | 89.19 (15) |
O9A—C2A—C3A—C4A | −152.92 (13) | O9B—C2B—C3B—C4B | −148.92 (13) |
C1A—C2A—C3A—C4A | −32.96 (16) | C1B—C2B—C3B—C4B | −29.01 (17) |
C12A—O3A—C4A—C5A | −1.92 (17) | C12B—O3B—C4B—C13B | 116.35 (14) |
C12A—O3A—C4A—C13A | 111.51 (15) | C12B—O3B—C4B—C5B | 2.69 (18) |
C12A—O3A—C4A—C3A | −122.70 (15) | C12B—O3B—C4B—C3B | −117.84 (15) |
O2A—C3A—C4A—O3A | −109.38 (16) | O2B—C3B—C4B—O3B | −109.10 (16) |
C2A—C3A—C4A—O3A | 132.90 (14) | C14B—C3B—C4B—O3B | 23.8 (2) |
C14A—C3A—C4A—O3A | 23.4 (2) | C2B—C3B—C4B—O3B | 133.07 (14) |
O2A—C3A—C4A—C5A | 128.79 (14) | O2B—C3B—C4B—C13B | 14.6 (2) |
C2A—C3A—C4A—C5A | 11.07 (16) | C14B—C3B—C4B—C13B | 147.53 (14) |
C14A—C3A—C4A—C5A | −98.42 (16) | C2B—C3B—C4B—C13B | −103.23 (15) |
O2A—C3A—C4A—C13A | 15.17 (19) | O2B—C3B—C4B—C5B | 129.76 (14) |
C2A—C3A—C4A—C13A | −102.55 (15) | C14B—C3B—C4B—C5B | −97.32 (16) |
C14A—C3A—C4A—C13A | 147.96 (15) | C2B—C3B—C4B—C5B | 11.93 (17) |
O3A—C4A—C5A—C6A | 128.63 (13) | O3B—C4B—C5B—C6B | 125.49 (13) |
C13A—C4A—C5A—C6A | 12.25 (16) | C13B—C4B—C5B—C6B | 9.70 (16) |
C3A—C4A—C5A—C6A | −105.97 (14) | C3B—C4B—C5B—C6B | −110.15 (14) |
O3A—C4A—C5A—C1A | −110.81 (14) | O3B—C4B—C5B—C1B | −115.28 (14) |
C13A—C4A—C5A—C1A | 132.81 (13) | C13B—C4B—C5B—C1B | 128.93 (13) |
C3A—C4A—C5A—C1A | 14.59 (16) | C3B—C4B—C5B—C1B | 9.08 (17) |
O3A—C4A—C5A—C9A | 17.50 (16) | O3B—C4B—C5B—C9B | 14.16 (16) |
C13A—C4A—C5A—C9A | −98.89 (14) | C13B—C4B—C5B—C9B | −101.63 (14) |
C3A—C4A—C5A—C9A | 142.90 (13) | C3B—C4B—C5B—C9B | 138.52 (13) |
O1A—C1A—C5A—C4A | −154.23 (13) | O1B—C1B—C5B—C4B | −144.86 (13) |
C2A—C1A—C5A—C4A | −34.51 (15) | C2B—C1B—C5B—C4B | −26.55 (16) |
O1A—C1A—C5A—C6A | −39.77 (19) | O1B—C1B—C5B—C6B | −30.71 (18) |
C2A—C1A—C5A—C6A | 79.96 (16) | C2B—C1B—C5B—C6B | 87.60 (15) |
O1A—C1A—C5A—C9A | 89.32 (17) | O1B—C1B—C5B—C9B | 97.02 (17) |
C2A—C1A—C5A—C9A | −150.95 (13) | C2B—C1B—C5B—C9B | −144.68 (14) |
C13A—O4A—C6A—C7A | 112.63 (15) | C13B—O4B—C6B—C7B | 116.95 (14) |
C13A—O4A—C6A—C5A | 0.33 (17) | C13B—O4B—C6B—C5B | 5.30 (17) |
C4A—C5A—C6A—O4A | −8.27 (16) | C4B—C5B—C6B—O4B | −9.29 (16) |
C1A—C5A—C6A—O4A | −122.93 (14) | C1B—C5B—C6B—O4B | −124.49 (14) |
C9A—C5A—C6A—O4A | 100.68 (13) | C9B—C5B—C6B—O4B | 100.06 (14) |
C4A—C5A—C6A—C7A | −122.87 (13) | C4B—C5B—C6B—C7B | −124.64 (13) |
C1A—C5A—C6A—C7A | 122.47 (14) | C1B—C5B—C6B—C7B | 120.16 (14) |
C9A—C5A—C6A—C7A | −13.92 (16) | C9B—C5B—C6B—C7B | −15.29 (16) |
O4A—C6A—C7A—O11A | 51.43 (18) | O4B—C6B—C7B—O11B | 55.60 (17) |
C5A—C6A—C7A—O11A | 164.96 (14) | C5B—C6B—C7B—O11B | 169.16 (13) |
O4A—C6A—C7A—C8A | −76.37 (15) | O4B—C6B—C7B—C8B | −73.92 (15) |
C5A—C6A—C7A—C8A | 37.16 (16) | C5B—C6B—C7B—C8B | 39.63 (15) |
O11A—C7A—C8A—C9A | −170.92 (14) | O11B—C7B—C8B—C9B | −174.74 (14) |
C6A—C7A—C8A—C9A | −45.49 (15) | C6B—C7B—C8B—C9B | −48.01 (15) |
O11A—C7A—C8A—C17A | 57.9 (2) | O11B—C7B—C8B—C17B | 53.4 (2) |
C6A—C7A—C8A—C17A | −176.69 (14) | C6B—C7B—C8B—C17B | −179.89 (13) |
C7A—C8A—C9A—C10A | −92.30 (15) | C7B—C8B—C9B—C10B | −91.47 (15) |
C17A—C8A—C9A—C10A | 36.7 (2) | C17B—C8B—C9B—C10B | 37.9 (2) |
C7A—C8A—C9A—C12A | 145.94 (13) | C7B—C8B—C9B—C12B | 146.83 (13) |
C17A—C8A—C9A—C12A | −85.07 (17) | C17B—C8B—C9B—C12B | −83.82 (18) |
C7A—C8A—C9A—C5A | 36.04 (14) | C7B—C8B—C9B—C5B | 37.28 (14) |
C17A—C8A—C9A—C5A | 165.03 (14) | C17B—C8B—C9B—C5B | 166.63 (13) |
C4A—C5A—C9A—C10A | −133.24 (13) | C4B—C5B—C9B—C10B | −132.54 (14) |
C6A—C5A—C9A—C10A | 116.60 (14) | C6B—C5B—C9B—C10B | 117.31 (14) |
C1A—C5A—C9A—C10A | −15.8 (2) | C1B—C5B—C9B—C10B | −13.0 (2) |
C4A—C5A—C9A—C12A | −24.43 (15) | C4B—C5B—C9B—C12B | −23.63 (15) |
C6A—C5A—C9A—C12A | −134.59 (13) | C6B—C5B—C9B—C12B | −133.78 (13) |
C1A—C5A—C9A—C12A | 93.04 (16) | C1B—C5B—C9B—C12B | 95.89 (16) |
C4A—C5A—C9A—C8A | 96.00 (13) | C4B—C5B—C9B—C8B | 95.97 (14) |
C6A—C5A—C9A—C8A | −14.16 (15) | C6B—C5B—C9B—C8B | −14.18 (15) |
C1A—C5A—C9A—C8A | −146.53 (14) | C1B—C5B—C9B—C8B | −144.51 (14) |
C12A—C9A—C10A—O5A | −153.96 (13) | C12B—C9B—C10B—O5B | −154.98 (13) |
C8A—C9A—C10A—O5A | 77.56 (18) | C8B—C9B—C10B—O5B | 76.99 (17) |
C5A—C9A—C10A—O5A | −45.82 (18) | C5B—C9B—C10B—O5B | −46.64 (18) |
C12A—C9A—C10A—C11A | −29.85 (15) | C12B—C9B—C10B—C11B | −31.09 (15) |
C8A—C9A—C10A—C11A | −158.33 (13) | C8B—C9B—C10B—C11B | −159.13 (13) |
C5A—C9A—C10A—C11A | 78.29 (15) | C5B—C9B—C10B—C11B | 77.25 (16) |
C12A—O7A—C11A—O6A | 174.33 (16) | C12B—O7B—C11B—O6B | 173.99 (15) |
C12A—O7A—C11A—C10A | −6.51 (17) | C12B—O7B—C11B—C10B | −6.06 (17) |
