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research papers
of the cytotoxic macrocyclic trichothecene Isororidin A
aDivision of Pharmacognosy and Natural Products Chemistry, Department of Pharmacy, School of Health Sciences, National and Kapodistrian University of Athens, Athens 15771, Greece, bDepartment of Chemistry, Faculty of Science, Al-Azhar University, Assiut branch, Assiut 71524, Egypt, cInstitute of Chemical Biology, National Hellenic Research Foundation, 48 Vassileos Constantinou Avenue, Athens 11635, Greece, and dBotany and Microbiology Department, Faculty of Science, Assiut University, Egypt
*Correspondence e-mail: echrysina@eie.gr, abatis@pharm.uoa.gr
The highly cytotoxic macrocyclic trichothecene Isororidin A (C29H40O9) was isolated from the fungus Myrothesium verrucaria endophytic on the wild medicinal plant `Datura' (Datura stramonium L.) and was characterized by one- (1D) and two-dimensional (2D) NMR spectroscopy. The three-dimensional structure of Isororidin A has been confirmed by X-ray crystallography at 0.81 Å resolution from crystals grown in the orthorhombic P212121, with one molecule per Isororidin A is the epimer of previously described (by X-ray crystallography) Roridin A at position C-13′ of the macrocyclic ring.
1. Introduction
Macrocyclic trichothecenes (MTs) constitute the second major group (the other being the simple trichothecenes) of a class of highly functionalized sesquiterpenoid ; Shank et al., 2011
; Wu et al., 2017
). Most trichothecenes are at least tetracyclic, as they contain a spiro-epoxide group in the 12–13 position of the `trichothecane' sesquiterpene skeleton. They also usually comprise a double bond at C9—C10; thus, they are considered as 12–13 epoxy-trichothec-9-ene derivatives [see (a) in Scheme 1
]. In MTs, an extra cyclic diester or triester ring is connected to the trichothecene core skeleton at C-4 and C-15, making them pentacyclic The presence of the spiro-epoxy group, the Δ9,10 bond and the macrocyclic ring in the molecule appear to be crucial for their biological properties, which include antifungal, antimalarial, antivirus and anticancer activity (de Carvalho et al., 2015
; Jarvis & Mazzola, 1982
; McCormick et al., 2011
; Wu et al., 2017
). The MTs are further classified into the subgroups of the Roridoids, to which Roridin A and Isororidin A belong [see (b) and (c) in Scheme 1
, respectively], the Baccharinoids, the Verrucaroids and the Trichoverroids, which are considered the biosynthetic precursors of the three former subgroups of MTs (Bräse et al., 2009
).
There has been a series of articles since the 1980s concerning the elucidation of the configuration of the stereogenic centres of the macrocyclic ring of the MTs, especially C-6′ and C-13′ in the Roridoids (Jarvis et al., 1982, 1987
, 1996
; Jarvis & Wang, 1999
). The task was based mainly on NMR spectroscopy (despite the technical limitations of the method at that time), as well as chemical manipulations when there were adequate quantities available, aided – in rare cases – by and X-ray diffraction analyses. In 1982, Jarvis and co-workers isolated Roridin A and Isororidin A from a large-scale of Myrothesium verrucaria and resolved the of Roridin A by X-ray crystallography. The of Roridin A was confirmed after oxidative cleavage of its hydroxyethyl moiety, which produced Verrucarin A, an MT whose absolute configuration had already been established (Jarvis et al., 1982
). The 1H and 13C NMR spectra of Roridin A and Isororidin A in CDCl3 were almost identical, except for carbon C-6′, which differed in the 13C NMR spectra by 1.1 ppm. The epimeric relation of the two fungal metabolites at C-13′ was deduced indirectly by the selective hydrogenation of Roridin A and Isororidin A to their respective tetrahydro derivatives, and then oxidation of the C-6′ hydroxyethyl group of these tetrahydro derivatives to an identical (in the 1H NMR spectrum) corresponding methyl ketone (Jarvis et al., 1982
). Even though Isororidin A was re-isolated a few times in subsequent years from different fungal strains and by different research groups, verification of its structure was performed only by comparison of the NMR data in CDCl3 with those reported in 1982, but without submitting the NMR data. Isororidin A is one of the most cytotoxic metabolites among all compounds containing C, H and O, and was on the shortlist of the National Cancer Institute (NCI) for the most promising anticancer agents in the 2000s (Amagata et al., 2003
; de Carvalho et al., 2015
; Sy-Cordero et al., 2010
). The mechanism of action of the macrocyclic trichothecenes is still underexplored, possibly due to their severe general cytotoxicity. However, there is evidence that MTs show large variations in both activity and selectivity against different cancer cell lines induced by alterations in their molecular structure. These findings indicate that MTs may still be considered as highly promising antitumour agents, as long as more detailed structure–activity relationship (SAR) and quantitative structure–activity relationship (QSAR) studies have been performed. For these studies, knowledge of the configuration and conformation of the MTs is undoubtedly critical (Wu et al., 2017
; Zhu et al., 2020
). In the current article, Isororidin A was isolated from the fungus Myrothesium verrucaria endophytic on the wild medicinal plant `Datura' (Datura stramonium L.) and was characterized by 1D and 2D NMR spectroscopy. Its is presented for the first time at 0.81 Å resolution.
