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The absolute configurations of spongia-13(16),14-dien-3-one [systematic name: (3bR,5aR,9aR,9bR)-3b,6,6,9a-tetra­methyl-4,5,5a,6,8,9,9a,9b,10,11-deca­hydro­phenanthro[1,2-c]furan-7(3bH)-one], C20H28O2, (I), epispongiadiol [systematic name: (3bR,5aR,6S,7R,9aR,9bR)-7-hydr­oxy-6-hydroxy­methyl-3b,6,9a-trimethyl-3b,5,5a,6,7,9,9a,9b,10,11-deca­hydro­phenanthro[1,2-c]furan-8(4H)-one], C20H28O4, (II), and spongiadiol [systematic name: (3bR,5aR,6S,7S,9aR,9bR)-7-hydr­oxy-6-hy­droxy­methyl-3b,6,9a-trimethyl-3b,5,5a,6,7,9,9a,9b,10,11-deca­hydro­phenanthro[1,2-c]furan-8(4H)-one], C20H28O4, (III), were assigned by analysis of anomalous dispersion data collected at 130 K with Cu K[alpha] radiation. Compounds (II) and (III) are epimers. The equatorial 3-hydroxyl group on the cyclo­hexa­none ring (A) of (II) is syn with respect to the 4-hydroxy­methyl group, leading to a chair conformation. In contrast, isomer (III), where the 3-hydroxyl group is anti to the 4-hydroxy­methyl group, is conformationally disordered between a major chair conformer where the OH group is axial and a minor boat conformer where it is equatorial. In compound (I), a carbonyl group is present at position 3 and ring A adopts a distorted-boat conformation.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109008816/sq3189sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109008816/sq3189Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109008816/sq3189IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109008816/sq3189IIIsup4.hkl
Contains datablock III

CCDC references: 730106; 730107; 730108

Comment top

Spongian diterpenoids [e.g. compounds (I)–(V)] are a group of tetracyclic compounds first isolated from Great Barrier Reef marine sponges of the genus Spongia (family Spongiidae, order Dictyoceratida) by Kazlauskas et al. (1979). Since then there have been a number of other reports of spongian diterpenes isolated from sponges of the orders Dictyoceratida and Dendroceratida (Keyzers et al., 2006). Spongivorous molluscs belonging to the species Glossodoris have also yielded spongian diterpenes (Dilip de Silva et al., 1982; Fontana et al., 1997; Somerville et al., 2006). In this paper, we report the crystal structures and absolute configurations of (+)-spongia-13 (16),14-dien-3-one, (I) (Somerville et al., 2006), (+)-epispongiadiol, (II), and (+)-spongiadiol, (III) (Kazlauskas et al., 1979), isolated from the nudibranch Glossodoris atromarginata. Compounds (I)–(III) are structurally very similar, indeed (II) and (III) are epimers. Notwithstanding this similarity, the three diterpenes exhibit diversity in their solid-state structures, particularly in the conformation of the cyclohexanone ring.

The crystal structure of (I) was determined at 130 K. The compound crystallizes with two independent molecules in the asymmetric unit. The tetracyclic structure of (I) is apparent in Fig. 1, where only one of the two molecules is displayed. A feature is the twisted-boat conformation of the cyclohexanone (A) ring. There are no classical hydrogen bonds in the structure and the six-membered B and C rings adopt their expected chair conformations, while the inflexible furan ring (D) is necessarily planar. The only significant intermolecular contact is a non-classical hydrogen bond donated by a furan H atom to the ketone O atom of an adjacent molecule [C16A—H···O1A(1 + x, y, z) = 2.49(s.u.?) Å]. The structure may be compared with that of 19-acetoxyspongia-13 (16),14-dien-3-one, (IV) (Ponomarenko et al., 2007), which exhibits a chair conformer of ring A. The two compounds only differ in the acetoxy group attached to C19 in (IV), which is absent in (I), yet this translates into a different conformation of ring A. Like (I), compound (IV) has no hydrogen-bond donors, so it appears that the two ring conformations are of very similar energy.

Compound (II) is structurally distinct in that the carbonyl group is at C2 on the cyclohexanone (A) ring while hydroxyl groups appear on atoms C3 and C19. The OH group at C3 is equatorially disposed (Fig. 2) and ring A is in a conventional chair conformation. The hydroxymethyl group donates an intramolecular hydrogen bond to atom O3 (Table 1).

The crystal structure of compound (III) reveals disorder of ring A, comprising a dominant chair conformer (71% occupancy) with the 3-hydroxyl substituent in an axial position (Fig. 3). The minor contribution is a distorted-boat conformer where the hydroxyl group adopts an equatorial position. A superposition of the two conformers is shown in Fig. 4, where the distinct positions of all C atoms within ring A (except those fused with ring B) and their substituents are apparent. The two conformers display different hydrogen-bonding patterns due to the movement of the hydroxyl groups by more than 2.2 Å from one conformation to the other. This compound is most closely related to the acetylated analogue, (V), which exclusively exhibits a boat conformation of ring A (Kazlauskas et al., 1979).

The absolute structures of (I), (II) and (III) were each determined by anomalous dispersion from an entire sphere of Cu Kα data. Apart from the conventional Flack parameter, the absolute structure was confirmed by the Bijvoet analysis of Hooft et al. (2008) implemented within the PLATON program (Spek, 2009). In each case, the P2 parameter was 1.00 for the chosen enantiomorph.

All three spongian diterpenes, (I)–(III), have the same absolute configuration, 5R,8R,9R,10R for (I), 3R,4S,5R,8R,9R,10R for (II) and 3S,4S,5R,8R,9R,10R for (III). The absolute structures of (-)-(IV) (Ponomarenko et al., 2007) and (+)-(V) (Kazlauskas et al., 1979) were assigned on the basis of circular dichroism (CD) data; Mo Kα radiation was used for these crystal structure analyses, which only afforded relative stereochemistry. The absolute configurations of other spongian diterpenes, for example (-)-(VI) (Searle & Molinski, 1994), (+)-(VII) (Fontana et al., 1997) and (-)-(VIII) (Carroll et al., 2008), have been deduced solely by Mosher ester analysis or by CD spectroscopy. So far, all the spongian diterpenes for which absolute configurations have been reported in the literature belong to the same enantiomeric series. This stereochemical uniformity is in contrast with the situation for sponge sesquiterpene metabolites, for which there are numerous reports of enantiomers in the literature, including recent examples from the furanosesquiterpenes (Gaspar et al., 2008) and sesquiterpene quinones (Yong et al., 2008).

The relative configuration of the structurally related chamaetexane A, (IX), was reported from its crystal structure analysis (Barba et al., 1992), but no absolute structure was reported. The pentacyclic sesterstatin epimers, (X) and (XI), are somewhat different, but again their absolute configurations were not determined crystallographically (Pettit et al., 1998).

There has been considerable interest in the synthesis of spongian diterpenes (González et al., 2008). Compound (I) has been previously reported as an intermediate in a diastereoselective synthesis starting from S-(+)-carvone (Arnó et al., 1999). The optical rotation value for the crystallized natural product (I) ([α]D +10.1°, c 0.37 CHCl3) closely matches that of the synthetic intermediate (Arnó et al., 1999; [α]D +11.8°, c 3.8 CHCl3).

The present study provides an important link between the absolute configuration of spongian diterpenes and their CD and optical rotation data, the latter being a somewhat ambiguous method for assigning chirality alone.

Experimental top

Compounds (I)–(III) were obtained from an acetone extract from the nudibranch G. atromarginata collected from the Inner Gneerings Reef, Mooloolaba, Queensland, Australia. Twenty three specimens (total mass?) of G. atromarginata were crushed and sonicated with Me2CO (Volume?). The solvent was then evaporated under reduced pressure to give an aqueous residue, which was partitioned with Et2O (Volume?). The organic layer was dried with anhydrous MgSO4 and concentrated under reduced pressure to give a dark-yellow oil (70 mg). The organic extract was subsequently purified by reverse-phase high-performance liquid chromatography (50–100% MeOH–H2O gradient over 40 min) to afford (+)-(I), (+)-(II) and (+)-(III), for which the [α]D and NMR spectra and MS data concur with those previously published (Kazlauskas et al., 1979; Somerville et al., 2006). Slow recrystallization of (I) and (II) from MeOH (100%) and (III) from a 1:1 MeOH–MeCN mixture provided crystals suitable for X-ray work.

Refinement top

Alkyl and heterocyclic H atoms were included at estimated positions using a riding model. Hydroxyl H atoms were constrained similarly but the H—O—C—C dihedral angle was refined. For compound (III), disorder in ring A was identified and refined with two sets of atoms, C1A/B, C2A/B, C3A/B, C18A/B, O1A/B, O3A/B and O4A/B. The A and B conformers were refined with complementary occupancies and the two rings were restrained to have the same bond lengths and angles. The major (71%) conformer of (III) has ring A in a chair conformer with the 3-hydroxyl group axial, while the minor conformer has the hydroxyl group equatorial and the ring in a twisted-boat conformation.