O5A—C10A—C11A—O6A | −32.9 (2) | O5B—C10B—C11B—O6B | −31.7 (2) |
C9A—C10A—C11A—O6A | −157.15 (17) | C9B—C10B—C11B—O6B | −155.94 (17) |
O5A—C10A—C11A—O7A | 148.00 (14) | O5B—C10B—C11B—O7B | 148.36 (13) |
C9A—C10A—C11A—O7A | 23.76 (16) | C9B—C10B—C11B—O7B | 24.11 (16) |
C4A—O3A—C12A—O7A | 99.00 (14) | C4B—O3B—C12B—O7B | 94.98 (14) |
C4A—O3A—C12A—C9A | −15.34 (17) | C4B—O3B—C12B—C9B | −19.36 (17) |
C11A—O7A—C12A—O3A | −130.56 (13) | C11B—O7B—C12B—O3B | −131.72 (13) |
C11A—O7A—C12A—C9A | −13.28 (16) | C11B—O7B—C12B—C9B | −14.61 (16) |
C10A—C9A—C12A—O3A | 143.27 (13) | C10B—C9B—C12B—O3B | 145.27 (13) |
C8A—C9A—C12A—O3A | −86.62 (16) | C8B—C9B—C12B—O3B | −84.21 (16) |
C5A—C9A—C12A—O3A | 25.12 (16) | C5B—C9B—C12B—O3B | 26.92 (16) |
C10A—C9A—C12A—O7A | 26.92 (15) | C10B—C9B—C12B—O7B | 28.47 (15) |
C8A—C9A—C12A—O7A | 157.03 (13) | C8B—C9B—C12B—O7B | 158.99 (12) |
C5A—C9A—C12A—O7A | −91.23 (13) | C5B—C9B—C12B—O7B | −89.88 (13) |
C6A—O4A—C13A—O8A | −170.71 (15) | C6B—O4B—C13B—O8B | −177.69 (16) |
C6A—O4A—C13A—C4A | 7.94 (18) | C6B—O4B—C13B—C4B | 1.15 (18) |
O3A—C4A—C13A—O8A | 49.2 (2) | O3B—C4B—C13B—O8B | 55.5 (2) |
C5A—C4A—C13A—O8A | 165.76 (16) | C5B—C4B—C13B—O8B | 171.69 (17) |
C3A—C4A—C13A—O8A | −78.8 (2) | C3B—C4B—C13B—O8B | −71.5 (2) |
O3A—C4A—C13A—O4A | −129.40 (13) | O3B—C4B—C13B—O4B | −123.30 (14) |
C5A—C4A—C13A—O4A | −12.80 (17) | C5B—C4B—C13B—O4B | −7.07 (18) |
C3A—C4A—C13A—O4A | 102.66 (15) | C3B—C4B—C13B—O4B | 109.78 (15) |
O2A—C3A—C14A—C15A | −83.24 (16) | O2B—C3B—C14B—C15B | −84.36 (17) |
C2A—C3A—C14A—C15A | 32.40 (15) | C2B—C3B—C14B—C15B | 30.85 (15) |
C4A—C3A—C14A—C15A | 143.40 (14) | C4B—C3B—C14B—C15B | 141.89 (14) |
O2A—C3A—C14A—C16A | 41.5 (2) | O2B—C3B—C14B—C16B | 41.4 (2) |
C2A—C3A—C14A—C16A | 157.14 (15) | C2B—C3B—C14B—C16B | 156.58 (16) |
C4A—C3A—C14A—C16A | −91.86 (18) | C4B—C3B—C14B—C16B | −92.38 (19) |
C2A—O9A—C15A—O10A | −175.77 (17) | C2B—O9B—C15B—O10B | −178.39 (17) |
C2A—O9A—C15A—C14A | 3.89 (19) | C2B—O9B—C15B—C14B | 2.70 (19) |
C16A—C14A—C15A—O10A | 28.5 (3) | C16B—C14B—C15B—O10B | 30.4 (3) |
C3A—C14A—C15A—O10A | 155.55 (19) | C3B—C14B—C15B—O10B | 158.99 (19) |
C16A—C14A—C15A—O9A | −151.13 (16) | C16B—C14B—C15B—O9B | −150.75 (16) |
C3A—C14A—C15A—O9A | −24.07 (18) | C3B—C14B—C15B—O9B | −22.19 (18) |
C7A—C8A—C17A—C19A | −71.80 (19) | C7B—C8B—C17B—C20B | 171.23 (14) |
C9A—C8A—C17A—C19A | 166.55 (15) | C9B—C8B—C17B—C20B | 49.8 (2) |
C7A—C8A—C17A—C18A | 46.5 (2) | C7B—C8B—C17B—C18B | 47.5 (2) |
C9A—C8A—C17A—C18A | −75.11 (19) | C9B—C8B—C17B—C18B | −74.01 (19) |
C7A—C8A—C17A—C20A | 172.26 (14) | C7B—C8B—C17B—C19B | −72.86 (18) |
C9A—C8A—C17A—C20A | 50.6 (2) | C9B—C8B—C17B—C19B | 165.67 (14) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1HA···O5A | 0.84 | 2.04 | 2.749 (2) | 142 |
O1A—H1HA···O4Ai | 0.84 | 2.58 | 3.141 (2) | 126 |
O2A—H2HA···O1Wii | 0.84 | 1.99 | 2.809 (2) | 164 |
O5A—H5HA···O3W | 0.84 | 2.09 | 2.839 (3) | 148 |
O5A—H5HA···O3W′ | 0.84 | 1.84 | 2.664 (3) | 169 |
O11A—H11A···O1Aiii | 0.84 | 2.29 | 2.991 (2) | 141 |
O1B—H1HB···O5B | 0.84 | 2.30 | 2.911 (2) | 131 |
O1B—H1HB···O8Biv | 0.84 | 2.41 | 3.052 (2) | 133 |
O1B—H1HB···O4Biv | 0.84 | 2.41 | 2.901 (2) | 118 |
O2B—H2HB···O10Aii | 0.84 | 2.12 | 2.924 (2) | 161 |
O5B—H5HB···O2Wiv | 0.84 | 1.98 | 2.786 (3) | 162 |
O5B—H5HB···O2W′iv | 0.84 | 2.07 | 2.821 (8) | 149 |
O11B—H11B···O9Bv | 0.84 | 2.37 | 2.943 (2) | 126 |
Symmetry codes: (i) −x, y+1/2, −z+1; (ii) −x+1, y−1/2, −z+1; (iii) −x, y−1/2, −z+1; (iv) −x+1, y+1/2, −z; (v) −x+1, y−1/2, −z. |
(IV) (1
S,2
R,3
S,3aS,4
R,6aR,7aR,7bR,8
S,10aS,11aS)
3-(1,1-dimethylethyl) hexahydro-2,4,7
b-trihydroxy-8-methyl-9
H-1,7a-(epoxymethano)-1H,
6aH-cyclopenta[
c]furo[2,3-
b]furo[3',2':3,4]cyclopenta[1,2-
d] furan-5,9,12(4
H)-trione dihydrate
top
Crystal data top
C20H24O10·2H2O | Dx = 1.518 Mg m−3 |
Mr = 460.42 | Melting point: 563 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.403 (2) Å | Cell parameters from 14293 reflections |
b = 12.950 (3) Å | θ = 2.8–27.9° |
c = 13.646 (3) Å | µ = 0.13 mm−1 |
V = 2015.0 (6) Å3 | T = 120 K |
Z = 4 | Fragment, colorless |
F(000) = 976 | 0.25 × 0.22 × 0.17 mm |
Data collection top
KappaCCD (with Oxford Cryosystems Cryostream cooler) diffractometer | 2586 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 27.9°, θmin = 2.8° |
ω scans with κ offsets | h = −14→15 |
14293 measured reflections | k = −16→17 |
2694 independent reflections | l = −17→17 |
Refinement top