2. Experimental
2.1. Isolation and crystallization
Isororidin A was isolated as a colourless solid (19.5 mg) after high-performance 3OD are reported for the first time (see the Analytical data section in the supporting information and Table 1). The of its chiral centres was deduced from a combined study of nuclear Overhauser effect (NOE) correlations and 3JHH coupling constants, and by comparison with the NMR data of other Roridoids having similar structures (Amagata et al., 2003
; Jarvis & Wang, 1999
). The of all its chiral centres was confirmed by the X-ray crystallographic analysis of its colourless needle-like crystals that were obtained after the slow evaporation of a solution in methanol from an NMR tube. Most of the Isororidin A crystals had morphological defects that may have led to twinned spots on the diffraction pattern and potential issues at the stage of processing and deconvolution. Therefore, a small fragment of an Isororidin A crystal, with the least morphological defects, was isolated and mounted on a litho loop to minimize the background contribution when exposed to X-rays. The loop was placed on the goniometer head and diffraction data were collected at 0.81 Å resolution.
|
2.2. Refinement
Crystal data, data collection and structure . Details of the geometry of the Isororidin A regarding bond lengths (Å), bond angles (°), torsion angles (°) and the geometry of the hydrogen bonds [distances (Å) and angles (°)] are presented in the supporting information (Tables S1–S5).
|
3. Results and discussion
3.1. Structural commentary
The M. verrucaria, after a series of chromatographic separations, is presented at 0.81 Å resolution and confirms the configuration at position C13′. Isororidin A crystallized in the orthorhombic P212121 (No. 19). A data set was initially collected at room temperature at 0.81 Å resolution (Table S1 in the supporting information) and the calculated (Flack, 1983; Parsons et al., 2013
) was 0.4 (4), which was not sufficient to assess the of Isororidin A. Therefore, a new data set was collected at 100 K. The and remained P212121, with unit-cell dimensions a = 9.2707 (4), b = 15.2236 (6), c = 20.0806 (8) Å and α = β = γ = 90°, and the calculated for this structure was −0.02 (3), confirming the of Isororidin A. The experimental details are summarized in Table 2
and Tables S2–S6 of the supporting information. The two experiments reveal no temperature-dependent phase change, as the unit-cell parameters are almost identical (Table 2
and Table S1). The measurement at 100 K resulted in an overall better data set with an improved R parameter and a higher precision Therefore, the structure analysis that follows focuses on the structure determined at 100 K.
The packing of the molecules is stabilized by two intermolecular hydrogen-bond interactions between atom O7, which acts as a donor to symmetry-related O8i and O8, which acts as a donor to symmetry-related O2ii, as well as intermolecular C—H⋯O interactions between C4 and O1iii, C13 and O9iv, and C7′ and O6v (see Table 3 for symmetry codes). A schematic representation of the showing the stereoconfiguration of Isororidin A and its packing within the is presented in Fig. 1
.
|
![]() | Figure 1 (a) Schematic representation of the Isororidin A X-ray diffraction solution, drawn with 50% probability displacement ellipsoids. O atoms are shown in red, C atoms in light grey and H atoms in pale pink. The absolute configurations of C6′ (R) and C13′ (S) shown in Scheme 1 ![]() |
Superposition of the et al., 1982) showed that the overall structure is the same; more pronounced differences are observed in the macrocyclic ring, more specifically, in the vicinity of the C13′ atom [Figs. 1
(a) and 2
]. Both saturated pyran rings adopt distorted chair conformations, with a torsion angle C5—C6—C11—O1 of −46.7 (2)° in Isororidin A versus −41.5° in Roridin A. The unsaturated cyclohexene rings adopt flattened half-chair conformations, while the five-membered rings in both structures adopt envelope conformations, with the C atom at position C12 (C11 for the Roridin A structure) pointing out of the plane. The differences observed between the two structures relate to the hydroxyethyl group and neighbouring atoms that include a significant rotation of the torsion angles O4—C6′—C13′—O8 and C7′—C6′—C13′—O8 by 106.7 and 104.6°, respectively. Additional differences are observed for torsion angles O7—C2′—C3′—C4′ by 18.4°, O7—C2′—C3′—C12′ by 17.2°, O9—C11′—C10′—C9′ by 17.7°, O5—C11′—C10′—C9′ by 16.2°, C7′—C6′—C13′—C14′ by 10.9°, O4—C6′—C13′—C14′ by 9.2° and O6—C1′—C2′—C3′ by 7.3°. The rest of the differences in the torsion angles observed in the 18-membered macrocyclic ring are less profound and in the range of 5°; for example, torsion angle O6—C1′—C2′—O7′ by 4.2° (Table S7 in the supporting information). These changes may be attributed to the intermolecular interactions formed in Isororidin A compared to Roridin A [Fig. 1
(b)].