Computing details top

For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLUTON (Spek, 1991); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Only one of the independent molecules is shown.
[Figure 2] Fig. 2. The molecular structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 3] Fig. 3. The molecular structure of the major conformer of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 4] Fig. 4. A plot of the disorder in (III). The minor conformer is shown with broken lines. H atoms have been omitted.
(I) (3bR,5aR,9aR,9bR)-3b,6,6,9a-tetramethyl-4,5,5a,6,8,9,9a,9b,10,11- decahydrophenanthro[1,2-c]furan-7(3bH)-one top
Crystal data top
C20H28O2F(000) = 656
Mr = 300.42Dx = 1.223 Mg m3
Monoclinic, P21Cu Kα radiation, λ = 1.5418 Å
Hall symbol: P 2ybCell parameters from 14597 reflections
a = 12.3336 (1) Åθ = 3.7–62.3°
b = 7.4124 (1) ŵ = 0.59 mm1
c = 18.2476 (1) ÅT = 130 K
β = 101.930 (1)°Prism, colourless
V = 1632.19 (3) Å30.3 × 0.3 × 0.1 mm
Z = 4
Data collection top
Oxford Diffraction Gemini S Ultra
diffractometer
4826 reflections with I > 2σ(I)
Radiation source: Ultra (Cu) X-ray sourceRint = 0.034
Mirror monochromatorθmax = 62.3°, θmin = 3.7°
Detector resolution: 16.0696 pixels mm-1h = 1414
ω scansk = 88
26930 measured reflectionsl = 2020
5168 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.027 w = 1/[σ2(Fo2) + (0.046P)2 + 0.0646P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.070(Δ/σ)max = 0.001
S = 1.05Δρmax = 0.17 e Å3
5168 reflectionsΔρmin = 0.14 e Å3
406 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0035 (4)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), with how many Friedel pairs?
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.06 (14)
Crystal data top
C20H28O2V = 1632.19 (3) Å3
Mr = 300.42Z = 4
Monoclinic, P21Cu Kα radiation
a = 12.3336 (1) ŵ = 0.59 mm1
b = 7.4124 (1) ÅT = 130 K
c = 18.2476 (1) Å0.3 × 0.3 × 0.1 mm
β = 101.930 (1)°
Data collection top
Oxford Diffraction Gemini S Ultra
diffractometer
4826 reflections with I > 2σ(I)
26930 measured reflectionsRint = 0.034
5168 independent reflectionsθmax = 62.3°
Refinement top
R[F2 > 2σ(F2)] = 0.027H-atom parameters constrained
wR(F2) = 0.070Δρmax = 0.17 e Å3
S = 1.05Δρmin = 0.14 e Å3
5168 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs?
406 parametersAbsolute structure parameter: 0.06 (14)
1 restraint
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
xyzUiso*/Ueq
C1A0.81069 (12)1.20326 (19)0.15478 (9)0.0215 (3)
H1A0.83181.25310.20610.026*
H1B0.85591.26510.12350.026*
C2A0.68728 (12)1.2457 (2)0.12339 (9)0.0229 (3)
H2A0.66581.35200.15000.027*
H2B0.67761.27770.06980.027*
C3A0.61155 (12)1.0922 (2)0.13099 (8)0.0212 (3)
C4A0.63493 (11)0.9158 (2)0.09383 (8)0.0195 (3)
C5A0.76043 (11)0.90527 (19)0.09059 (8)0.0179 (3)
H5A0.76790.97630.04530.021*
C6A0.79725 (12)0.7130 (2)0.07622 (9)0.0218 (3)
H6A0.79460.63660.12030.026*
H6B0.74540.66140.03250.026*
C7A0.91449 (12)0.7116 (2)0.06135 (9)0.0233 (3)
H7A0.91620.78380.01600.028*
H7B0.93540.58620.05170.028*
C8A0.99923 (12)0.7889 (2)0.12784 (8)0.0200 (3)
C9A0.96038 (11)0.98049 (19)0.14673 (8)0.0184 (3)
H9A0.96241.05390.10110.022*
C10A0.83879 (12)0.99820 (19)0.15742 (8)0.0181 (3)
C11A1.04752 (12)1.0690 (2)0.20909 (8)0.0231 (3)
H11A1.01641.18060.22620.028*
H11B1.06580.98570.25230.028*
C12A1.15309 (12)1.1146 (2)0.18126 (10)0.0285 (4)
H12A1.14151.22690.15130.034*
H12B1.21461.13550.22470.034*
C13A1.18363 (12)0.9646 (2)0.13421 (8)0.0235 (3)
C14A1.11035 (12)0.8178 (2)0.10692 (8)0.0210 (3)
C15A1.16359 (12)0.7170 (2)0.06398 (9)0.0282 (4)
H15A1.13440.61030.03850.034*
C16A1.27537 (12)0.9408 (2)0.10581 (9)0.0286 (4)
H16A1.33801.01850.11500.034*
C17A1.01733 (13)0.6527 (2)0.19337 (9)0.0238 (3)
H17A1.04490.53870.17710.036*
H17B0.94690.63160.20890.036*
H17C1.07160.70160.23560.036*
C18A0.56576 (12)0.9265 (2)0.01287 (9)0.0261 (3)
H18A0.48670.93010.01410.039*
H18B0.58090.82030.01540.039*
H18C0.58581.03590.01140.039*
C19A0.59174 (12)0.7551 (2)0.13250 (9)0.0256 (4)
H19A0.63540.74300.18360.038*
H19B0.59840.64450.10430.038*
H19C0.51380.77510.13420.038*
C20A0.82365 (12)0.9245 (2)0.23354 (8)0.0226 (3)
H20A0.75320.96780.24380.034*
H20B0.88480.96650.27310.034*
H20C0.82340.79230.23220.034*
O1A0.53320 (9)1.10851 (15)0.16183 (6)0.0319 (3)
O2A1.26582 (8)0.78912 (17)0.06188 (6)0.0326 (3)
C1B0.54817 (12)0.8852 (2)0.36487 (9)0.0242 (3)
H1C0.55020.95790.41060.029*
H1D0.60530.93410.33930.029*
C2B0.43381 (12)0.9086 (2)0.31285 (10)0.0301 (4)
H2C0.40291.02730.32290.036*
H2D0.44290.90850.26020.036*
C3B0.35319 (12)0.7637 (2)0.32253 (8)0.0236 (3)
C4B0.38911 (12)0.5715 (2)0.30928 (8)0.0208 (3)
C5B0.51896 (12)0.56161 (19)0.32500 (8)0.0184 (3)
H5B0.54000.60750.27830.022*
C6B0.56151 (11)0.36727 (19)0.33358 (9)0.0210 (3)
H6C0.54680.31550.38060.025*
H6D0.52140.29370.29130.025*
C7B0.68587 (12)0.3602 (2)0.33511 (9)0.0217 (3)
H7C0.69970.40690.28700.026*
H7D0.71100.23320.34020.026*
C8B0.75357 (12)0.47132 (19)0.39984 (8)0.0190 (3)
C9B0.70646 (12)0.66700 (19)0.39510 (8)0.0185 (3)
H9B0.71990.71420.34640.022*
C10B0.57910 (12)0.68707 (19)0.38848 (8)0.0192 (3)
C11B0.77821 (12)0.7880 (2)0.45470 (8)0.0233 (3)
H11C0.74060.90540.45660.028*
H11D0.78670.73030.50450.028*
C12B0.89311 (12)0.8198 (2)0.43708 (8)0.0240 (3)
H12C0.88810.91580.39880.029*
H12D0.94480.86120.48290.029*
C13B0.93760 (12)0.6508 (2)0.40885 (8)0.0210 (3)
C14B0.87265 (12)0.48971 (19)0.39060 (8)0.0201 (3)
C15B0.93894 (11)0.3695 (2)0.36568 (9)0.0250 (4)
H15B0.91750.25030.34990.030*
C16B1.03768 (12)0.6147 (2)0.39269 (8)0.0261 (4)
H16B1.09750.69780.39890.031*
C17B0.75585 (12)0.3723 (2)0.47461 (9)0.0259 (4)
H17D0.79270.25530.47390.039*
H17E0.67980.35350.48120.039*
H17F0.79650.44520.51610.039*
C18B0.34419 (13)0.5330 (2)0.22540 (9)0.0276 (4)
H18D0.26300.53270.21510.041*
H18E0.37100.41510.21250.041*
H18F0.37010.62690.19530.041*
C19B0.33256 (12)0.4392 (2)0.35432 (9)0.0253 (3)
H19D0.35910.46130.40800.038*
H19E0.35040.31510.34250.038*
H19F0.25210.45680.34120.038*
C20B0.54232 (13)0.6512 (2)0.46314 (8)0.0249 (3)
H20D0.46630.69460.45940.037*
H20E0.59200.71470.50380.037*
H20F0.54530.52130.47350.037*
O1B0.26387 (9)0.79797 (15)0.33814 (7)0.0322 (3)