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)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.074 | w = 1/[σ2(Fo2) + (0.0386P)2 + 0.6511P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2694 reflections | Δρmax = 0.26 e Å−3 |
309 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.013 (3) |
Crystal data top
C20H24O10·2H2O | V = 2015.0 (6) Å3 |
Mr = 460.42 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.403 (2) Å | µ = 0.13 mm−1 |
b = 12.950 (3) Å | T = 120 K |
c = 13.646 (3) Å | 0.25 × 0.22 × 0.17 mm |
Data collection top
KappaCCD (with Oxford Cryosystems Cryostream cooler) diffractometer | 2586 reflections with I > 2σ(I) |
14293 measured reflections | Rint = 0.019 |
2694 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.074 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.26 e Å−3 |
2694 reflections | Δρmin = −0.17 e Å−3 |
309 parameters | |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
O2 | 0.89516 (11) | 0.43124 (9) | 0.08845 (9) | 0.0162 (3) | |
H2O | 0.9031 | 0.4894 | 0.0620 | 0.024* | |
O3 | 0.63959 (10) | 0.55267 (9) | 0.18044 (9) | 0.0145 (2) | |
O4 | 0.63682 (11) | 0.36463 (9) | 0.00180 (8) | 0.0181 (3) | |
O5 | 0.44990 (12) | 0.27533 (9) | 0.31404 (9) | 0.0190 (3) | |
H5O | 0.4012 | 0.2569 | 0.3568 | 0.029* | |
O6 | 0.53218 (12) | 0.42106 (10) | 0.46168 (9) | 0.0203 (3) | |
O7 | 0.55683 (11) | 0.53109 (9) | 0.33608 (8) | 0.0172 (3) | |
O8 | 0.70092 (12) | 0.52541 (10) | −0.02604 (9) | 0.0194 (3) | |
O9 | 0.90598 (11) | 0.33764 (10) | 0.29614 (9) | 0.0191 (3) | |
O10 | 1.02699 (12) | 0.45612 (12) | 0.35842 (10) | 0.0252 (3) | |
O11 | 0.41869 (13) | 0.27086 (10) | −0.01610 (9) | 0.0225 (3) | |
H11O | 0.4234 | 0.2065 | −0.0228 | 0.034* | |
C1 | 0.69230 (15) | 0.31630 (13) | 0.25775 (12) | 0.0160 (3) | |
H1A | 0.6809 | 0.3494 | 0.3225 | 0.019* | |
H1B | 0.6738 | 0.2418 | 0.2631 | 0.019* | |
C2 | 0.81734 (15) | 0.33285 (13) | 0.22017 (12) | 0.0160 (3) | |
H2 | 0.8379 | 0.2780 | 0.1716 | 0.019* | |
C3 | 0.81882 (14) | 0.43986 (13) | 0.17012 (11) | 0.0137 (3) | |
C4 | 0.68881 (14) | 0.45976 (12) | 0.14137 (11) | 0.0131 (3) | |
C5 | 0.61617 (15) | 0.36872 (12) | 0.17859 (12) | 0.0136 (3) | |
C6 | 0.59242 (15) | 0.30448 (13) | 0.08526 (12) | 0.0161 (3) | |
H6 | 0.6290 | 0.2344 | 0.0889 | 0.019* | |
C7 | 0.45905 (16) | 0.29877 (13) | 0.07781 (12) | 0.0168 (3) | |
H7 | 0.4297 | 0.2471 | 0.1264 | 0.020* | |
C8 | 0.41981 (15) | 0.40776 (13) | 0.11068 (13) | 0.0151 (3) | |
H8 | 0.4523 | 0.4573 | 0.0615 | 0.018* | |
C9 | 0.49548 (14) | 0.42006 (12) | 0.20512 (12) | 0.0136 (3) | |
C10 | 0.44483 (15) | 0.38219 (12) | 0.30251 (12) | 0.0153 (3) | |
H10 | 0.3610 | 0.4044 | 0.3067 | 0.018* | |
C11 | 0.51543 (15) | 0.44340 (13) | 0.37697 (12) | 0.0163 (3) | |
C12 | 0.53437 (15) | 0.53106 (12) | 0.22918 (12) | 0.0144 (3) | |
H12 | 0.4721 | 0.5821 | 0.2114 | 0.017* | |
C13 | 0.67654 (14) | 0.45726 (13) | 0.03025 (12) | 0.0154 (3) | |
C14 | 0.86641 (15) | 0.51005 (13) | 0.25073 (12) | 0.0161 (3) | |
H14 | 0.7989 | 0.5280 | 0.2943 | 0.019* | |
C15 | 0.94412 (15) | 0.43648 (14) | 0.30749 (12) | 0.0186 (3) | |
C16 | 0.92400 (16) | 0.61125 (14) | 0.22032 (14) | 0.0209 (4) | |
H16A | 0.9571 | 0.6453 | 0.2782 | 0.031* | |
H16B | 0.8653 | 0.6564 | 0.1901 | 0.031* | |
H16C | 0.9867 | 0.5971 | 0.1731 | 0.031* | |
C17 | 0.28463 (15) | 0.42727 (13) | 0.11447 (13) | 0.0191 (4) | |
C18 | 0.21603 (16) | 0.33658 (15) | 0.15828 (15) | 0.0246 (4) | |
H18A | 0.2423 | 0.3244 | 0.2257 | 0.037* | |
H18B | 0.2298 | 0.2745 | 0.1189 | 0.037* | |
H18C | 0.1321 | 0.3529 | 0.1583 | 0.037* | |
C19 | 0.24266 (16) | 0.44408 (15) | 0.00800 (14) | 0.0247 (4) | |
H19A | 0.1569 | 0.4491 | 0.0069 | 0.037* | |
H19B | 0.2677 | 0.3857 | −0.0327 | 0.037* | |
H19C | 0.2767 | 0.5081 | −0.0177 | 0.037* | |
C20 | 0.25540 (16) | 0.52809 (14) | 0.16890 (15) | 0.0245 (4) | |
H20A | 0.3020 | 0.5847 | 0.1415 | 0.037* | |
H20B | 0.2738 | 0.5201 | 0.2386 | 0.037* | |
H20C | 0.1718 | 0.5436 | 0.1612 | 0.037* | |
O1W | 0.81086 (15) | 0.26008 (11) | 0.53321 (12) | 0.0322 (3) | |
H1W | 0.731 (3) | 0.233 (2) | 0.521 (2) | 0.048* | |
H2W | 0.812 (3) | 0.324 (2) | 0.514 (2) | 0.048* | |
O2W | 0.58843 (14) | 0.18812 (13) | 0.49780 (13) | 0.0344 (4) | |
H3W | 0.553 (3) | 0.152 (2) | 0.552 (2) | 0.052* | |
H4W | 0.541 (3) | 0.234 (3) | 0.490 (2) | 0.052* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O2 | 0.0187 (6) | 0.0163 (5) | 0.0135 (6) | 0.0022 (5) | 0.0050 (5) | 0.0002 (5) |
O3 | 0.0141 (5) | 0.0117 (5) | 0.0177 (6) | 0.0004 (4) | 0.0023 (5) | −0.0006 (4) |