![]() | Figure 2 Superposition of the three-dimensional structures of determined Isororidin A (with an S configuration at C13′) and its stereoisomer (epimeric at C28 with an R configuration) Roridin A. Isororidin A is shown in red and Roridin A in grey. |
3.2. Supramolecular features
A schematic representation of the structure of Isororidin A and its packing with symmetry-related molecules within the crystal is shown in Fig. 3. Isororidin A crystallized in the orthorhombic P212121. The difference observed in the epimeric C atom seems to foster the intermolecular interactions within the Atom O8 is hydrogen bonded to O2 of a symmetry-related molecule within the while in the case of Roridin A, the same atom interacts with O1.
![]() | Figure 3 Schematic representation of the supramolecular structure of Isororidin A. The asymmetric unit is highlighted in black and the hydrogen bonds are indicated in blue. [Symmetry codes: (i) −x+, y − |
3.3. Database survey
One entry is available in the Cambridge Structural Database (CSD; Groom et al., 2016) for the structure of Roridin A (CCDC deposition No. 1110357, CSD refcode BIDPIN10; Jarvis et al., 1982
) determined in the P21 with unit-cell dimensions a = 10.197 (3), b = 14.079 (4), c = 9.606 (2) Å, α = γ = 90° and β = 94.6 (1)°.
Supporting information
https://doi.org/10.1107/S2053229624006144/ux3006sup1.cif
contains datablocks I, II, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2053229624006144/ux3006Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2053229624006144/ux3006Isup3.cdx
Additional data for the room-temperature determination. DOI: https://doi.org/10.1107/S2053229624006144/ux3006sup4.pdf
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2053229624006144/ux3006IIsup5.hkl
C29H40O9 | Dx = 1.248 Mg m−3 |
Mr = 532.61 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, P212121 | Cell parameters from 9959 reflections |
a = 9.2707 (4) Å | θ = 4.4–74.9° |
b = 15.2236 (6) Å | µ = 0.76 mm−1 |
c = 20.0806 (8) Å | T = 100 K |
V = 2834.0 (2) Å3 | Irregular, colourless |
Z = 4 | 0.08 × 0.06 × 0.04 mm |
F(000) = 1144 |
Bruker APEXII diffractometer | 5548 independent reflections |
Radiation source: sealed x-ray tube | 5338 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
φ or ω oscillation scans | θmax = 72.1°, θmin = 3.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2021) | h = −11→11 |
Tmin = 0.673, Tmax = 0.754 | k = −18→18 |
101717 measured reflections | l = −24→24 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.041 | w = 1/[σ2(Fo2) + (0.0618P)2 + 1.0952P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.109 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 0.34 e Å−3 |
5548 reflections | Δρmin = −0.22 e Å−3 |
349 parameters | Absolute structure: Flack x determined using 2264 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