O2B1.04116 (8)0.44232 (15)0.36619 (6)0.0277 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.0192 (8)0.0191 (8)0.0261 (8)0.0012 (6)0.0046 (6)0.0019 (6)
C2A0.0238 (8)0.0189 (8)0.0262 (8)0.0027 (6)0.0055 (7)0.0002 (6)
C3A0.0167 (8)0.0240 (8)0.0212 (8)0.0022 (6)0.0000 (6)0.0015 (6)
C4A0.0167 (7)0.0202 (8)0.0213 (8)0.0013 (6)0.0035 (6)0.0019 (6)
C5A0.0177 (7)0.0184 (7)0.0173 (7)0.0016 (6)0.0029 (6)0.0013 (6)
C6A0.0212 (8)0.0190 (8)0.0237 (8)0.0016 (6)0.0011 (6)0.0039 (6)
C7A0.0246 (8)0.0206 (8)0.0250 (8)0.0009 (6)0.0056 (6)0.0051 (6)
C8A0.0172 (7)0.0209 (7)0.0221 (8)0.0018 (6)0.0046 (6)0.0016 (6)
C9A0.0191 (7)0.0183 (7)0.0175 (7)0.0003 (6)0.0033 (6)0.0013 (6)
C10A0.0173 (7)0.0179 (7)0.0190 (7)0.0003 (6)0.0039 (6)0.0007 (6)
C11A0.0210 (8)0.0217 (8)0.0254 (8)0.0019 (6)0.0021 (7)0.0037 (7)
C12A0.0187 (7)0.0248 (8)0.0405 (10)0.0036 (6)0.0029 (7)0.0051 (7)
C13A0.0183 (7)0.0272 (9)0.0248 (8)0.0024 (6)0.0039 (6)0.0055 (7)
C14A0.0197 (7)0.0237 (8)0.0192 (8)0.0032 (6)0.0028 (6)0.0010 (6)
C15A0.0198 (8)0.0388 (9)0.0260 (8)0.0008 (7)0.0051 (6)0.0032 (7)
C16A0.0203 (8)0.0346 (9)0.0301 (9)0.0007 (7)0.0035 (7)0.0059 (8)
C17A0.0221 (8)0.0213 (8)0.0287 (8)0.0036 (6)0.0065 (7)0.0024 (6)
C18A0.0195 (7)0.0294 (8)0.0277 (8)0.0021 (7)0.0005 (6)0.0007 (7)
C19A0.0188 (7)0.0236 (8)0.0348 (9)0.0019 (6)0.0061 (7)0.0032 (7)
C20A0.0207 (7)0.0262 (8)0.0212 (8)0.0018 (7)0.0054 (6)0.0009 (7)
O1A0.0224 (6)0.0345 (7)0.0417 (7)0.0009 (5)0.0132 (5)0.0050 (5)
O2A0.0224 (6)0.0492 (7)0.0284 (6)0.0032 (5)0.0104 (5)0.0008 (6)
C1B0.0233 (8)0.0186 (8)0.0317 (9)0.0006 (6)0.0081 (7)0.0019 (6)
C2B0.0250 (8)0.0192 (8)0.0457 (10)0.0030 (7)0.0068 (7)0.0063 (7)
C3B0.0207 (8)0.0237 (8)0.0254 (8)0.0020 (6)0.0026 (7)0.0026 (7)
C4B0.0179 (7)0.0197 (7)0.0248 (8)0.0005 (6)0.0049 (6)0.0007 (6)
C5B0.0178 (7)0.0182 (7)0.0200 (7)0.0017 (6)0.0059 (6)0.0003 (6)
C6B0.0185 (7)0.0182 (7)0.0259 (8)0.0019 (6)0.0035 (6)0.0020 (6)
C7B0.0204 (7)0.0178 (7)0.0270 (8)0.0001 (6)0.0052 (6)0.0025 (6)
C8B0.0178 (7)0.0185 (8)0.0205 (7)0.0016 (6)0.0038 (6)0.0001 (6)
C9B0.0203 (7)0.0178 (7)0.0177 (7)0.0012 (6)0.0052 (6)0.0007 (6)
C10B0.0206 (7)0.0170 (8)0.0209 (8)0.0013 (6)0.0066 (6)0.0004 (6)
C11B0.0253 (8)0.0211 (8)0.0236 (8)0.0023 (6)0.0057 (6)0.0040 (7)
C12B0.0262 (8)0.0239 (8)0.0211 (8)0.0077 (6)0.0028 (6)0.0020 (6)
C13B0.0207 (7)0.0259 (8)0.0146 (7)0.0026 (6)0.0004 (6)0.0019 (6)
C14B0.0198 (7)0.0226 (8)0.0164 (7)0.0005 (6)0.0004 (6)0.0013 (6)
C15B0.0178 (7)0.0293 (8)0.0267 (8)0.0025 (6)0.0018 (6)0.0029 (7)
C16B0.0234 (8)0.0329 (9)0.0207 (8)0.0059 (7)0.0014 (6)0.0004 (7)
C17B0.0232 (8)0.0245 (8)0.0300 (9)0.0018 (6)0.0052 (7)0.0066 (7)
C18B0.0216 (8)0.0307 (9)0.0287 (9)0.0014 (7)0.0011 (7)0.0002 (7)
C19B0.0177 (7)0.0222 (8)0.0371 (9)0.0017 (6)0.0081 (7)0.0018 (7)
C20B0.0236 (8)0.0282 (8)0.0240 (8)0.0016 (7)0.0079 (6)0.0042 (7)
O1B0.0229 (6)0.0282 (6)0.0472 (7)0.0042 (5)0.0109 (5)0.0002 (6)
O2B0.0197 (5)0.0360 (6)0.0276 (6)0.0009 (5)0.0054 (4)0.0039 (5)
Geometric parameters (Å, º) top
C1A—C2A1.544 (2)C1B—C2B1.539 (2)
C1A—C10A1.558 (2)C1B—C10B1.555 (2)
C1A—H1A0.9900C1B—H1C0.9900
C1A—H1B0.9900C1B—H1D0.9900
C2A—C3A1.496 (2)C2B—C3B1.499 (2)
C2A—H2A0.9900C2B—H2C0.9900
C2A—H2B0.9900C2B—H2D0.9900
C3A—O1A1.2205 (18)C3B—O1B1.2202 (18)
C3A—C4A1.528 (2)C3B—C4B1.526 (2)
C4A—C19A1.535 (2)C4B—C19B1.537 (2)
C4A—C18A1.548 (2)C4B—C18B1.543 (2)
C4A—C5A1.5631 (18)C4B—C5B1.5693 (19)
C5A—C6A1.534 (2)C5B—C6B1.530 (2)
C5A—C10A1.5519 (19)C5B—C10B1.550 (2)
C5A—H5A1.0000C5B—H5B1.0000
C6A—C7A1.525 (2)C6B—C7B1.5291 (19)
C6A—H6A0.9900C6B—H6C0.9900
C6A—H6B0.9900C6B—H6D0.9900
C7A—C8A1.539 (2)C7B—C8B1.537 (2)
C7A—H7A0.9900C7B—H7C0.9900
C7A—H7B0.9900C7B—H7D0.9900
C8A—C14A1.512 (2)C8B—C14B1.519 (2)
C8A—C17A1.545 (2)C8B—C17B1.544 (2)
C8A—C9A1.560 (2)C8B—C9B1.558 (2)
C9A—C11A1.5410 (19)C9B—C11B1.540 (2)
C9A—C10A1.557 (2)C9B—C10B1.557 (2)
C9A—H9A1.0000C9B—H9B1.0000
C10A—C20A1.539 (2)C10B—C20B1.545 (2)
C11A—C12A1.530 (2)C11B—C12B1.535 (2)
C11A—H11A0.9900C11B—H11C0.9900
C11A—H11B0.9900C11B—H11D0.9900
C12A—C13A1.500 (2)C12B—C13B1.501 (2)
C12A—H12A0.9900C12B—H12C0.9900
C12A—H12B0.9900C12B—H12D0.9900
C13A—C16A1.350 (2)C13B—C16B1.354 (2)
C13A—C14A1.436 (2)C13B—C14B1.438 (2)
C14A—C15A1.348 (2)C14B—C15B1.350 (2)
C15A—O2A1.3772 (19)C15B—O2B1.3696 (18)
C15A—H15A0.9500C15B—H15B0.9500
C16A—O2A1.372 (2)C16B—O2B1.370 (2)
C16A—H16A0.9500C16B—H16B0.9500
C17A—H17A0.9800C17B—H17D0.9800
C17A—H17B0.9800C17B—H17E0.9800
C17A—H17C0.9800C17B—H17F0.9800
C18A—H18A0.9800C18B—H18D0.9800
C18A—H18B0.9800C18B—H18E0.9800
C18A—H18C0.9800C18B—H18F0.9800
C19A—H19A0.9800C19B—H19D0.9800
C19A—H19B0.9800C19B—H19E0.9800
C19A—H19C0.9800C19B—H19F0.9800
C20A—H20A0.9800C20B—H20D0.9800
C20A—H20B0.9800C20B—H20E0.9800
C20A—H20C0.9800C20B—H20F0.9800
C2A—C1A—C10A113.97 (12)C2B—C1B—C10B114.75 (12)
C2A—C1A—H1A108.8C2B—C1B—H1C108.6
C10A—C1A—H1A108.8C10B—C1B—H1C108.6
C2A—C1A—H1B108.8C2B—C1B—H1D108.6
C10A—C1A—H1B108.8C10B—C1B—H1D108.6
H1A—C1A—H1B107.7H1C—C1B—H1D107.6
C3A—C2A—C1A113.40 (12)C3B—C2B—C1B113.09 (13)
C3A—C2A—H2A108.9C3B—C2B—H2C109.0
C1A—C2A—H2A108.9C1B—C2B—H2C109.0
C3A—C2A—H2B108.9C3B—C2B—H2D109.0
C1A—C2A—H2B108.9C1B—C2B—H2D109.0
H2A—C2A—H2B107.7H2C—C2B—H2D107.8
O1A—C3A—C2A122.43 (14)O1B—C3B—C2B122.11 (14)
O1A—C3A—C4A121.97 (13)O1B—C3B—C4B122.46 (13)
C2A—C3A—C4A115.52 (12)C2B—C3B—C4B115.41 (13)
C3A—C4A—C19A110.18 (12)C3B—C4B—C19B109.42 (12)
C3A—C4A—C18A105.23 (12)C3B—C4B—C18B105.86 (12)
C19A—C4A—C18A107.65 (12)C19B—C4B—C18B107.64 (12)
C3A—C4A—C5A109.81 (11)C3B—C4B—C5B109.47 (12)
C19A—C4A—C5A114.78 (12)C19B—C4B—C5B115.55 (12)
C18A—C4A—C5A108.73 (12)C18B—C4B—C5B108.43 (12)
C6A—C5A—C10A112.84 (11)C6B—C5B—C10B112.79 (11)
C6A—C5A—C4A112.53 (11)C6B—C5B—C4B112.22 (11)
C10A—C5A—C4A114.13 (12)C10B—C5B—C4B114.91 (12)
C6A—C5A—H5A105.5C6B—C5B—H5B105.3
C10A—C5A—H5A105.5C10B—C5B—H5B105.3
C4A—C5A—H5A105.5C4B—C5B—H5B105.3
C7A—C6A—C5A111.21 (12)C7B—C6B—C5B110.82 (11)
C7A—C6A—H6A109.4C7B—C6B—H6C109.5
C5A—C6A—H6A109.4C5B—C6B—H6C109.5
C7A—C6A—H6B109.4C7B—C6B—H6D109.5
C5A—C6A—H6B109.4C5B—C6B—H6D109.5
H6A—C6A—H6B108.0H6C—C6B—H6D108.1
C6A—C7A—C8A111.80 (12)C6B—C7B—C8B112.28 (12)
C6A—C7A—H7A109.3C6B—C7B—H7C109.1
C8A—C7A—H7A109.3C8B—C7B—H7C109.1
C6A—C7A—H7B109.3C6B—C7B—H7D109.1
C8A—C7A—H7B109.3C8B—C7B—H7D109.1
H7A—C7A—H7B107.9H7C—C7B—H7D107.9
C14A—C8A—C7A110.91 (11)C14B—C8B—C7B110.30 (12)