O4 | 0.0233 (6) | 0.0178 (6) | 0.0133 (5) | −0.0006 (5) | 0.0017 (5) | −0.0021 (5) |
O5 | 0.0237 (6) | 0.0144 (5) | 0.0190 (6) | −0.0039 (5) | 0.0039 (5) | 0.0012 (5) |
O6 | 0.0238 (6) | 0.0225 (6) | 0.0147 (6) | −0.0024 (5) | 0.0003 (5) | −0.0019 (5) |
O7 | 0.0217 (6) | 0.0160 (5) | 0.0139 (5) | −0.0045 (5) | 0.0005 (5) | −0.0032 (4) |
O8 | 0.0225 (6) | 0.0210 (6) | 0.0145 (5) | −0.0008 (5) | 0.0002 (5) | 0.0027 (5) |
O9 | 0.0178 (6) | 0.0217 (6) | 0.0179 (6) | 0.0024 (5) | −0.0030 (5) | 0.0040 (5) |
O10 | 0.0196 (6) | 0.0337 (7) | 0.0222 (6) | 0.0009 (6) | −0.0063 (5) | 0.0010 (6) |
O11 | 0.0319 (7) | 0.0174 (6) | 0.0183 (6) | −0.0011 (5) | −0.0077 (6) | −0.0057 (5) |
C1 | 0.0181 (8) | 0.0147 (7) | 0.0153 (7) | 0.0015 (6) | 0.0005 (6) | 0.0020 (6) |
C2 | 0.0174 (7) | 0.0158 (7) | 0.0147 (7) | 0.0024 (6) | −0.0016 (7) | 0.0020 (6) |
C3 | 0.0159 (7) | 0.0147 (7) | 0.0104 (7) | 0.0013 (6) | 0.0017 (6) | 0.0009 (6) |
C4 | 0.0163 (7) | 0.0119 (7) | 0.0110 (7) | 0.0015 (6) | −0.0007 (6) | −0.0007 (6) |
C5 | 0.0159 (7) | 0.0120 (7) | 0.0128 (7) | 0.0013 (6) | −0.0004 (6) | −0.0004 (6) |
C6 | 0.0205 (8) | 0.0135 (7) | 0.0143 (7) | 0.0009 (6) | −0.0001 (7) | −0.0015 (6) |
C7 | 0.0207 (8) | 0.0148 (7) | 0.0149 (7) | −0.0010 (6) | −0.0030 (7) | −0.0015 (6) |
C8 | 0.0166 (7) | 0.0142 (7) | 0.0146 (7) | −0.0005 (6) | −0.0028 (6) | −0.0006 (6) |
C9 | 0.0148 (7) | 0.0121 (7) | 0.0138 (7) | −0.0002 (6) | −0.0005 (6) | −0.0010 (6) |
C10 | 0.0174 (7) | 0.0143 (7) | 0.0143 (7) | −0.0009 (6) | 0.0008 (7) | −0.0009 (6) |
C11 | 0.0159 (7) | 0.0170 (7) | 0.0159 (8) | 0.0002 (6) | 0.0028 (6) | −0.0031 (6) |
C12 | 0.0150 (7) | 0.0150 (7) | 0.0131 (7) | −0.0005 (6) | −0.0003 (6) | −0.0016 (6) |
C13 | 0.0140 (7) | 0.0191 (8) | 0.0131 (7) | 0.0026 (6) | −0.0007 (6) | −0.0026 (6) |
C14 | 0.0147 (7) | 0.0208 (8) | 0.0129 (7) | 0.0014 (6) | −0.0008 (6) | −0.0020 (6) |
C15 | 0.0166 (8) | 0.0257 (8) | 0.0135 (7) | 0.0031 (7) | 0.0019 (6) | −0.0003 (7) |
C16 | 0.0211 (8) | 0.0186 (8) | 0.0230 (9) | −0.0026 (7) | −0.0013 (7) | −0.0028 (7) |
C17 | 0.0158 (7) | 0.0186 (8) | 0.0228 (9) | 0.0002 (7) | −0.0023 (7) | −0.0023 (7) |
C18 | 0.0183 (8) | 0.0264 (9) | 0.0292 (9) | −0.0066 (7) | −0.0005 (8) | −0.0013 (8) |
C19 | 0.0207 (8) | 0.0266 (9) | 0.0266 (9) | 0.0000 (8) | −0.0087 (8) | 0.0005 (8) |
C20 | 0.0174 (8) | 0.0240 (9) | 0.0322 (10) | 0.0032 (7) | −0.0021 (8) | −0.0055 (8) |
O1W | 0.0398 (8) | 0.0215 (7) | 0.0353 (8) | −0.0014 (6) | −0.0159 (7) | 0.0042 (6) |
O2W | 0.0295 (7) | 0.0339 (8) | 0.0399 (9) | 0.0050 (7) | 0.0022 (7) | 0.0138 (7) |
Geometric parameters (Å, º) top
O2—C3 | 1.419 (2) | C7—H7 | 1.0000 |
O2—H2O | 0.8400 | C8—C9 | 1.559 (2) |
O3—C12 | 1.400 (2) | C8—C17 | 1.563 (2) |
O3—C4 | 1.431 (2) | C8—H8 | 1.0000 |
O4—C13 | 1.340 (2) | C9—C10 | 1.530 (2) |
O4—C6 | 1.470 (2) | C9—C12 | 1.540 (2) |
O5—C10 | 1.394 (2) | C10—C11 | 1.519 (2) |
O5—H5O | 0.8400 | C10—H10 | 1.0000 |
O6—C11 | 1.207 (2) | C12—H12 | 1.0000 |
O7—C11 | 1.350 (2) | C14—C15 | 1.514 (2) |
O7—C12 | 1.481 (2) | C14—C16 | 1.523 (2) |
O8—C13 | 1.203 (2) | C14—H14 | 1.0000 |
O9—C15 | 1.361 (2) | C16—H16A | 0.9800 |
O9—C2 | 1.449 (2) | C16—H16B | 0.9800 |
O10—C15 | 1.200 (2) | C16—H16C | 0.9800 |
O11—C7 | 1.409 (2) | C17—C18 | 1.533 (3) |
O11—H11O | 0.8400 | C17—C20 | 1.539 (2) |
C1—C2 | 1.530 (2) | C17—C19 | 1.545 (2) |
C1—C5 | 1.543 (2) | C18—H18A | 0.9800 |
C1—H1A | 0.9900 | C18—H18B | 0.9800 |
C1—H1B | 0.9900 | C18—H18C | 0.9800 |
C2—C3 | 1.545 (2) | C19—H19A | 0.9800 |
C2—H2 | 1.0000 | C19—H19B | 0.9800 |
C3—C14 | 1.527 (2) | C19—H19C | 0.9800 |
C3—C4 | 1.555 (2) | C20—H20A | 0.9800 |
C4—C13 | 1.523 (2) | C20—H20B | 0.9800 |
C4—C5 | 1.528 (2) | C20—H20C | 0.9800 |
C5—C6 | 1.545 (2) | O1W—H1W | 0.98 (3) |
C5—C9 | 1.571 (2) | O1W—H2W | 0.87 (3) |
C6—C7 | 1.526 (2) | O2W—H3W | 0.96 (3) |
C6—H6 | 1.0000 | O2W—H4W | 0.81 (3) |
C7—C8 | 1.547 (2) | | |
| | | |
C3—O2—H2O | 109.5 | C8—C9—C5 | 104.54 (13) |
C12—O3—C4 | 110.19 (12) | O5—C10—C11 | 114.86 (14) |
C13—O4—C6 | 111.49 (12) | O5—C10—C9 | 113.61 (13) |
C10—O5—H5O | 109.5 | C11—C10—C9 | 102.34 (13) |
C11—O7—C12 | 110.26 (12) | O5—C10—H10 | 108.6 |
C15—O9—C2 | 110.16 (13) | C11—C10—H10 | 108.6 |
C7—O11—H11O | 109.5 | C9—C10—H10 | 108.6 |
C2—C1—C5 | 103.18 (13) | O6—C11—O7 | 122.82 (16) |
C2—C1—H1A | 111.1 | O6—C11—C10 | 126.82 (16) |
C5—C1—H1A | 111.1 | O7—C11—C10 | 110.34 (14) |
C2—C1—H1B | 111.1 | O3—C12—O7 | 108.64 (13) |
C5—C1—H1B | 111.1 | O3—C12—C9 | 109.40 (13) |