0 restraints | Absolute structure parameter: −0.02 (3) |
Primary atom site location: difference Fourier map |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.88908 (18) | 0.27189 (12) | 0.51273 (8) | 0.0240 (4) | |
O2 | 0.9025 (2) | 0.38349 (12) | 0.67471 (9) | 0.0272 (4) | |
O3 | 0.55743 (19) | 0.51939 (11) | 0.47181 (9) | 0.0247 (4) | |
O4 | 0.1743 (2) | 0.69785 (13) | 0.64506 (9) | 0.0308 (4) | |
O5 | 0.55825 (19) | 0.34501 (11) | 0.66449 (8) | 0.0220 (4) | |
O6 | 0.3838 (2) | 0.49608 (15) | 0.39552 (11) | 0.0424 (5) | |
O7 | 0.2988 (2) | 0.66973 (14) | 0.40501 (10) | 0.0397 (5) | |
H7 | 0.337967 | 0.671580 | 0.367303 | 0.060* | |
O8 | −0.0389 (2) | 0.80771 (13) | 0.70903 (10) | 0.0361 (5) | |
H8 | 0.003475 | 0.841615 | 0.735599 | 0.054* | |
O9 | 0.37443 (19) | 0.41830 (12) | 0.61579 (9) | 0.0269 (4) | |
C2 | 0.8665 (3) | 0.27417 (17) | 0.58343 (12) | 0.0239 (5) | |
H2 | 0.941895 | 0.239374 | 0.607361 | 0.029* | |
C3 | 0.7140 (3) | 0.24545 (15) | 0.60435 (12) | 0.0237 (5) | |
H3A | 0.714192 | 0.222712 | 0.650543 | 0.028* | |
H3B | 0.677134 | 0.199050 | 0.574293 | 0.028* | |
C4 | 0.6207 (3) | 0.32912 (15) | 0.59909 (11) | 0.0198 (5) | |
H4 | 0.543332 | 0.321485 | 0.564896 | 0.024* | |
C5 | 0.7257 (2) | 0.40513 (16) | 0.57878 (12) | 0.0189 (5) | |
C6 | 0.7370 (3) | 0.40627 (15) | 0.50005 (11) | 0.0194 (5) | |
C7 | 0.8563 (3) | 0.46869 (17) | 0.47578 (13) | 0.0255 (5) | |
H7A | 0.835163 | 0.528884 | 0.491673 | 0.031* | |
H7B | 0.949524 | 0.450303 | 0.495403 | 0.031* | |
C8 | 0.8701 (3) | 0.46984 (18) | 0.39997 (13) | 0.0301 (6) | |
H8A | 0.790742 | 0.505592 | 0.381129 | 0.036* | |
H8B | 0.962284 | 0.498322 | 0.387684 | 0.036* | |
C9 | 0.8652 (3) | 0.37965 (19) | 0.36967 (12) | 0.0280 (6) | |
C10 | 0.8205 (3) | 0.31031 (17) | 0.40345 (12) | 0.0250 (5) | |
H10 | 0.818015 | 0.255442 | 0.380946 | 0.030* | |
C11 | 0.7731 (3) | 0.31230 (16) | 0.47532 (11) | 0.0209 (5) | |
H11 | 0.684913 | 0.275005 | 0.480016 | 0.025* | |
C12 | 0.8689 (3) | 0.36850 (17) | 0.60468 (12) | 0.0226 (5) | |
C13 | 0.9983 (3) | 0.4175 (2) | 0.62296 (13) | 0.0289 (6) | |
H13A | 0.998626 | 0.481667 | 0.614993 | 0.035* | |
H13B | 1.092774 | 0.388245 | 0.616854 | 0.035* | |
C14 | 0.6885 (3) | 0.49472 (15) | 0.60854 (13) | 0.0228 (5) | |
H14A | 0.758586 | 0.538439 | 0.593183 | 0.034* | |
H14B | 0.691533 | 0.491081 | 0.657245 | 0.034* | |
H14C | 0.591501 | 0.512065 | 0.594273 | 0.034* | |
C15 | 0.5923 (3) | 0.42707 (16) | 0.46636 (12) | 0.0221 (5) | |
H15A | 0.597356 | 0.410455 | 0.418753 | 0.027* | |
H15B | 0.515051 | 0.391867 | 0.487463 | 0.027* | |
C16 | 0.9125 (3) | 0.3731 (2) | 0.29815 (14) | 0.0380 (7) | |
H16A | 1.014581 | 0.389273 | 0.294656 | 0.057* | |
H16B | 0.854565 | 0.413067 | 0.270815 | 0.057* | |
H16C | 0.899321 | 0.312700 | 0.282417 | 0.057* | |