C14A—C8A—C17A107.12 (12)C14B—C8B—C17B107.42 (11)
C7A—C8A—C17A109.44 (12)C7B—C8B—C17B109.39 (12)
C14A—C8A—C9A105.23 (11)C14B—C8B—C9B105.57 (11)
C7A—C8A—C9A108.88 (11)C7B—C8B—C9B108.60 (11)
C17A—C8A—C9A115.18 (12)C17B—C8B—C9B115.46 (12)
C11A—C9A—C10A114.48 (11)C11B—C9B—C10B114.97 (12)
C11A—C9A—C8A110.57 (11)C11B—C9B—C8B110.47 (12)
C10A—C9A—C8A116.88 (11)C10B—C9B—C8B116.86 (11)
C11A—C9A—H9A104.5C11B—C9B—H9B104.3
C10A—C9A—H9A104.5C10B—C9B—H9B104.3
C8A—C9A—H9A104.5C8B—C9B—H9B104.3
C20A—C10A—C5A112.30 (12)C20B—C10B—C5B111.92 (12)
C20A—C10A—C9A112.50 (11)C20B—C10B—C1B107.87 (12)
C5A—C10A—C9A108.88 (11)C5B—C10B—C1B107.91 (11)
C20A—C10A—C1A107.84 (13)C20B—C10B—C9B112.97 (12)
C5A—C10A—C1A108.08 (12)C5B—C10B—C9B108.65 (11)
C9A—C10A—C1A107.00 (11)C1B—C10B—C9B107.30 (11)
C12A—C11A—C9A111.13 (12)C12B—C11B—C9B111.23 (12)
C12A—C11A—H11A109.4C12B—C11B—H11C109.4
C9A—C11A—H11A109.4C9B—C11B—H11C109.4
C12A—C11A—H11B109.4C12B—C11B—H11D109.4
C9A—C11A—H11B109.4C9B—C11B—H11D109.4
H11A—C11A—H11B108.0H11C—C11B—H11D108.0
C13A—C12A—C11A110.98 (13)C13B—C12B—C11B111.27 (12)
C13A—C12A—H12A109.4C13B—C12B—H12C109.4
C11A—C12A—H12A109.4C11B—C12B—H12C109.4
C13A—C12A—H12B109.4C13B—C12B—H12D109.4
C11A—C12A—H12B109.4C11B—C12B—H12D109.4
H12A—C12A—H12B108.0H12C—C12B—H12D108.0
C16A—C13A—C14A106.58 (14)C16B—C13B—C14B105.93 (13)
C16A—C13A—C12A130.26 (14)C16B—C13B—C12B130.88 (14)
C14A—C13A—C12A123.06 (13)C14B—C13B—C12B123.15 (13)
C15A—C14A—C13A105.91 (13)C15B—C14B—C13B106.19 (13)
C15A—C14A—C8A130.12 (14)C15B—C14B—C8B130.17 (13)
C13A—C14A—C8A123.92 (13)C13B—C14B—C8B123.64 (13)
C14A—C15A—O2A111.10 (14)C14B—C15B—O2B111.01 (14)
C14A—C15A—H15A124.4C14B—C15B—H15B124.5
O2A—C15A—H15A124.4O2B—C15B—H15B124.5
C13A—C16A—O2A110.72 (14)C13B—C16B—O2B110.98 (13)
C13A—C16A—H16A124.6C13B—C16B—H16B124.5
O2A—C16A—H16A124.6O2B—C16B—H16B124.5
C8A—C17A—H17A109.5C8B—C17B—H17D109.5
C8A—C17A—H17B109.5C8B—C17B—H17E109.5
H17A—C17A—H17B109.5H17D—C17B—H17E109.5
C8A—C17A—H17C109.5C8B—C17B—H17F109.5
H17A—C17A—H17C109.5H17D—C17B—H17F109.5
H17B—C17A—H17C109.5H17E—C17B—H17F109.5
C4A—C18A—H18A109.5C4B—C18B—H18D109.5
C4A—C18A—H18B109.5C4B—C18B—H18E109.5
H18A—C18A—H18B109.5H18D—C18B—H18E109.5
C4A—C18A—H18C109.5C4B—C18B—H18F109.5
H18A—C18A—H18C109.5H18D—C18B—H18F109.5
H18B—C18A—H18C109.5H18E—C18B—H18F109.5
C4A—C19A—H19A109.5C4B—C19B—H19D109.5
C4A—C19A—H19B109.5C4B—C19B—H19E109.5
H19A—C19A—H19B109.5H19D—C19B—H19E109.5
C4A—C19A—H19C109.5C4B—C19B—H19F109.5
H19A—C19A—H19C109.5H19D—C19B—H19F109.5
H19B—C19A—H19C109.5H19E—C19B—H19F109.5
C10A—C20A—H20A109.5C10B—C20B—H20D109.5
C10A—C20A—H20B109.5C10B—C20B—H20E109.5
H20A—C20A—H20B109.5H20D—C20B—H20E109.5
C10A—C20A—H20C109.5C10B—C20B—H20F109.5
H20A—C20A—H20C109.5H20D—C20B—H20F109.5
H20B—C20A—H20C109.5H20E—C20B—H20F109.5
C16A—O2A—C15A105.69 (12)C15B—O2B—C16B105.89 (12)
C10A—C1A—C2A—C3A23.85 (19)C10B—C1B—C2B—C3B27.3 (2)
C1A—C2A—C3A—O1A125.51 (15)C1B—C2B—C3B—O1B123.30 (16)
C1A—C2A—C3A—C4A57.67 (17)C1B—C2B—C3B—C4B58.42 (18)
O1A—C3A—C4A—C19A28.35 (18)O1B—C3B—C4B—C19B28.07 (19)
C2A—C3A—C4A—C19A154.82 (13)C2B—C3B—C4B—C19B153.66 (13)
O1A—C3A—C4A—C18A87.43 (16)O1B—C3B—C4B—C18B87.67 (17)
C2A—C3A—C4A—C18A89.40 (15)C2B—C3B—C4B—C18B90.60 (15)
O1A—C3A—C4A—C5A155.72 (13)O1B—C3B—C4B—C5B155.64 (14)
C2A—C3A—C4A—C5A27.45 (16)C2B—C3B—C4B—C5B26.08 (17)
C3A—C4A—C5A—C6A162.89 (12)C3B—C4B—C5B—C6B164.58 (12)
C19A—C4A—C5A—C6A38.13 (17)C19B—C4B—C5B—C6B40.52 (17)
C18A—C4A—C5A—C6A82.48 (15)C18B—C4B—C5B—C6B80.38 (15)
C3A—C4A—C5A—C10A32.62 (16)C3B—C4B—C5B—C10B33.95 (16)
C19A—C4A—C5A—C10A92.14 (15)C19B—C4B—C5B—C10B90.11 (16)
C18A—C4A—C5A—C10A147.26 (12)C18B—C4B—C5B—C10B148.99 (12)
C10A—C5A—C6A—C7A57.88 (16)C10B—C5B—C6B—C7B58.20 (16)
C4A—C5A—C6A—C7A171.20 (11)C4B—C5B—C6B—C7B170.10 (12)
C5A—C6A—C7A—C8A59.59 (16)C5B—C6B—C7B—C8B59.41 (16)
C6A—C7A—C8A—C14A169.72 (12)C6B—C7B—C8B—C14B169.30 (12)
C6A—C7A—C8A—C17A72.31 (15)C6B—C7B—C8B—C17B72.77 (15)
C6A—C7A—C8A—C9A54.38 (16)C6B—C7B—C8B—C9B54.06 (16)
C14A—C8A—C9A—C11A56.67 (14)C14B—C8B—C9B—C11B56.71 (15)
C7A—C8A—C9A—C11A175.62 (12)C7B—C8B—C9B—C11B174.99 (12)
C17A—C8A—C9A—C11A61.05 (16)C17B—C8B—C9B—C11B61.77 (16)
C14A—C8A—C9A—C10A169.98 (12)C14B—C8B—C9B—C10B169.34 (12)
C7A—C8A—C9A—C10A51.03 (16)C7B—C8B—C9B—C10B51.06 (16)
C17A—C8A—C9A—C10A72.30 (16)C17B—C8B—C9B—C10B72.19 (16)
C6A—C5A—C10A—C20A74.55 (15)C6B—C5B—C10B—C20B73.70 (15)
C4A—C5A—C10A—C20A55.57 (15)C4B—C5B—C10B—C20B56.65 (16)
C6A—C5A—C10A—C9A50.73 (15)C6B—C5B—C10B—C1B167.77 (12)
C4A—C5A—C10A—C9A179.16 (11)C4B—C5B—C10B—C1B61.87 (15)
C6A—C5A—C10A—C1A166.62 (12)C6B—C5B—C10B—C9B51.74 (15)
C4A—C5A—C10A—C1A63.27 (15)C4B—C5B—C10B—C9B177.91 (11)
C11A—C9A—C10A—C20A55.38 (16)C2B—C1B—C10B—C20B92.41 (16)
C8A—C9A—C10A—C20A76.20 (15)C2B—C1B—C10B—C5B28.68 (18)
C11A—C9A—C10A—C5A179.46 (12)C2B—C1B—C10B—C9B145.60 (13)
C8A—C9A—C10A—C5A48.96 (16)C11B—C9B—C10B—C20B56.85 (16)
C11A—C9A—C10A—C1A62.88 (15)C8B—C9B—C10B—C20B75.08 (16)
C8A—C9A—C10A—C1A165.54 (12)C11B—C9B—C10B—C5B178.33 (12)
C2A—C1A—C10A—C20A89.23 (15)C8B—C9B—C10B—C5B49.74 (16)
C2A—C1A—C10A—C5A32.41 (18)C11B—C9B—C10B—C1B61.90 (16)
C2A—C1A—C10A—C9A149.52 (12)C8B—C9B—C10B—C1B166.17 (12)
C10A—C9A—C11A—C12A156.96 (12)C10B—C9B—C11B—C12B156.75 (13)
C8A—C9A—C11A—C12A68.49 (16)C8B—C9B—C11B—C12B68.36 (15)
C9A—C11A—C12A—C13A41.93 (17)C9B—C11B—C12B—C13B40.31 (16)
C11A—C12A—C13A—C16A171.99 (15)C11B—C12B—C13B—C16B174.03 (15)
C11A—C12A—C13A—C14A12.0 (2)C11B—C12B—C13B—C14B8.5 (2)
C16A—C13A—C14A—C15A0.14 (17)C16B—C13B—C14B—C15B0.54 (16)
C12A—C13A—C14A—C15A176.68 (14)C12B—C13B—C14B—C15B178.52 (14)
C16A—C13A—C14A—C8A177.61 (13)C16B—C13B—C14B—C8B179.68 (13)
C12A—C13A—C14A—C8A5.6 (2)C12B—C13B—C14B—C8B1.7 (2)
C7A—C8A—C14A—C15A38.2 (2)C7B—C8B—C14B—C15B37.9 (2)
C17A—C8A—C14A—C15A81.21 (18)C17B—C8B—C14B—C15B81.26 (19)
C9A—C8A—C14A—C15A155.75 (15)C9B—C8B—C14B—C15B155.02 (15)
C7A—C8A—C14A—C13A144.67 (14)C7B—C8B—C14B—C13B142.39 (14)
C17A—C8A—C14A—C13A95.96 (16)C17B—C8B—C14B—C13B98.46 (16)
C9A—C8A—C14A—C13A27.08 (18)C9B—C8B—C14B—C13B25.26 (17)
C13A—C14A—C15A—O2A0.02 (17)C13B—C14B—C15B—O2B0.39 (16)
C8A—C14A—C15A—O2A177.58 (14)C8B—C14B—C15B—O2B179.85 (13)
C14A—C13A—C16A—O2A0.24 (17)C14B—C13B—C16B—O2B0.50 (16)
C12A—C13A—C16A—O2A176.26 (15)C12B—C13B—C16B—O2B178.27 (14)