H1A—C1—H1B | 109.1 | O7—C12—C9 | 105.07 (13) |
O9—C2—C1 | 114.59 (13) | O3—C12—H12 | 111.2 |
O9—C2—C3 | 105.68 (13) | O7—C12—H12 | 111.2 |
C1—C2—C3 | 106.49 (13) | C9—C12—H12 | 111.2 |
O9—C2—H2 | 110.0 | O8—C13—O4 | 123.38 (15) |
C1—C2—H2 | 110.0 | O8—C13—C4 | 126.80 (16) |
C3—C2—H2 | 110.0 | O4—C13—C4 | 109.79 (14) |
O2—C3—C14 | 113.25 (13) | C15—C14—C16 | 115.36 (15) |
O2—C3—C2 | 106.47 (13) | C15—C14—C3 | 101.65 (13) |
C14—C3—C2 | 102.67 (13) | C16—C14—C3 | 117.97 (14) |
O2—C3—C4 | 113.57 (13) | C15—C14—H14 | 107.1 |
C14—C3—C4 | 114.96 (13) | C16—C14—H14 | 107.1 |
C2—C3—C4 | 104.46 (13) | C3—C14—H14 | 107.1 |
O3—C4—C13 | 110.66 (13) | O10—C15—O9 | 121.12 (17) |
O3—C4—C5 | 108.20 (12) | O10—C15—C14 | 128.58 (17) |
C13—C4—C5 | 105.35 (13) | O9—C15—C14 | 110.28 (14) |
O3—C4—C3 | 114.79 (13) | C14—C16—H16A | 109.5 |
C13—C4—C3 | 109.58 (13) | C14—C16—H16B | 109.5 |
C5—C4—C3 | 107.77 (13) | H16A—C16—H16B | 109.5 |
C4—C5—C1 | 105.50 (13) | C14—C16—H16C | 109.5 |
C4—C5—C6 | 103.68 (13) | H16A—C16—H16C | 109.5 |
C1—C5—C6 | 116.02 (13) | H16B—C16—H16C | 109.5 |
C4—C5—C9 | 103.01 (12) | C18—C17—C20 | 110.57 (15) |
C1—C5—C9 | 121.18 (13) | C18—C17—C19 | 108.47 (15) |
C6—C5—C9 | 105.33 (13) | C20—C17—C19 | 105.50 (15) |
O4—C6—C7 | 108.50 (14) | C18—C17—C8 | 113.10 (15) |
O4—C6—C5 | 107.04 (13) | C20—C17—C8 | 111.52 (14) |
C7—C6—C5 | 104.81 (13) | C19—C17—C8 | 107.29 (15) |
O4—C6—H6 | 112.0 | C17—C18—H18A | 109.5 |
C7—C6—H6 | 112.0 | C17—C18—H18B | 109.5 |
C5—C6—H6 | 112.0 | H18A—C18—H18B | 109.5 |
O11—C7—C6 | 113.49 (15) | C17—C18—H18C | 109.5 |
O11—C7—C8 | 113.79 (14) | H18A—C18—H18C | 109.5 |
C6—C7—C8 | 102.98 (14) | H18B—C18—H18C | 109.5 |
O11—C7—H7 | 108.8 | C17—C19—H19A | 109.5 |
C6—C7—H7 | 108.8 | C17—C19—H19B | 109.5 |
C8—C7—H7 | 108.8 | H19A—C19—H19B | 109.5 |
C7—C8—C9 | 99.95 (13) | C17—C19—H19C | 109.5 |
C7—C8—C17 | 116.25 (14) | H19A—C19—H19C | 109.5 |
C9—C8—C17 | 120.14 (15) | H19B—C19—H19C | 109.5 |
C7—C8—H8 | 106.5 | C17—C20—H20A | 109.5 |
C9—C8—H8 | 106.5 | C17—C20—H20B | 109.5 |
C17—C8—H8 | 106.5 | H20A—C20—H20B | 109.5 |
C10—C9—C12 | 102.87 (13) | C17—C20—H20C | 109.5 |
C10—C9—C8 | 118.45 (14) | H20A—C20—H20C | 109.5 |
C12—C9—C8 | 115.53 (13) | H20B—C20—H20C | 109.5 |
C10—C9—C5 | 113.30 (13) | H1W—O1W—H2W | 107 (3) |
C12—C9—C5 | 101.07 (12) | H3W—O2W—H4W | 100 (3) |
| | | |
C15—O9—C2—C1 | −106.89 (16) | C1—C5—C9—C10 | −19.3 (2) |
C15—O9—C2—C3 | 10.03 (17) | C6—C5—C9—C10 | 114.89 (14) |
C5—C1—C2—O9 | 151.68 (13) | C4—C5—C9—C12 | −27.40 (15) |
C5—C1—C2—C3 | 35.23 (16) | C1—C5—C9—C12 | 90.01 (17) |
O9—C2—C3—O2 | 93.77 (14) | C6—C5—C9—C12 | −135.77 (13) |
C1—C2—C3—O2 | −143.96 (13) | C4—C5—C9—C8 | 92.89 (14) |
O9—C2—C3—C14 | −25.46 (16) | C1—C5—C9—C8 | −149.70 (14) |
C1—C2—C3—C14 | 96.81 (15) | C6—C5—C9—C8 | −15.47 (16) |
O9—C2—C3—C4 | −145.77 (13) | C12—C9—C10—O5 | −153.82 (14) |
C1—C2—C3—C4 | −23.50 (16) | C8—C9—C10—O5 | 77.38 (19) |
C12—O3—C4—C13 | 107.78 (15) | C5—C9—C10—O5 | −45.59 (19) |
C12—O3—C4—C5 | −7.17 (16) | C12—C9—C10—C11 | −29.39 (15) |
C12—O3—C4—C3 | −127.55 (13) | C8—C9—C10—C11 | −158.19 (14) |
O2—C3—C4—O3 | −121.28 (14) | C5—C9—C10—C11 | 78.83 (16) |
C14—C3—C4—O3 | 11.42 (19) | C12—O7—C11—O6 | 173.33 (16) |
C2—C3—C4—O3 | 123.13 (14) | C12—O7—C11—C10 | −8.16 (18) |
O2—C3—C4—C13 | 3.96 (19) | O5—C10—C11—O6 | −33.7 (2) |
C14—C3—C4—C13 | 136.66 (15) | C9—C10—C11—O6 | −157.25 (17) |
C2—C3—C4—C13 | −111.63 (14) | O5—C10—C11—O7 | 147.91 (15) |
O2—C3—C4—C5 | 118.10 (14) | C9—C10—C11—O7 | 24.32 (17) |
C14—C3—C4—C5 | −109.20 (15) | C4—O3—C12—O7 | 102.28 (14) |
C2—C3—C4—C5 | 2.51 (16) | C4—O3—C12—C9 | −11.91 (17) |
O3—C4—C5—C1 | −105.61 (14) | C11—O7—C12—O3 | −128.49 (14) |
C13—C4—C5—C1 | 136.00 (13) | C11—O7—C12—C9 | −11.50 (17) |
C3—C4—C5—C1 | 19.07 (16) | C10—C9—C12—O3 | 142.18 (13) |
O3—C4—C5—C6 | 131.98 (13) | C8—C9—C12—O3 | −87.23 (16) |
C13—C4—C5—C6 | 13.59 (16) | C5—C9—C12—O3 | 24.92 (16) |
C3—C4—C5—C6 | −103.35 (14) | C10—C9—C12—O7 | 25.70 (16) |
O3—C4—C5—C9 | 22.38 (15) | C8—C9—C12—O7 | 156.29 (13) |
C13—C4—C5—C9 | −96.02 (14) | C5—C9—C12—O7 | −91.56 (14) |
C3—C4—C5—C9 | 147.05 (13) | C6—O4—C13—O8 | −168.71 (16) |
C2—C1—C5—C4 | −33.15 (16) | C6—O4—C13—C4 | 13.12 (18) |
C2—C1—C5—C6 | 80.96 (17) | O3—C4—C13—O8 | 48.2 (2) |
C2—C1—C5—C9 | −149.31 (14) | C5—C4—C13—O8 | 164.88 (17) |
C13—O4—C6—C7 | 108.74 (15) | C3—C4—C13—O8 | −79.4 (2) |
C13—O4—C6—C5 | −3.88 (18) | O3—C4—C13—O4 | −133.75 (14) |
C4—C5—C6—O4 | −6.70 (16) | C5—C4—C13—O4 | −17.02 (18) |