C1' | 0.4428 (3) | 0.54367 (19) | 0.43490 (13) | 0.0296 (6) | |
C2' | 0.3983 (3) | 0.63724 (18) | 0.45204 (13) | 0.0287 (6) | |
H2' | 0.485817 | 0.675635 | 0.452173 | 0.034* | |
C3' | 0.3294 (3) | 0.63843 (18) | 0.52177 (14) | 0.0291 (6) | |
H3' | 0.395944 | 0.606240 | 0.552451 | 0.035* | |
C4' | 0.3149 (4) | 0.7322 (2) | 0.54813 (16) | 0.0407 (7) | |
H4'A | 0.399591 | 0.766598 | 0.533323 | 0.049* | |
H4'B | 0.228023 | 0.759272 | 0.528101 | 0.049* | |
C5' | 0.3034 (4) | 0.7386 (2) | 0.62343 (17) | 0.0407 (7) | |
H5'A | 0.387367 | 0.709419 | 0.644329 | 0.049* | |
H5'B | 0.303563 | 0.801101 | 0.637090 | 0.049* | |
C6' | 0.1495 (3) | 0.69731 (18) | 0.71470 (13) | 0.0274 (5) | |
H6' | 0.209471 | 0.744725 | 0.735249 | 0.033* | |
C7' | 0.1896 (3) | 0.61153 (17) | 0.74684 (13) | 0.0277 (5) | |
H7' | 0.166965 | 0.605138 | 0.792725 | 0.033* | |
C8' | 0.2536 (3) | 0.54364 (17) | 0.71731 (13) | 0.0265 (5) | |
H8' | 0.270664 | 0.545400 | 0.670677 | 0.032* | |
C9' | 0.2979 (3) | 0.46714 (17) | 0.75504 (13) | 0.0281 (5) | |
H9' | 0.264277 | 0.463987 | 0.799677 | 0.034* | |
C10' | 0.3807 (3) | 0.40016 (17) | 0.73433 (12) | 0.0267 (5) | |
H10' | 0.406954 | 0.356344 | 0.765766 | 0.032* | |
C11' | 0.4333 (3) | 0.39102 (15) | 0.66526 (12) | 0.0231 (5) | |
C12' | 0.1877 (3) | 0.5878 (2) | 0.51995 (15) | 0.0372 (6) | |
H12A | 0.122060 | 0.615490 | 0.487947 | 0.056* | |
H12B | 0.143561 | 0.588379 | 0.564304 | 0.056* | |
H12C | 0.206171 | 0.526987 | 0.506428 | 0.056* | |
C13' | −0.0095 (3) | 0.71915 (18) | 0.72682 (13) | 0.0298 (6) | |
H13' | −0.031032 | 0.711192 | 0.775237 | 0.036* | |
C14' | −0.1081 (3) | 0.65997 (19) | 0.68701 (15) | 0.0334 (6) | |
H14D | −0.208572 | 0.677363 | 0.694432 | 0.050* | |
H14E | −0.094561 | 0.598944 | 0.701241 | 0.050* | |
H14F | −0.085000 | 0.665237 | 0.639549 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0212 (8) | 0.0305 (9) | 0.0202 (8) | 0.0080 (7) | 0.0008 (7) | 0.0009 (7) |
O2 | 0.0247 (9) | 0.0368 (10) | 0.0201 (8) | −0.0014 (8) | −0.0056 (7) | 0.0005 (7) |
O3 | 0.0238 (8) | 0.0235 (8) | 0.0268 (9) | 0.0042 (7) | −0.0031 (7) | 0.0025 (7) |
O4 | 0.0297 (10) | 0.0358 (10) | 0.0268 (9) | −0.0051 (8) | 0.0036 (8) | −0.0023 (8) |
O5 | 0.0215 (8) | 0.0251 (8) | 0.0194 (8) | 0.0011 (7) | 0.0014 (7) | −0.0021 (7) |
O6 | 0.0451 (12) | 0.0461 (12) | 0.0359 (11) | 0.0143 (10) | −0.0180 (10) | −0.0071 (9) |
O7 | 0.0404 (11) | 0.0464 (12) | 0.0324 (10) | 0.0195 (10) | 0.0088 (9) | 0.0164 (9) |
O8 | 0.0454 (12) | 0.0303 (9) | 0.0326 (10) | 0.0084 (9) | −0.0132 (9) | −0.0085 (8) |
O9 | 0.0213 (8) | 0.0327 (9) | 0.0268 (9) | 0.0046 (7) | −0.0003 (8) | −0.0053 (8) |
C2 | 0.0220 (12) | 0.0292 (13) | 0.0205 (11) | 0.0070 (10) | −0.0013 (9) | 0.0027 (10) |
C3 | 0.0282 (12) | 0.0215 (12) | 0.0216 (11) | 0.0034 (10) | 0.0038 (10) | 0.0021 (9) |