C13A—C16A—O2A—C15A0.25 (16)C14B—C15B—O2B—C16B0.10 (16)
C14A—C15A—O2A—C16A0.16 (16)C13B—C16B—O2B—C15B0.27 (16)
(II) (3bR,5aR,6S,7R,9aR,9bR)-7-hydroxy- 6-hydroxymethyl-3b,6,9a-trimethyl-3b,5,5a,6,7,9,9a,9b,10,11- decahydrophenanthro[1,2-c]furan-8(4H)-one top
Crystal data top
C20H28O4F(000) = 360
Mr = 332.42Dx = 1.283 Mg m3
Monoclinic, P21Cu Kα radiation, λ = 1.5418 Å
Hall symbol: P 2ybCell parameters from 12951 reflections
a = 9.5317 (1) Åθ = 3.9–62.6°
b = 7.8958 (1) ŵ = 0.71 mm1
c = 11.6742 (1) ÅT = 130 K
β = 101.734 (1)°Prism, colourless
V = 860.24 (2) Å30.3 × 0.2 × 0.2 mm
Z = 2
Data collection top
Oxford Diffraction Gemini S Ultra
diffractometer
2583 reflections with I > 2σ(I)
Radiation source: Ultra (Cu) X-ray sourceRint = 0.024
Mirror monochromatorθmax = 62.6°, θmin = 3.9°
Detector resolution: 16.0696 pixels mm-1h = 1010
ω scansk = 88
16202 measured reflectionsl = 1313
2624 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.119 w = 1/[σ2(Fo2) + (0.0899P)2 + 0.1625P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
2624 reflectionsΔρmax = 0.22 e Å3
222 parametersΔρmin = 0.21 e Å3
1 restraintAbsolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.2 (2)
Crystal data top
C20H28O4V = 860.24 (2) Å3
Mr = 332.42Z = 2
Monoclinic, P21Cu Kα radiation
a = 9.5317 (1) ŵ = 0.71 mm1
b = 7.8958 (1) ÅT = 130 K
c = 11.6742 (1) Å0.3 × 0.2 × 0.2 mm
β = 101.734 (1)°
Data collection top
Oxford Diffraction Gemini S Ultra
diffractometer
2583 reflections with I > 2σ(I)
16202 measured reflectionsRint = 0.024
2624 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.119Δρmax = 0.22 e Å3
S = 1.11Δρmin = 0.21 e Å3
2624 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs?
222 parametersAbsolute structure parameter: 0.2 (2)
1 restraint
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
xyzUiso*/Ueq
C10.3847 (2)0.2927 (3)0.77259 (19)0.0247 (5)
H1A0.43980.18590.77680.03*
H1B0.36350.31490.85080.03*
C20.2472 (2)0.2751 (3)0.68433 (18)0.0239 (5)
C30.1513 (2)0.4288 (3)0.67319 (17)0.0217 (4)
H30.13120.45420.75220.026*
C40.2287 (2)0.5834 (3)0.63400 (16)0.0197 (4)
C50.3774 (2)0.6006 (3)0.71893 (17)0.0190 (4)
H50.35330.62140.79720.023*
C60.4619 (2)0.7582 (3)0.69689 (19)0.0254 (5)
H6A0.50350.74020.62680.031*
H6B0.39650.85680.6820.031*
C70.5816 (2)0.7943 (3)0.80250 (19)0.0250 (5)
H7A0.53880.81940.87110.03*
H7B0.63530.89590.78630.03*
C80.6865 (2)0.6447 (3)0.83213 (17)0.0221 (5)
C90.5993 (2)0.4808 (3)0.84426 (16)0.0200 (5)
H90.55010.50490.91040.024*
C100.4751 (2)0.4407 (3)0.73779 (16)0.0197 (4)
C110.7004 (2)0.3320 (3)0.88729 (18)0.0264 (5)
H11A0.64470.22530.8810.032*
H11B0.77240.32160.83740.032*
C120.7767 (2)0.3597 (3)1.01490 (18)0.0287 (5)
H12A0.70910.33771.06720.034*
H12B0.85750.2791.03540.034*
C130.8318 (2)0.5364 (3)1.03252 (18)0.0271 (5)
C140.7852 (2)0.6706 (3)0.95000 (18)0.0246 (5)
C150.8535 (2)0.8125 (3)0.99663 (19)0.0306 (5)
H150.84250.92110.96080.037*
C160.9252 (2)0.6084 (4)1.12249 (19)0.0335 (6)
H160.97350.54951.19010.04*
C170.7841 (2)0.6366 (3)0.74076 (19)0.0303 (5)
H17A0.72450.62950.66190.045*
H17B0.84580.53640.75570.045*
H17C0.84360.73870.7470.045*
C180.1370 (2)0.7391 (3)0.64762 (19)0.0229 (5)
H18A0.17050.83640.60850.034*
H18B0.14540.76450.73090.034*
H18C0.03660.71570.61220.034*
C190.2389 (2)0.5642 (3)0.50441 (17)0.0239 (5)
H19A0.30830.64820.48610.029*
H19B0.27640.450.49250.029*
C200.5318 (2)0.3821 (3)0.62996 (18)0.0280 (5)
H20A0.62280.32210.65540.042*
H20B0.54680.48090.58310.042*
H20C0.46190.3060.58270.042*
O10.21615 (17)0.1502 (2)0.62367 (15)0.0340 (4)
O20.94054 (16)0.7782 (2)1.10250 (14)0.0357 (4)
O30.01897 (15)0.40461 (19)0.59522 (13)0.0270 (4)
H3A0.00740.30360.59890.041*
O40.10442 (16)0.5870 (2)0.42447 (12)0.0258 (4)
H40.04170.52630.44540.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0233 (10)0.0186 (11)0.0293 (10)0.0007 (9)0.0017 (8)0.0041 (9)
C20.0239 (11)0.0197 (12)0.0261 (10)0.0041 (9)0.0004 (9)0.0032 (9)
C30.0192 (10)0.0240 (11)0.0197 (9)0.0028 (8)0.0008 (7)0.0011 (8)
C40.0188 (10)0.0195 (11)0.0199 (10)0.0002 (8)0.0016 (8)0.0004 (8)
C50.0193 (10)0.0194 (11)0.0182 (9)0.0014 (8)0.0040 (8)0.0002 (8)
C60.0220 (11)0.0237 (12)0.0291 (11)0.0031 (9)0.0018 (9)0.0039 (9)
C70.0208 (10)0.0222 (11)0.0309 (11)0.0045 (8)0.0022 (8)0.0003 (9)
C80.0183 (10)0.0266 (12)0.0214 (10)0.0026 (9)0.0036 (8)0.0020 (8)
C90.0169 (10)0.0242 (11)0.0183 (9)0.0002 (8)0.0020 (7)0.0011 (8)
C100.0179 (10)0.0214 (11)0.0194 (10)0.0007 (8)0.0028 (8)0.0014 (8)
C110.0197 (10)0.0287 (13)0.0279 (11)0.0012 (9)0.0019 (8)0.0013 (9)
C120.0218 (10)0.0363 (14)0.0263 (11)0.0000 (9)0.0008 (9)0.0051 (10)
C130.0170 (10)0.0419 (15)0.0228 (10)0.0007 (9)0.0049 (8)0.0042 (9)
C140.0163 (10)0.0355 (13)0.0230 (10)0.0022 (9)0.0063 (8)0.0063 (9)
C150.0204 (10)0.0401 (14)0.0306 (11)0.0026 (10)0.0038 (9)0.0075 (10)
C160.0234 (12)0.0513 (17)0.0251 (11)0.0010 (10)0.0033 (9)0.0063 (10)
C170.0224 (10)0.0441 (14)0.0257 (10)0.0066 (10)0.0079 (9)0.0016 (10)
C180.0227 (10)0.0204 (11)0.0237 (10)0.0016 (8)0.0005 (8)0.0012 (8)
C190.0196 (10)0.0308 (12)0.0195 (10)0.0015 (8)0.0000 (8)0.0022 (9)
C200.0235 (10)0.0358 (13)0.0235 (10)0.0049 (9)0.0020 (8)0.0081 (9)
O10.0310 (9)0.0219 (9)0.0435 (9)0.0030 (7)0.0056 (7)0.0048 (7)
O20.0222 (8)0.0521 (11)0.0309 (8)0.0034 (7)0.0006 (7)0.0162 (8)
O30.0205 (7)0.0241 (8)0.0322 (7)0.0040 (6)0.0047 (6)0.0015 (6)
O40.0252 (7)0.0276 (9)0.0217 (7)0.0022 (6)0.0026 (6)0.0016 (6)
Geometric parameters (Å, º) top
C1—C21.500 (3)C11—C121.535 (3)
C1—C101.554 (3)C11—H11A0.99
C1—H1A0.99C11—H11B0.99
C1—H1B0.99C12—C131.491 (4)
C2—O11.215 (3)C12—H12A0.99
C2—C31.509 (3)C12—H12B0.99
C3—O31.410 (2)C13—C161.356 (3)
C3—C41.543 (3)C13—C141.440 (3)
C3—H31C14—C151.353 (3)
C4—C181.535 (3)C15—O21.368 (3)
C4—C191.543 (3)C15—H150.95
C4—C51.562 (3)C16—O21.374 (4)
C5—C61.532 (3)C16—H160.95
C5—C101.558 (3)C17—H17A0.98
C5—H51C17—H17B0.98
C6—C71.527 (3)C17—H17C0.98
C6—H6A0.99C18—H18A0.98
C6—H6B0.99C18—H18B0.98
C7—C81.541 (3)C18—H18C0.98
C7—H7A0.99C19—O41.435 (2)
C7—H7B0.99C19—H19A0.99
C8—C141.515 (3)C19—H19B0.99
C8—C171.553 (3)C20—H20A0.98
C8—C91.560 (3)C20—H20B0.98
C9—C111.538 (3)C20—H20C0.98
C9—C101.564 (3)O3—H3A0.84
C9—H91O4—H40.84
C10—C201.538 (3)
C2—C1—C10110.11 (16)C20—C10—C9112.11 (16)
C2—C1—H1A109.6C1—C10—C9108.35 (15)