C1—C5—C6—O4 | −121.84 (15) | C3—C4—C13—O4 | 98.67 (15) |
C9—C5—C6—O4 | 101.17 (14) | O2—C3—C14—C15 | −84.48 (16) |
C4—C5—C6—C7 | −121.81 (14) | C2—C3—C14—C15 | 29.90 (16) |
C1—C5—C6—C7 | 123.05 (15) | C4—C3—C14—C15 | 142.67 (14) |
C9—C5—C6—C7 | −13.94 (17) | O2—C3—C14—C16 | 42.7 (2) |
O4—C6—C7—O11 | 47.91 (18) | C2—C3—C14—C16 | 157.11 (14) |
C5—C6—C7—O11 | 162.00 (13) | C4—C3—C14—C16 | −90.12 (17) |
O4—C6—C7—C8 | −75.55 (15) | C2—O9—C15—O10 | −171.24 (16) |
C5—C6—C7—C8 | 38.53 (16) | C2—O9—C15—C14 | 10.22 (18) |
O11—C7—C8—C9 | −170.61 (14) | C16—C14—C15—O10 | 26.7 (3) |
C6—C7—C8—C9 | −47.34 (15) | C3—C14—C15—O10 | 155.60 (18) |
O11—C7—C8—C17 | 58.5 (2) | C16—C14—C15—O9 | −154.89 (15) |
C6—C7—C8—C17 | −178.25 (15) | C3—C14—C15—O9 | −26.00 (17) |
C7—C8—C9—C10 | −89.10 (16) | C7—C8—C17—C18 | 42.1 (2) |
C17—C8—C9—C10 | 39.3 (2) | C9—C8—C17—C18 | −78.49 (19) |
C7—C8—C9—C12 | 148.25 (14) | C7—C8—C17—C20 | 167.48 (15) |
C17—C8—C9—C12 | −83.35 (19) | C9—C8—C17—C20 | 46.9 (2) |
C7—C8—C9—C5 | 38.15 (15) | C7—C8—C17—C19 | −77.46 (18) |
C17—C8—C9—C5 | 166.54 (14) | C9—C8—C17—C19 | 161.94 (14) |
C4—C5—C9—C10 | −136.75 (13) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O6i | 0.84 | 1.94 | 2.709 (2) | 152 |
O5—H5O···O1Wii | 0.84 | 1.83 | 2.659 (2) | 167 |
O11—H11O···O2iii | 0.84 | 2.02 | 2.810 (2) | 156 |
O1W—H1W···O2W | 0.98 (3) | 1.76 (3) | 2.745 (2) | 178 (3) |
O1W—H2W···O8iv | 0.87 (3) | 2.03 (3) | 2.896 (2) | 175 (3) |
O2W—H3W···O10ii | 0.96 (3) | 1.89 (3) | 2.798 (2) | 158 (3) |
O2W—H3W···O9ii | 0.96 (3) | 2.67 (3) | 3.514 (2) | 147 (2) |
O2W—H4W···O6 | 0.81 (3) | 2.46 (3) | 3.123 (2) | 140 (3) |
O2W—H4W···O1Wii | 0.81 (3) | 2.64 (3) | 3.263 (2) | 135 (3) |
O2W—H4W···O5 | 0.81 (3) | 2.67 (3) | 3.172 (2) | 122 (3) |
Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) x−1/2, −y+1/2, −z+1; (iii) x−1/2, −y+1/2, −z; (iv) −x+3/2, −y+1, z+1/2. |
Experimental details
| (I) | (III) | (IV) |
Crystal data |
Chemical formula | C20H24O9·H2O | C20H24O11·1.5H2O | C20H24O10·2H2O |
Mr | 426.41 | 467.42 | 460.42 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, P21 | Orthorhombic, P212121 |
Temperature (K) | 120 | 120 | 120 |
a, b, c (Å) | 8.931 (2), 12.338 (2), 17.779 (3) | 7.4945 (15), 12.973 (3), 20.934 (4) | 11.403 (2), 12.950 (3), 13.646 (3) |
α, β, γ (°) | 90, 90, 90 | 90, 91.00 (2), 90 | 90, 90, 90 |
V (Å3) | 1959.2 (6) | 2035.0 (7) | 2015.0 (6) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.12 | 0.13 | 0.13 |
Crystal size (mm) | 0.48 × 0.37 × 0.35 | 0.47 × 0.27 × 0.25 | 0.25 × 0.22 × 0.17 |
|
Data collection |
Diffractometer | KappaCCD (with Oxford Cryosystems Cryostream cooler) diffractometer | KappaCCD (with Oxford Cryosystems Cryostream cooler) diffractometer | KappaCCD (with Oxford Cryosystems Cryostream cooler) diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19931, 4144, 3936 | 22429, 5921, 5752 | 14293, 2694, 2586 |
Rint | 0.017 | 0.019 | 0.019 |
(sin θ/λ)max (Å−1) | 0.770 | 0.695 | 0.658 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.083, 1.06 | 0.031, 0.086, 1.05 | 0.029, 0.074, 1.03 |
No. of reflections | 4144 | 5921 | 2694 |
No. of parameters | 283 | 622 | 309 |
No. of restraints | 0 | 1 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.21 | 0.37, −0.18 | 0.26, −0.17 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O1Wi | 0.84 | 1.89 | 2.694 (2) | 160 |
O5—H5O···O1Wii | 0.84 | 1.93 | 2.764 (2) | 172 |
O1W—H1W···O8 | 0.86 (2) | 1.98 (2) | 2.831 (2) | 175 (2) |
O1W—H2W···O10iii | 0.83 (2) | 1.90 (2) | 2.711 (2) | 169 (2) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) −x+1/2, −y+1, z−1/2. |
Endocyclic torsion angles (°) in ginkgolides A, C, and J hydrates topAtoms | Ginkgolide A | Ginkgolide C | Ginkgolide C | Ginkgolide J |
| | Molecule A | Molecule B | |
Ring A | | | | |
C1-C2-C3-C4 | 27.84 (12) | -32.96 (16) | -29.01 (17) | -23.50 (16) |
C2-C3-C4-C5 | -24.67 (12) | 11.07 (16) | 11.93 (17) | 2.51 (16) |
C3-C4-C5-C1 | 12.57 (12) | 14.59 (16) | 9.08 (17) | 19.07 (16) |
C4-C5-C1-C2 | 4.88 (12) | -34.51 (15) | -26.55 (16) | -33.15 (16) |
C5-C1-C2-C3 | -20.79 (12) | 42.12 (15) | 34.63 (17) | 35.23 (16) |
| | | | |
Ring B | | | | |
C9-C5-C6-C7 | -13.21 (12) | -13.92 (16) | -15.29 (16) | -13.94 (17) |
C5-C6-C7-C8 | 35.47 (12) | 37.16 (16) | 39.63 (15) | 38.53 (16) |
C6-C7-C8-C9 | -43.50 (12) | -45.49 (15) | -48.01 (15) | -47.34 (15) |
C7-C8-C9-C5 | 34.67 (11) | 36.04 (14) | 37.28 (14) | 38.15 (15) |
C8-C9-C5-C6 | -13.49 (11) | -14.16 (15) | -14.18 (15) | -15.47 (16) |