C4 | 0.0208 (11) | 0.0216 (11) | 0.0171 (11) | 0.0007 (9) | 0.0011 (9) | −0.0025 (8) |
C5 | 0.0165 (10) | 0.0210 (11) | 0.0192 (11) | 0.0011 (9) | −0.0027 (9) | −0.0016 (9) |
C6 | 0.0180 (11) | 0.0217 (11) | 0.0184 (11) | −0.0007 (9) | −0.0013 (9) | −0.0004 (9) |
C7 | 0.0232 (12) | 0.0268 (12) | 0.0265 (13) | −0.0043 (10) | −0.0015 (10) | 0.0020 (10) |
C8 | 0.0286 (13) | 0.0345 (14) | 0.0272 (13) | −0.0061 (11) | 0.0013 (11) | 0.0074 (11) |
C9 | 0.0228 (12) | 0.0406 (15) | 0.0206 (12) | 0.0018 (11) | −0.0005 (10) | 0.0004 (10) |
C10 | 0.0237 (12) | 0.0300 (12) | 0.0212 (12) | 0.0055 (11) | −0.0008 (10) | −0.0033 (10) |
C11 | 0.0194 (11) | 0.0237 (11) | 0.0196 (11) | 0.0023 (9) | 0.0002 (9) | −0.0009 (9) |
C12 | 0.0197 (11) | 0.0314 (13) | 0.0167 (11) | 0.0022 (10) | −0.0012 (9) | 0.0019 (9) |
C13 | 0.0196 (11) | 0.0413 (15) | 0.0258 (12) | −0.0022 (11) | −0.0042 (10) | 0.0028 (11) |
C14 | 0.0221 (11) | 0.0212 (11) | 0.0252 (12) | −0.0005 (9) | −0.0014 (10) | −0.0034 (9) |
C15 | 0.0211 (12) | 0.0213 (11) | 0.0240 (12) | 0.0006 (9) | −0.0042 (9) | −0.0003 (9) |
C16 | 0.0398 (17) | 0.0503 (17) | 0.0239 (13) | 0.0020 (14) | 0.0043 (12) | 0.0043 (12) |
C1' | 0.0300 (13) | 0.0345 (14) | 0.0243 (13) | 0.0043 (12) | 0.0010 (11) | 0.0051 (11) |
C2' | 0.0276 (13) | 0.0294 (13) | 0.0289 (13) | 0.0047 (11) | 0.0065 (10) | 0.0065 (10) |
C3' | 0.0295 (13) | 0.0306 (13) | 0.0272 (13) | 0.0022 (11) | 0.0054 (11) | 0.0037 (10) |
C4' | 0.0431 (17) | 0.0292 (14) | 0.0498 (18) | −0.0002 (14) | 0.0197 (15) | 0.0049 (13) |
C5' | 0.0394 (16) | 0.0319 (15) | 0.0506 (18) | −0.0101 (13) | 0.0124 (14) | −0.0109 (13) |
C6' | 0.0306 (13) | 0.0275 (12) | 0.0242 (12) | −0.0018 (11) | −0.0019 (10) | −0.0061 (10) |
C7' | 0.0275 (13) | 0.0318 (13) | 0.0238 (12) | 0.0003 (11) | −0.0022 (10) | −0.0052 (10) |
C8' | 0.0253 (12) | 0.0294 (13) | 0.0247 (12) | −0.0017 (10) | 0.0008 (10) | −0.0056 (10) |
C9' | 0.0261 (12) | 0.0326 (13) | 0.0256 (12) | −0.0030 (11) | 0.0057 (10) | −0.0040 (11) |
C10' | 0.0283 (12) | 0.0273 (12) | 0.0245 (12) | −0.0005 (11) | 0.0048 (10) | −0.0003 (10) |
C11' | 0.0222 (12) | 0.0211 (11) | 0.0259 (12) | −0.0040 (10) | 0.0024 (10) | −0.0039 (10) |
C12' | 0.0342 (15) | 0.0449 (16) | 0.0325 (14) | −0.0029 (14) | 0.0073 (12) | 0.0003 (12) |
C13' | 0.0366 (14) | 0.0313 (14) | 0.0215 (12) | 0.0046 (12) | 0.0012 (11) | −0.0049 (10) |
C14' | 0.0300 (14) | 0.0328 (14) | 0.0373 (15) | −0.0024 (12) | 0.0009 (11) | −0.0014 (11) |
O1—C2 | 1.436 (3) | C12—C13 | 1.460 (4) |
O1—C11 | 1.449 (3) | C13—H13A | 0.9900 |
O2—C12 | 1.458 (3) | C13—H13B | 0.9900 |
O2—C13 | 1.462 (3) | C14—H14A | 0.9800 |
O3—C1' | 1.347 (3) | C14—H14B | 0.9800 |
O3—C15 | 1.446 (3) | C14—H14C | 0.9800 |
O4—C5' | 1.416 (4) | C15—H15A | 0.9900 |
O4—C6' | 1.417 (3) | C15—H15B | 0.9900 |
O5—C11' | 1.354 (3) | C16—H16A | 0.9800 |
O5—C4 | 1.456 (3) | C16—H16B | 0.9800 |