C10—C1—H1A109.6C5—C10—C9106.37 (16)
C2—C1—H1B109.6C12—C11—C9110.50 (18)
C10—C1—H1B109.6C12—C11—H11A109.6
H1A—C1—H1B108.2C9—C11—H11A109.6
O1—C2—C1123.4 (2)C12—C11—H11B109.6
O1—C2—C3122.09 (18)C9—C11—H11B109.6
C1—C2—C3114.46 (18)H11A—C11—H11B108.1
O3—C3—C2113.15 (17)C13—C12—C11110.57 (18)
O3—C3—C4109.55 (15)C13—C12—H12A109.5
C2—C3—C4110.13 (16)C11—C12—H12A109.5
O3—C3—H3107.9C13—C12—H12B109.5
C2—C3—H3107.9C11—C12—H12B109.5
C4—C3—H3107.9H12A—C12—H12B108.1
C18—C4—C19109.34 (17)C16—C13—C14105.9 (2)
C18—C4—C3106.61 (16)C16—C13—C12131.0 (2)
C19—C4—C3110.00 (17)C14—C13—C12123.00 (19)
C18—C4—C5109.11 (16)C15—C14—C13106.40 (19)
C19—C4—C5113.64 (16)C15—C14—C8129.5 (2)
C3—C4—C5107.89 (15)C13—C14—C8123.9 (2)
C6—C5—C10111.26 (15)C14—C15—O2110.7 (2)
C6—C5—C4113.82 (16)C14—C15—H15124.7
C10—C5—C4117.32 (16)O2—C15—H15124.7
C6—C5—H5104.3C13—C16—O2110.7 (2)
C10—C5—H5104.3C13—C16—H16124.7
C4—C5—H5104.3O2—C16—H16124.7
C7—C6—C5110.38 (17)C8—C17—H17A109.5
C7—C6—H6A109.6C8—C17—H17B109.5
C5—C6—H6A109.6H17A—C17—H17B109.5
C7—C6—H6B109.6C8—C17—H17C109.5
C5—C6—H6B109.6H17A—C17—H17C109.5
H6A—C6—H6B108.1H17B—C17—H17C109.5
C6—C7—C8112.47 (18)C4—C18—H18A109.5
C6—C7—H7A109.1C4—C18—H18B109.5
C8—C7—H7A109.1H18A—C18—H18B109.5
C6—C7—H7B109.1C4—C18—H18C109.5
C8—C7—H7B109.1H18A—C18—H18C109.5
H7A—C7—H7B107.8H18B—C18—H18C109.5
C14—C8—C7110.81 (18)O4—C19—C4113.51 (16)
C14—C8—C17106.33 (16)O4—C19—H19A108.9
C7—C8—C17109.24 (18)C4—C19—H19A108.9
C14—C8—C9105.89 (16)O4—C19—H19B108.9
C7—C8—C9108.85 (15)C4—C19—H19B108.9
C17—C8—C9115.65 (18)H19A—C19—H19B107.7
C11—C9—C8110.69 (16)C10—C20—H20A109.5
C11—C9—C10115.29 (17)C10—C20—H20B109.5
C8—C9—C10115.27 (16)H20A—C20—H20B109.5
C11—C9—H9104.7C10—C20—H20C109.5
C8—C9—H9104.7H20A—C20—H20C109.5
C10—C9—H9104.7H20B—C20—H20C109.5
C20—C10—C1107.09 (17)C15—O2—C16106.31 (17)
C20—C10—C5115.29 (16)C3—O3—H3A109.5
C1—C10—C5107.37 (15)C19—O4—H4109.5
C10—C1—C2—O1116.6 (2)C6—C5—C10—C1173.99 (15)
C10—C1—C2—C361.3 (2)C4—C5—C10—C152.5 (2)
O1—C2—C3—O36.0 (3)C6—C5—C10—C958.2 (2)
C1—C2—C3—O3176.14 (16)C4—C5—C10—C9168.33 (16)
O1—C2—C3—C4117.0 (2)C11—C9—C10—C2059.6 (2)
C1—C2—C3—C460.9 (2)C8—C9—C10—C2071.3 (2)
O3—C3—C4—C1865.5 (2)C11—C9—C10—C158.4 (2)
C2—C3—C4—C18169.39 (16)C8—C9—C10—C1170.69 (16)
O3—C3—C4—C1952.9 (2)C11—C9—C10—C5173.55 (16)
C2—C3—C4—C1972.2 (2)C8—C9—C10—C555.5 (2)
O3—C3—C4—C5177.37 (16)C8—C9—C11—C1269.3 (2)
C2—C3—C4—C552.3 (2)C10—C9—C11—C12157.62 (17)
C18—C4—C5—C659.8 (2)C9—C11—C12—C1345.6 (2)
C19—C4—C5—C662.5 (2)C11—C12—C13—C16166.9 (2)
C3—C4—C5—C6175.22 (17)C11—C12—C13—C1415.5 (3)
C18—C4—C5—C10167.86 (16)C16—C13—C14—C150.2 (2)
C19—C4—C5—C1069.8 (2)C12—C13—C14—C15177.91 (19)
C3—C4—C5—C1052.4 (2)C16—C13—C14—C8176.12 (18)
C10—C5—C6—C761.6 (2)C12—C13—C14—C85.8 (3)
C4—C5—C6—C7163.21 (18)C7—C8—C14—C1542.3 (3)
C5—C6—C7—C858.4 (2)C17—C8—C14—C1576.3 (3)
C6—C7—C8—C14168.76 (17)C9—C8—C14—C15160.1 (2)
C6—C7—C8—C1774.4 (2)C7—C8—C14—C13142.3 (2)
C6—C7—C8—C952.7 (2)C17—C8—C14—C1399.1 (2)
C14—C8—C9—C1154.5 (2)C9—C8—C14—C1324.4 (2)
C7—C8—C9—C11173.67 (16)C13—C14—C15—O20.3 (2)
C17—C8—C9—C1163.0 (2)C8—C14—C15—O2175.79 (18)
C14—C8—C9—C10172.41 (17)C14—C13—C16—O20.1 (2)
C7—C8—C9—C1053.2 (2)C12—C13—C16—O2177.8 (2)
C17—C8—C9—C1070.1 (2)C18—C4—C19—O444.5 (2)
C2—C1—C10—C2071.3 (2)C3—C4—C19—O472.3 (2)
C2—C1—C10—C553.1 (2)C5—C4—C19—O4166.63 (17)
C2—C1—C10—C9167.58 (17)C14—C15—O2—C160.2 (2)
C6—C5—C10—C2066.8 (2)C13—C16—O2—C150.1 (2)
C4—C5—C10—C2066.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O4i0.841.942.760 (2)166
O4—H4···O30.842.052.715 (2)136
Symmetry code: (i) x, y1/2, z+1.
(III) (3bR,5aR,6S,7S,9aR,9bR)-7-hydroxy- 6-hydroxymethyl-3b,6,9a-trimethyl-3b,5,5a,6,7,9,9a,9b,10,11- decahydrophenanthro[1,2-c]furan-8(4H)-one top
Crystal data top
C20H28O4F(000) = 720
Mr = 332.42Dx = 1.302 Mg m3
Orthorhombic, P212121Cu Kα radiation, λ = 1.5418 Å
Hall symbol: P 2ac 2abCell parameters from 12054 reflections
a = 6.1411 (1) Åθ = 3.5–62.4°
b = 12.7415 (3) ŵ = 0.72 mm1
c = 21.6714 (5) ÅT = 130 K
V = 1695.72 (6) Å3Prism, colourless
Z = 40.5 × 0.5 × 0.15 mm
Data collection top
Oxford Diffraction Gemini S Ultra
diffractometer
2683 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray source2448 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.038
Detector resolution: 16.0696 pixels mm-1θmax = 62.5°, θmin = 4.0°
ω scansh = 77
Absorption correction: multi-scan
[CrysAlis RED (Oxford Diffraction, 2008); empirical (using intensity measurements) absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm]
k = 1414
Tmin = 0.640, Tmax = 1.000l = 2424
26592 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.056 w = 1/[σ2(Fo2) + (0.0813P)2 + 0.7996P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.155(Δ/σ)max < 0.001
S = 1.09Δρmax = 0.42 e Å3
2683 reflectionsΔρmin = 0.24 e Å3
253 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
9 restraintsExtinction coefficient: 0.0048 (11)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), with how many Friedel pairs?
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.1 (5)
Crystal data top
C20H28O4V = 1695.72 (6) Å3
Mr = 332.42Z = 4
Orthorhombic, P212121Cu Kα radiation
a = 6.1411 (1) ŵ = 0.72 mm1
b = 12.7415 (3) ÅT = 130 K
c = 21.6714 (5) Å0.5 × 0.5 × 0.15 mm
Data collection top
Oxford Diffraction Gemini S Ultra
diffractometer
2683 independent reflections
Absorption correction: multi-scan
[CrysAlis RED (Oxford Diffraction, 2008); empirical (using intensity measurements) absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm]
2448 reflections with I > 2σ(I)
Tmin = 0.640, Tmax = 1.000Rint = 0.038
26592 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.056H-atom parameters constrained
wR(F2) = 0.155Δρmax = 0.42 e Å3
S = 1.09Δρmin = 0.24 e Å3
2683 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs?
253 parametersAbsolute structure parameter: 0.1 (5)
9 restraints
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
xyzUiso*/UeqOcc. (<1)
C40.0346 (5)1.0064 (3)0.99891 (16)0.0550 (8)
C50.0858 (4)0.9388 (2)0.94038 (13)0.0414 (7)
H50.2470.94560.93510.05*
C60.0495 (5)0.8215 (2)0.94902 (13)0.0486 (7)
H6A0.10580.79950.98980.058*
H6B0.10830.80590.94760.058*
C70.1663 (5)0.7609 (2)0.89824 (14)0.0508 (8)
H7A0.32480.77410.90150.061*