| | | | |
Ring C | | | | |
C12-C9-C10-C11 | -32.36 (11) | -29.85 (15) | -31.09 (15) | -29.39 (15) |
C9-C10-C11-O7 | 29.50 (12) | 23.76 (16) | 24.11 (16) | 24.32 (17) |
C10-C11-O7-C12 | -13.07 (13) | -6.51 (17) | -6.06 (17) | -8.16 (18) |
C11-O7-C12-C9 | -8.61 (12) | -13.28 (16) | -14.61 (16) | -11.50 (17) |
O7-C12-C9-C10 | 25.99 (11) | 26.92 (15) | 28.47 (15) | 25.70 (16) |
| | | | |
Ring D | | | | |
O3-C4-C5-C9 | 16.88 (11) | 17.50 (16) | 14.16 (16) | 22.38 (15) |
C4-C5-C9-C12 | -23.49 (10) | -24.43 (15) | -23.63 (15) | -27.40 (15) |
C5-C9-C12-O3 | 23.62 (11) | 25.12 (16) | 26.92 (16) | 24.92 (16) |
C9-C12-O3-C4 | -14.06 (12) | -15.34 (17) | -19.36 (17) | -11.91 (17) |
C5-C4-O3-C12 | -2.29 (12) | -1.92 (17) | 2.69 (18) | -7.17 (16) |
| | | | |
Ring E | | | | |
C13-C4-C5-C6 | 10.27 (11) | 12.25 (16) | 9.70 (16) | 13.59 (16) |
C4-C5-C6-O4 | -6.06 (12) | -8.27 (16) | -9.29 (16) | -6.70 (16) |
C5-C6-O4-C13 | -1.17 (13) | 0.33 (17) | 5.30 (17) | -3.88 (18) |
C6-O4-C13-C4 | 8.17 (13) | 7.94 (18) | 1.15 (18) | 13.12 (18) |
O4-C13-C4-C5 | -11.80 (13) | -12.80 (17) | -7.07 (18) | -17.02 (18) |
| | | | |
Ring F | | | | |
O9-C2-C3-C14 | 29.98 (11) | -31.97 (15) | -30.72 (16) | -25.46 (16) |
C2-C3-C14-C15 | -24.93 (11) | 32.40 (15) | 30.85 (15) | 29.90 (16) |
C3-C14-C15-O9 | 11.65 (13) | -24.07 (18) | -22.19 (18) | -26.00 (17) |
C14-C15-O9-C2 | 7.87 (13) | 3.89 (19) | 2.70 (19) | 10.22 (18) |
C15-O9-C2-C3 | -23.99 (12) | 18.37 (17) | 18.23 (17) | 10.03 (17) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1HA···O5A | 0.84 | 2.04 | 2.749 (2) | 142.2 |
O1A—H1HA···O4Ai | 0.84 | 2.58 | 3.141 (2) | 125.7 |
O2A—H2HA···O1Wii | 0.84 | 1.99 | 2.809 (2) | 164.1 |
O5A—H5HA···O3W | 0.84 | 2.09 | 2.839 (3) | 147.7 |
O5A—H5HA···O3W' | 0.84 | 1.84 | 2.664 (3) | 168.6 |
O11A—H11A···O1Aiii | 0.84 | 2.29 | 2.991 (2) | 140.7 |
O1B—H1HB···O5B | 0.84 | 2.30 | 2.911 (2) | 130.5 |
O1B—H1HB···O8Biv | 0.84 | 2.41 | 3.052 (2) | 133.3 |
O1B—H1HB···O4Biv | 0.84 | 2.41 | 2.901 (2) | 118.0 |
O2B—H2HB···O10Aii | 0.84 | 2.12 | 2.924 (2) | 160.7 |
O5B—H5HB···O2Wiv | 0.84 | 1.98 | 2.786 (3) | 161.5 |
O5B—H5HB···O2W'iv | 0.84 | 2.07 | 2.821 (8) | 149.4 |
O11B—H11B···O9Bv | 0.84 | 2.37 | 2.943 (2) | 125.6 |
Symmetry codes: (i) −x, y+1/2, −z+1; (ii) −x+1, y−1/2, −z+1; (iii) −x, y−1/2, −z+1; (iv) −x+1, y+1/2, −z; (v) −x+1, y−1/2, −z. |
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O6i | 0.84 | 1.94 | 2.709 (2) | 152 |
O5—H5O···O1Wii | 0.84 | 1.83 | 2.659 (2) | 167 |
O11—H11O···O2iii | 0.84 | 2.02 | 2.810 (2) | 156 |
O1W—H1W···O2W | 0.98 (3) | 1.76 (3) | 2.745 (2) | 178 (3) |
O1W—H2W···O8iv | 0.87 (3) | 2.03 (3) | 2.896 (2) | 175 (3) |
O2W—H3W···O10ii | 0.96 (3) | 1.89 (3) | 2.798 (2) | 158 (3) |
O2W—H3W···O9ii | 0.96 (3) | 2.67 (3) | 3.514 (2) | 147 (2) |
O2W—H4W···O6 | 0.81 (3) | 2.46 (3) | 3.123 (2) | 140 (3) |
O2W—H4W···O1Wii | 0.81 (3) | 2.64 (3) | 3.263 (2) | 135 (3) |
O2W—H4W···O5 | 0.81 (3) | 2.67 (3) | 3.172 (2) | 122 (3) |
Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) x−1/2, −y+1/2, −z+1; (iii) x−1/2, −y+1/2, −z; (iv) −x+3/2, −y+1, z+1/2. |
The highly oxygenated diterpene trilactone-type caged molecules ginkgolide A, B, C and J were isolated from standardized extracts of Ginkgo biloba L. and were characterized by detailed high-field two-dimensional NMR studies. They are the major biochemical markers of Ginkgo biloba, which is considered an important vascular and neurological botanical and displays potent antagonistic activity against platelet-activating factor (PAF, PAF/acether, AGEPC) (Braquet, 1988; Braquet & Godfroid, 1986; Van Beek et al., 1998).
Out of five reported ginkgolides (Roumestand et al., 1989; Van Beek & Lankhorst, 1996; Weinges et al., 1987), the relative stereochemistries of ginkgolide A, B and C were previously determined by X-ray crystallography (Dupont et al., 1986; Sakabe et al., 1967; Sbit et al., 1987) in a study of the monohydrates of (I) and (II), and the ethanol 1.5-hydrate of (III). In order to prove conclusively the configurations of all 11 asymmetric centers of ginkgolide J, (IV), and especially to ascertain how it correlates with other ginkgolides [(I) and (III)], crystal structure determinations were undertaken. Crystallization from undried solvents yielded hydrates, namely ginkgolide A monohydrate (C20H24O9·H2O), ginkgolide C sesquihydrate (C20H24O11·1.5H2O), and ginkgolide J dihydrate (C20H24O10·2H2O), which also allowed direct determination of their comparative caged configurations. The structures reported herein are in agreement with the tentative assignments using NMR methods.