O6—C1' | 1.204 (4) | C16—H16C | 0.9800 |
O7—C2' | 1.409 (3) | C1'—C2' | 1.523 (4) |
O7—H7 | 0.8400 | C2'—C3' | 1.539 (4) |
O8—C13' | 1.421 (3) | C2'—H2' | 1.0000 |
O8—H8 | 0.8400 | C3'—C12' | 1.524 (4) |
O9—C11' | 1.207 (3) | C3'—C4' | 1.528 (4) |
C2—C12 | 1.498 (4) | C3'—H3' | 1.0000 |
C2—C3 | 1.538 (3) | C4'—C5' | 1.519 (4) |
C2—H2 | 1.0000 | C4'—H4'A | 0.9900 |
C3—C4 | 1.543 (3) | C4'—H4'B | 0.9900 |
C3—H3A | 0.9900 | C5'—H5'A | 0.9900 |
C3—H3B | 0.9900 | C5'—H5'B | 0.9900 |
C4—C5 | 1.566 (3) | C6'—C7' | 1.503 (4) |
C4—H4 | 1.0000 | C6'—C13' | 1.530 (4) |
C5—C14 | 1.528 (3) | C6'—H6' | 1.0000 |
C5—C12 | 1.531 (3) | C7'—C8' | 1.331 (4) |
C5—C6 | 1.584 (3) | C7'—H7' | 0.9500 |
C6—C15 | 1.535 (3) | C8'—C9' | 1.449 (4) |
C6—C7 | 1.538 (3) | C8'—H8' | 0.9500 |
C6—C11 | 1.551 (3) | C9'—C10' | 1.343 (4) |
C7—C8 | 1.528 (4) | C9'—H9' | 0.9500 |
C7—H7A | 0.9900 | C10'—C11' | 1.477 (3) |
C7—H7B | 0.9900 | C10'—H10' | 0.9500 |
C8—C9 | 1.502 (4) | C12'—H12A | 0.9800 |
C8—H8A | 0.9900 | C12'—H12B | 0.9800 |
C8—H8B | 0.9900 | C12'—H12C | 0.9800 |
C9—C10 | 1.321 (4) | C13'—C14' | 1.512 (4) |
C9—C16 | 1.505 (4) | C13'—H13' | 1.0000 |
C10—C11 | 1.509 (3) | C14'—H14D | 0.9800 |
C10—H10 | 0.9500 | C14'—H14E | 0.9800 |
C11—H11 | 1.0000 | C14'—H14F | 0.9800 |
C2—O1—C11 | 113.23 (17) | O3—C15—C6 | 111.26 (19) |
C12—O2—C13 | 59.98 (16) | O3—C15—H15A | 109.4 |
C1'—O3—C15 | 113.7 (2) | C6—C15—H15A | 109.4 |
C5'—O4—C6' | 116.2 (2) | O3—C15—H15B | 109.4 |
C11'—O5—C4 | 115.90 (18) | C6—C15—H15B | 109.4 |
C2'—O7—H7 | 109.5 | H15A—C15—H15B | 108.0 |
C13'—O8—H8 | 109.5 | C9—C16—H16A | 109.5 |
O1—C2—C12 | 107.62 (19) | C9—C16—H16B | 109.5 |
O1—C2—C3 | 113.4 (2) | H16A—C16—H16B | 109.5 |
C12—C2—C3 | 102.03 (19) | C9—C16—H16C | 109.5 |
O1—C2—H2 | 111.1 | H16A—C16—H16C | 109.5 |
C12—C2—H2 | 111.1 | H16B—C16—H16C | 109.5 |
C3—C2—H2 | 111.1 | O6—C1'—O3 | 123.7 (3) |
C2—C3—C4 | 105.16 (19) | O6—C1'—C2' | 126.0 (3) |
C2—C3—H3A | 110.7 | O3—C1'—C2' | 110.3 (2) |
C4—C3—H3A | 110.7 | O7—C2'—C1' | 110.7 (2) |
C2—C3—H3B | 110.7 | O7—C2'—C3' | 109.5 (2) |
C4—C3—H3B | 110.7 | C1'—C2'—C3' | 109.2 (2) |
H3A—C3—H3B | 108.8 | O7—C2'—H2' | 109.1 |
O5—C4—C3 | 107.36 (18) | C1'—C2'—H2' | 109.1 |
O5—C4—C5 | 111.07 (18) | C3'—C2'—H2' | 109.1 |
C3—C4—C5 | 106.24 (19) | C12'—C3'—C4' | 113.9 (2) |
O5—C4—H4 | 110.7 | C12'—C3'—C2' | 109.3 (2) |
C3—C4—H4 | 110.7 | C4'—C3'—C2' | 111.3 (2) |
C5—C4—H4 | 110.7 | C12'—C3'—H3' | 107.4 |
C14—C5—C12 | 112.8 (2) | C4'—C3'—H3' | 107.4 |
C14—C5—C4 | 114.66 (19) | C2'—C3'—H3' | 107.4 |
C12—C5—C4 | 100.44 (19) | C5'—C4'—C3' | 114.3 (2) |
C14—C5—C6 | 113.28 (19) | C5'—C4'—H4'A | 108.7 |
C12—C5—C6 | 106.61 (18) | C3'—C4'—H4'A | 108.7 |
C4—C5—C6 | 107.99 (18) | C5'—C4'—H4'B | 108.7 |
C15—C6—C7 | 111.19 (19) | C3'—C4'—H4'B | 108.7 |
C15—C6—C11 | 103.77 (18) | H4'A—C4'—H4'B | 107.6 |