H7B0.1420.68480.90460.061*
C80.0898 (5)0.7907 (2)0.83346 (13)0.0431 (7)
C90.1006 (5)0.9121 (2)0.82613 (13)0.0427 (7)
H90.25910.92930.82950.051*
C100.0094 (5)0.9779 (2)0.87791 (14)0.0426 (7)
C110.0386 (7)0.9432 (3)0.75967 (15)0.0616 (9)
H11A0.02171.02030.7570.074*
H11B0.10240.91060.74860.074*
C120.2146 (7)0.9071 (3)0.71404 (15)0.0707 (11)
H12A0.33790.95710.7150.085*
H12B0.15380.90710.67170.085*
C130.2956 (6)0.7995 (3)0.72936 (14)0.0570 (9)
C140.2399 (5)0.7472 (2)0.78524 (14)0.0501 (7)
C150.3486 (5)0.6543 (3)0.78380 (16)0.0582 (9)
H150.34310.60270.81540.07*
C160.4313 (6)0.7352 (3)0.69864 (17)0.0682 (10)
H160.49370.75090.65960.082*
C170.1383 (5)0.7425 (3)0.82164 (17)0.0604 (9)
H17A0.13160.66630.82740.091*
H17B0.24330.77270.85070.091*
H17C0.1840.75820.77930.091*
C190.1943 (8)0.9971 (5)1.0221 (2)0.0975 (17)
H19A0.2350.92351.02210.117*0.711 (4)
H19B0.28951.03280.99320.117*0.711 (4)
H19C0.25491.06721.01930.117*0.289 (4)
H19D0.18150.98161.06580.117*0.289 (4)
C200.2603 (5)0.9735 (3)0.87376 (15)0.0536 (8)
H20A0.30430.9680.83040.08*
H20B0.31370.91220.89650.08*
H20C0.32211.03750.89170.08*
O20.4677 (4)0.6453 (2)0.73026 (11)0.0691 (7)
C1A0.068 (2)1.0936 (5)0.8739 (3)0.064 (3)0.711 (4)
H1A0.00261.12770.83820.077*0.711 (4)
H1B0.22761.09460.86670.077*0.711 (4)
C2A0.0194 (11)1.1557 (4)0.9307 (3)0.075 (2)0.711 (4)
C3A0.1167 (9)1.1153 (4)0.9885 (2)0.0696 (16)0.711 (4)
H3A0.07291.15961.02340.083*0.711 (4)
C18A0.1600 (9)0.9578 (5)1.0566 (2)0.0728 (17)0.711 (4)
H18A0.15261.00681.09130.109*0.711 (4)
H18B0.09180.89121.06830.109*0.711 (4)
H18C0.31260.94551.04550.109*0.711 (4)
O1A0.0553 (13)1.2433 (4)0.9264 (2)0.138 (3)0.711 (4)
O3A0.3520 (7)1.1171 (4)0.9831 (3)0.122 (2)0.711 (4)
H3C0.40021.17340.99790.184*0.711 (4)
O4A0.2338 (7)1.0376 (3)1.08184 (14)0.0747 (12)0.711 (4)
H4A0.31321.09211.07980.112*0.711 (4)
C1B0.061 (4)1.0965 (10)0.8597 (5)0.036 (4)*0.289 (4)
H1C0.04691.12660.83080.043*0.289 (4)
H1D0.20441.09530.83870.043*0.289 (4)
C2B0.075 (2)1.1633 (8)0.9161 (3)0.038 (3)*0.289 (4)
C3B0.0392 (16)1.1235 (6)0.9713 (4)0.047 (3)*0.289 (4)
H3B0.19481.11950.96140.056*0.289 (4)
C18B0.234 (2)1.0258 (11)1.0353 (6)0.068 (4)*0.289 (4)
H18D0.22921.09671.05270.102*0.289 (4)
H18E0.24390.97441.06880.102*0.289 (4)
H18F0.3621.01911.00850.102*0.289 (4)
O1B0.1966 (15)1.2381 (7)0.9173 (4)0.078 (3)*0.289 (4)
O3B0.0141 (14)1.1955 (6)1.0224 (3)0.062 (2)*0.289 (4)
H3D0.11781.21951.04430.094*0.289 (4)
O4B0.333 (3)0.9385 (14)1.0034 (7)0.133 (5)*0.289 (4)
H4B0.37460.89941.03220.2*0.289 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C40.0435 (17)0.064 (2)0.0571 (18)0.0035 (15)0.0039 (15)0.0157 (15)
C50.0296 (13)0.0474 (16)0.0471 (15)0.0006 (12)0.0008 (11)0.0038 (12)
C60.0516 (17)0.0500 (17)0.0441 (15)0.0054 (14)0.0016 (14)0.0111 (12)
C70.0579 (18)0.0356 (15)0.0589 (18)0.0045 (14)0.0027 (15)0.0057 (13)
C80.0385 (16)0.0410 (15)0.0498 (16)0.0043 (12)0.0066 (12)0.0029 (13)
C90.0425 (16)0.0397 (15)0.0457 (15)0.0006 (12)0.0001 (13)0.0067 (12)
C100.0382 (15)0.0377 (15)0.0518 (16)0.0007 (12)0.0036 (13)0.0066 (12)
C110.070 (2)0.067 (2)0.0480 (17)0.0027 (18)0.0007 (16)0.0122 (15)
C120.081 (3)0.087 (3)0.0449 (17)0.003 (2)0.0136 (18)0.0046 (17)
C130.053 (2)0.066 (2)0.0520 (17)0.0077 (16)0.0009 (15)0.0141 (16)
C140.0412 (15)0.0509 (17)0.0581 (17)0.0077 (14)0.0045 (14)0.0156 (14)
C150.0500 (18)0.0565 (19)0.068 (2)0.0066 (16)0.0044 (16)0.0235 (17)
C160.065 (2)0.082 (3)0.0569 (19)0.006 (2)0.0017 (17)0.0231 (19)
C170.0490 (18)0.058 (2)0.074 (2)0.0157 (16)0.0023 (16)0.0117 (17)
C190.083 (3)0.139 (4)0.071 (3)0.020 (3)0.030 (2)0.034 (3)
C200.0413 (16)0.063 (2)0.0564 (18)0.0124 (15)0.0027 (15)0.0145 (15)
O20.0577 (14)0.0758 (17)0.0738 (16)0.0007 (13)0.0050 (12)0.0355 (14)
C1A0.089 (5)0.042 (3)0.061 (4)0.004 (2)0.026 (4)0.015 (3)
C2A0.115 (6)0.037 (3)0.073 (4)0.008 (3)0.035 (4)0.002 (3)
C3A0.076 (4)0.062 (3)0.071 (3)0.001 (3)0.008 (3)0.034 (3)
C18A0.064 (3)0.112 (5)0.043 (2)0.007 (3)0.010 (2)0.022 (3)
O1A0.206 (7)0.083 (3)0.125 (4)0.080 (4)0.018 (4)0.032 (3)
O3A0.066 (3)0.105 (4)0.197 (6)0.014 (3)0.014 (3)0.080 (4)
O4A0.076 (2)0.099 (3)0.0491 (18)0.026 (2)0.0184 (17)0.0074 (17)
Geometric parameters (Å, º) top
C4—C18B1.479 (13)C17—H17A0.98
C4—C3A1.494 (6)C17—H17B0.98
C4—C191.498 (6)C17—H17C0.98
C4—C51.565 (4)C19—O4B1.201 (17)
C4—C18A1.593 (6)C19—O4A1.414 (5)
C4—C3B1.671 (10)C19—H19A0.97
C5—C61.522 (4)C19—H19B0.9699
C5—C101.557 (4)C19—H19C0.97
C5—H51C19—H19D0.97
C6—C71.524 (4)C20—H20A0.98
C6—H6A0.99C20—H20B0.98
C6—H6B0.99C20—H20C0.98
C7—C81.529 (4)C1A—C2A1.492 (7)
C7—H7A0.99C1A—H1A0.99
C7—H7B0.99C1A—H1B0.99
C8—C141.500 (4)C2A—O1A1.210 (6)
C8—C171.550 (4)C2A—C3A1.481 (8)
C8—C91.557 (4)C3A—O3A1.450 (6)
C9—C111.541 (4)C3A—H3A0.98
C9—C101.555 (4)C18A—H18A0.98
C9—H91C18A—H18B0.98
C10—C201.545 (4)C18A—H18C0.98
C10—C1A1.552 (7)O3A—H3C0.84
C10—C1B1.621 (14)O4A—H4A0.8505
C11—C121.535 (5)C1B—C2B1.491 (7)
C11—H11A0.99C1B—H1C0.99
C11—H11B0.99C1B—H1D0.99
C12—C131.495 (6)C2B—O1B1.210 (6)
C12—H12A0.99C2B—C3B1.477 (8)
C12—H12B0.99C3B—O3B1.447 (7)
C13—C161.345 (5)C3B—H3B0.98
C13—C141.424 (5)C18B—H18D0.98
C14—C151.359 (5)C18B—H18E0.98
C15—O21.376 (4)C18B—H18F0.98
C15—H150.95O3B—H3D0.8504
C16—O21.353 (5)O4B—H4B0.84
C16—H160.95
C18B—C4—C19127.8 (6)C13—C16—H16124.2
C3A—C4—C19116.2 (4)O2—C16—H16124.2
C18B—C4—C5110.9 (6)C8—C17—H17A109.5
C3A—C4—C5108.8 (3)C8—C17—H17B109.5
C19—C4—C5114.7 (3)H17A—C17—H17B109.5
C3A—C4—C18A108.4 (4)C8—C17—H17C109.5
C19—C4—C18A99.2 (4)H17A—C17—H17C109.5
C5—C4—C18A108.9 (3)H17B—C17—H17C109.5
C18B—C4—C3B105.5 (6)O4B—C19—C4126.8 (9)
C19—C4—C3B86.4 (4)O4A—C19—C4116.1 (4)
C5—C4—C3B104.8 (3)O4A—C19—H19A108
C6—C5—C10111.5 (2)C4—C19—H19A108.5
C6—C5—C4114.3 (2)O4A—C19—H19B108.4
C10—C5—C4116.9 (2)C4—C19—H19B108.2
C6—C5—H5104.1H19A—C19—H19B107.3
C10—C5—H5104.1O4B—C19—H19C106.3
C4—C5—H5104.1C4—C19—H19C105.4
C5—C6—C7109.9 (2)O4B—C19—H19D105.1
C5—C6—H6A109.7C4—C19—H19D105.5
C7—C6—H6A109.7H19C—C19—H19D106.2
C5—C6—H6B109.7C10—C20—H20A109.5
C7—C6—H6B109.7C10—C20—H20B109.5
H6A—C6—H6B108.2H20A—C20—H20B109.5
C6—C7—C8113.1 (2)C10—C20—H20C109.5
C6—C7—H7A109H20A—C20—H20C109.5
C8—C7—H7A109H20B—C20—H20C109.5
C6—C7—H7B109C16—O2—C15105.6 (3)
C8—C7—H7B109C2A—C1A—C10113.3 (5)
H7A—C7—H7B107.8C2A—C1A—H1A108.9
C14—C8—C7111.0 (2)C10—C1A—H1A108.9