Our low-temperature determination of ginkgolide A monohydrate, (I)·H2O, with Mo Kα data confirms the earlier results of Sbit et al. (1987) and represents a substantial improvement in precision over their room-temperature structure. We have also measured room-temperature data with Cu Kα radiation at 296 K, and refinement using 3776 reflections (1439 Friedel pairs) yielded R = 0.028 and a Flack (1983) parameter of -0.02 (12). We have adopted this absolute structure for all three compounds reported herein, and it is consistent with the absolute configuration reported by Sakabe et al. (1967) for the p-bromobenzoate ester at C3. Their absolute configuration, determined from the diethanol solvate, was somewhat in doubt because of a rather high R value (0.190) from visually estimated film data with no absorption correction. Our room-temperature cell dimensions for the monohydrate are a = 8.992 (2), b = 12.438 (2), c = 17.819 (3) Å and V = 1992.9 (6) Å2, based on 25 reflections having 22.8 < θ < 43.1°, measured on an Enraf–Nonius CAD-4 diffractometer. The results of the Cu Kα refinement have been deposited as supplementary data.
Our low-temperature determination of the structure of ginkgolide C as the sesquihydrate, (III)·1.5H2O, represents an increase in precision of a factor of four over that of Sbit et al. (1987) for the sesquihydrate monoethanol solvate at room temperature. For their structure, as well as ours, Z' = 2. In both independent molecules of our structure, there is an intramolecular hydrogen bond between OH groups O1 and O5, with O1 as donor. The conformations of all the OH groups agree well between the A and B molecules, despite the differences in intermolecular hydrogen bonding (Table 3). In the structure of Sbit et al., the intramolecular hydrogen bond is reported to have O5 as the donor and O1 as the acceptor, although they were unable to locate all hydroxy H atoms. In the present structure, there are three independent water molecules, two of which are disordered into pairs of sites. O2W occupies sites of occupancy 0.72 (3) and 0.28 (3), separated by 0.641 (17) Å, while O3W occupies sites of equal occupancy [0.494 (10) and 0.506 (10)], separated by 0.849 (4) Å. All five water sites accept hydrogen bonds from ginkgolide C molecules; hydrogen bonding between water molecules is less unambiguous, because of the inability to locate the water H atoms.
The structure of the trihydroxy compound ginkgolide J, (IV), for which no crystal structure has been previously reported, is shown in Fig. 3 as the dihydrate, i.e. (IV)·2H2O. The configurations of all the asymmetric centers in the basic ginkgolide skeleton are shown to agree with those of ginkgolides A, B, and C. The OH groups have been confirmed to lie at C3, C7, and C10, with the same configurations as the OH groups at those positions in ginkgolide C.
The conformations of the six five-membered rings (A—F in the Scheme) of the ginkgolide skeleton have been discussed by Dupont et al. (1986) and Sbit et al. (1987). They found that the skeleton was fairly rigid, with the conformations of rings B—E differing little in ginkgolides A, B, and C, while those of the A and F rings of ginkgolide A differed from the pattern. They suggested that the anomalous A– and F-ring conformations of ginkgolide A are related to hydrogen bonding, as ginkgolide A carries no OH group at C1, while ginkgolides B and C do. Our results for the endocyclic torsion angles of the five-membered rings are given in Table 1. We also note little variation (11° or less) across the entire spectrum of torsion angles, except for the A and F rings of ginkgolide A. Notably, the conformations of the A and F rings in ginkgolide J, which, like ginkgolide A, carries no OH group at C1, fits the normal pattern.
The hydrogen bonding to the two independent molecules in ginkgolide C sesquihydrate differs (Table 3), which allows direct observation of the conformational differences caused by differences in intermolecular hydrogen bonding. The differences in torsion angles (Table 1) are small, with the overall mean deviation among 30 pairs of torsion angles only 2.7°. The A ring shows the largest deviation, with a mean of 5.1°, with the other rings having mean deviations as follows: B 1.6, C 1.0, D 2.9, E 4.1, F 1.2°.