C14—C8—C17107.1 (2)C2A—C1A—H1B108.9
C7—C8—C17109.3 (3)C10—C1A—H1B108.9
C14—C8—C9105.7 (2)H1A—C1A—H1B107.7
C7—C8—C9109.1 (2)O1A—C2A—C3A122.6 (5)
C17—C8—C9114.5 (3)O1A—C2A—C1A120.1 (6)
C11—C9—C10115.4 (2)C3A—C2A—C1A115.6 (5)
C11—C9—C8109.9 (3)C1A—C2A—H3B111.7
C10—C9—C8116.3 (2)O3A—C3A—C2A109.1 (5)
C11—C9—H9104.6O3A—C3A—C4111.3 (4)
C10—C9—H9104.6C2A—C3A—C4108.3 (4)
C8—C9—H9104.6O3A—C3A—H3A109.1
C20—C10—C1A109.8 (5)C2A—C3A—H3A110
C20—C10—C9111.8 (3)C4—C3A—H3A109
C1A—C10—C9109.8 (3)C4—C18A—H18A109.5
C20—C10—C5114.4 (2)C4—C18A—H18B109.5
C1A—C10—C5103.7 (4)C4—C18A—H18C109.5
C9—C10—C5107.0 (2)C19—O4A—H4A110.4
C20—C10—C1B106.7 (9)C2B—C1B—C10110.3 (7)
C9—C10—C1B102.1 (5)C2B—C1B—H1C109.6
C5—C10—C1B114.2 (6)C10—C1B—H1C109.6
C12—C11—C9110.6 (3)C2B—C1B—H1D109.6
C12—C11—H11A109.5C10—C1B—H1D109.6
C9—C11—H11A109.5H1C—C1B—H1D108.1
C12—C11—H11B109.5O1B—C2B—C3B123.0 (5)
C9—C11—H11B109.5O1B—C2B—C1B120.2 (8)
H11A—C11—H11B108.1C3B—C2B—C1B116.1 (6)
C13—C12—C11111.4 (3)O3B—C3B—C2B110.6 (5)
C13—C12—H12A109.3O3B—C3B—C4105.2 (6)
C11—C12—H12A109.3C2B—C3B—C4117.9 (8)
C13—C12—H12B109.3C2B—C3B—H3A107.8
C11—C12—H12B109.3O3B—C3B—H3B107.7
H12A—C12—H12B108C2B—C3B—H3B107.7
C16—C13—C14106.5 (3)C4—C3B—H3B107.2
C16—C13—C12130.9 (3)C4—C18B—H18D109.5
C14—C13—C12122.6 (3)C4—C18B—H18E109.5
C15—C14—C13105.7 (3)H18D—C18B—H18E109.5
C15—C14—C8129.8 (3)C4—C18B—H18F109.5
C13—C14—C8124.5 (3)H18D—C18B—H18F109.5
C14—C15—O2110.7 (3)H18E—C18B—H18F109.5
C14—C15—H15124.7C3B—O3B—H3D125.1
O2—C15—H15124.7C19—O4B—H4B109.5
C13—C16—O2111.6 (3)
C18B—C4—C5—C694.9 (7)C14—C13—C16—O20.0 (4)
C3A—C4—C5—C6169.2 (3)C12—C13—C16—O2177.8 (3)
C19—C4—C5—C658.9 (4)C18B—C4—C19—O4B142.7 (13)
C18A—C4—C5—C651.2 (4)C3A—C4—C19—O4B134.2 (12)
C3B—C4—C5—C6151.7 (4)C5—C4—C19—O4B5.9 (13)
C18B—C4—C5—C10132.2 (7)C18A—C4—C19—O4B110.0 (12)
C3A—C4—C5—C1058.0 (4)C3B—C4—C19—O4B110.5 (12)
C19—C4—C5—C1074.0 (4)C18B—C4—C19—O4A17.8 (9)
C18A—C4—C5—C10176.0 (3)C3A—C4—C19—O4A65.3 (6)
C3B—C4—C5—C1018.9 (4)C5—C4—C19—O4A166.4 (4)
C10—C5—C6—C761.8 (3)C18A—C4—C19—O4A50.6 (6)
C4—C5—C6—C7162.8 (2)C3B—C4—C19—O4A89.0 (5)
C5—C6—C7—C859.0 (3)C13—C16—O2—C150.2 (4)
C6—C7—C8—C14167.8 (3)C14—C15—O2—C160.3 (3)
C6—C7—C8—C1774.3 (3)C20—C10—C1A—C2A71.9 (8)
C6—C7—C8—C951.7 (3)C9—C10—C1A—C2A164.8 (6)
C14—C8—C9—C1156.8 (3)C5—C10—C1A—C2A50.8 (9)
C7—C8—C9—C11176.2 (3)C1B—C10—C1A—C2A147 (7)
C17—C8—C9—C1160.8 (4)C10—C1A—C2A—O1A135.3 (8)
C14—C8—C9—C10169.8 (2)C10—C1A—C2A—C3A59.3 (10)
C7—C8—C9—C1050.3 (3)O1A—C2A—C3A—O3A103.1 (8)
C17—C8—C9—C1072.6 (3)C1A—C2A—C3A—O3A61.9 (7)
C11—C9—C10—C2057.5 (3)O1A—C2A—C3A—C4135.6 (7)
C8—C9—C10—C2073.4 (3)C1A—C2A—C3A—C459.4 (7)
C11—C9—C10—C1A64.6 (6)C18B—C4—C3A—O3A41.1 (7)
C8—C9—C10—C1A164.5 (5)C19—C4—C3A—O3A164.0 (4)
C11—C9—C10—C5176.5 (3)C5—C4—C3A—O3A64.9 (5)
C8—C9—C10—C552.6 (3)C18A—C4—C3A—O3A53.4 (5)
C11—C9—C10—C1B56.2 (8)C3B—C4—C3A—O3A155.0 (7)
C8—C9—C10—C1B172.9 (8)C18B—C4—C3A—C2A161.0 (7)
C6—C5—C10—C2067.4 (3)C19—C4—C3A—C2A76.1 (5)
C4—C5—C10—C2066.7 (4)C5—C4—C3A—C2A55.1 (4)
C6—C5—C10—C1A173.1 (4)C18A—C4—C3A—C2A173.4 (4)
C4—C5—C10—C1A52.8 (5)C3B—C4—C3A—C2A35.0 (4)
C6—C5—C10—C957.1 (3)C20—C10—C1B—C2B91.6 (14)
C4—C5—C10—C9168.8 (2)C1A—C10—C1B—C2B16 (5)
C6—C5—C10—C1B169.3 (8)C9—C10—C1B—C2B150.9 (12)
C4—C5—C10—C1B56.6 (8)C5—C10—C1B—C2B35.8 (17)
C10—C9—C11—C12157.5 (3)C10—C1B—C2B—O1B152.4 (13)
C8—C9—C11—C1268.6 (4)C10—C1B—C2B—C3B19 (2)
C9—C11—C12—C1341.5 (4)O1B—C2B—C3B—O3B9.5 (17)
C11—C12—C13—C16172.7 (4)C1B—C2B—C3B—O3B179.7 (13)
C11—C12—C13—C149.7 (5)O1B—C2B—C3B—C4111.6 (12)
C16—C13—C14—C150.2 (3)C1B—C2B—C3B—C459.2 (15)
C12—C13—C14—C15177.9 (3)C18B—C4—C3B—O3B43.6 (9)
C16—C13—C14—C8179.5 (3)C3A—C4—C3B—O3B59.2 (7)
C12—C13—C14—C82.4 (5)C19—C4—C3B—O3B84.6 (6)
C7—C8—C14—C1536.6 (4)C5—C4—C3B—O3B160.8 (5)
C17—C8—C14—C1582.7 (4)C18A—C4—C3B—O3B15.2 (10)
C9—C8—C14—C15154.8 (3)C18B—C4—C3B—C2B80.2 (9)
C7—C8—C14—C13143.8 (3)C3A—C4—C3B—C2B64.7 (7)
C17—C8—C14—C1396.9 (3)C19—C4—C3B—C2B151.5 (6)
C9—C8—C14—C1325.6 (4)C5—C4—C3B—C2B37.0 (7)
C13—C14—C15—O20.3 (3)C18A—C4—C3B—C2B108.6 (7)
C8—C14—C15—O2179.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3A—H3C···O1Ai0.841.972.709 (6)146
O3B—H3D···O1Bii0.851.512.362 (13)180
Symmetry codes: (i) x1/2, y+5/2, z+2; (ii) x+1/2, y+5/2, z+2.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC20H28O2C20H28O4C20H28O4
Mr300.42332.42332.42
Crystal system, space groupMonoclinic, P21Monoclinic, P21Orthorhombic, P212121
Temperature (K)130130130
a, b, c (Å)12.3336 (1), 7.4124 (1), 18.2476 (1)9.5317 (1), 7.8958 (1), 11.6742 (1)6.1411 (1), 12.7415 (3), 21.6714 (5)
α, β, γ (°)90, 101.930 (1), 9090, 101.734 (1), 9090, 90, 90
V3)1632.19 (3)860.24 (2)1695.72 (6)
Z424
Radiation typeCu KαCu KαCu Kα
µ (mm1)0.590.710.72
Crystal size (mm)0.3 × 0.3 × 0.10.3 × 0.2 × 0.20.5 × 0.5 × 0.15
Data collection
DiffractometerOxford Diffraction Gemini S Ultra
diffractometer
Oxford Diffraction Gemini S Ultra
diffractometer
Oxford Diffraction Gemini S Ultra
diffractometer
Absorption correctionMulti-scan
[CrysAlis RED (Oxford Diffraction, 2008); empirical (using intensity measurements) absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm]
Tmin, Tmax0.640, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
26930, 5168, 4826 16202, 2624, 2583 26592, 2683, 2448
Rint0.0340.0240.038
θmax (°)62.362.662.5
(sin θ/λ)max1)0.5740.5760.575
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.070, 1.05 0.045, 0.119, 1.11 0.056, 0.155, 1.09
No. of reflections516826242683
No. of parameters406222253
No. of restraints119
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.17, 0.140.22, 0.210.42, 0.24
Absolute structureFlack (1983), with how many Friedel pairs?Flack (1983), with how many Friedel pairs?Flack (1983), with how many Friedel pairs?
Absolute structure parameter0.06 (14)0.2 (2)0.1 (5)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLUTON (Spek, 1991), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O4i0.841.942.760 (2)166
O4—H4···O30.842.052.715 (2)136.2
Symmetry code: (i) x, y1/2, z+1.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
O3A—H3C···O1Ai0.841.972.709 (6)145.7
O3B—H3D···O1Bii0.851.512.362 (13)179.5
Symmetry codes: (i) x1/2, y+5/2, z+2; (ii) x+1/2, y+5/2, z+2.
 

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