C7—C6—C11 | 108.23 (19) | O4—C5'—C4' | 109.7 (3) |
C15—C6—C5 | 112.62 (19) | O4—C5'—H5'A | 109.7 |
C7—C6—C5 | 111.73 (19) | C4'—C5'—H5'A | 109.7 |
C11—C6—C5 | 108.88 (18) | O4—C5'—H5'B | 109.7 |
C8—C7—C6 | 112.5 (2) | C4'—C5'—H5'B | 109.7 |
C8—C7—H7A | 109.1 | H5'A—C5'—H5'B | 108.2 |
C6—C7—H7A | 109.1 | O4—C6'—C7' | 112.9 (2) |
C8—C7—H7B | 109.1 | O4—C6'—C13' | 108.2 (2) |
C6—C7—H7B | 109.1 | C7'—C6'—C13' | 111.0 (2) |
H7A—C7—H7B | 107.8 | O4—C6'—H6' | 108.2 |
C9—C8—C7 | 113.0 (2) | C7'—C6'—H6' | 108.2 |
C9—C8—H8A | 109.0 | C13'—C6'—H6' | 108.2 |
C7—C8—H8A | 109.0 | C8'—C7'—C6' | 126.4 (3) |
C9—C8—H8B | 109.0 | C8'—C7'—H7' | 116.8 |
C7—C8—H8B | 109.0 | C6'—C7'—H7' | 116.8 |
H8A—C8—H8B | 107.8 | C7'—C8'—C9' | 121.2 (2) |
C10—C9—C8 | 122.1 (2) | C7'—C8'—H8' | 119.4 |
C10—C9—C16 | 121.9 (3) | C9'—C8'—H8' | 119.4 |
C8—C9—C16 | 116.0 (2) | C10'—C9'—C8' | 127.6 (2) |
C9—C10—C11 | 124.5 (2) | C10'—C9'—H9' | 116.2 |
C9—C10—H10 | 117.8 | C8'—C9'—H9' | 116.2 |
C11—C10—H10 | 117.8 | C9'—C10'—C11' | 123.5 (2) |
O1—C11—C10 | 105.75 (18) | C9'—C10'—H10' | 118.3 |
O1—C11—C6 | 112.71 (18) | C11'—C10'—H10' | 118.3 |
C10—C11—C6 | 112.8 (2) | O9—C11'—O5 | 123.7 (2) |
O1—C11—H11 | 108.5 | O9—C11'—C10' | 126.3 (2) |
C10—C11—H11 | 108.5 | O5—C11'—C10' | 110.0 (2) |
C6—C11—H11 | 108.5 | C3'—C12'—H12A | 109.5 |
O2—C12—C13 | 60.13 (16) | C3'—C12'—H12B | 109.5 |
O2—C12—C2 | 115.3 (2) | H12A—C12'—H12B | 109.5 |
C13—C12—C2 | 125.0 (2) | C3'—C12'—H12C | 109.5 |
O2—C12—C5 | 117.1 (2) | H12A—C12'—H12C | 109.5 |
C13—C12—C5 | 127.7 (2) | H12B—C12'—H12C | 109.5 |
C2—C12—C5 | 103.9 (2) | O8—C13'—C14' | 108.4 (2) |
C12—C13—O2 | 59.90 (15) | O8—C13'—C6' | 110.6 (2) |
C12—C13—H13A | 117.8 | C14'—C13'—C6' | 111.6 (2) |
O2—C13—H13A | 117.8 | O8—C13'—H13' | 108.7 |
C12—C13—H13B | 117.8 | C14'—C13'—H13' | 108.7 |
O2—C13—H13B | 117.8 | C6'—C13'—H13' | 108.7 |
H13A—C13—H13B | 114.9 | C13'—C14'—H14D | 109.5 |
C5—C14—H14A | 109.5 | C13'—C14'—H14E | 109.5 |
C5—C14—H14B | 109.5 | H14D—C14'—H14E | 109.5 |
H14A—C14—H14B | 109.5 | C13'—C14'—H14F | 109.5 |
C5—C14—H14C | 109.5 | H14D—C14'—H14F | 109.5 |
H14A—C14—H14C | 109.5 | H14E—C14'—H14F | 109.5 |
H14B—C14—H14C | 109.5 | ||
C11—O1—C2—C12 | −65.2 (2) | O1—C2—C12—C5 | 72.8 (2) |
C11—O1—C2—C3 | 46.9 (3) | C3—C2—C12—C5 | −46.8 (2) |
O1—C2—C3—C4 | −85.5 (2) | C14—C5—C12—O2 | 38.1 (3) |
C12—C2—C3—C4 | 30.0 (2) | C4—C5—C12—O2 | −84.4 (2) |
C11'—O5—C4—C3 | −154.6 (2) | C6—C5—C12—O2 | 163.10 (19) |
C11'—O5—C4—C5 | 89.7 (2) | C14—C5—C12—C13 | −33.7 (3) |
C2—C3—C4—O5 | −121.9 (2) | C4—C5—C12—C13 | −156.3 (2) |
C2—C3—C4—C5 | −3.0 (2) | C6—C5—C12—C13 | 91.2 (3) |
O5—C4—C5—C14 | −29.1 (3) | C14—C5—C12—C2 | 166.5 (2) |
C3—C4—C5—C14 | −145.6 (2) | C4—C5—C12—C2 | 44.0 (2) |
O5—C4—C5—C12 | 92.1 (2) | C6—C5—C12—C2 | −68.5 (2) |
C3—C4—C5—C12 | −24.3 (2) | C2—C12—C13—O2 | −101.5 (3) |
O5—C4—C5—C6 | −156.44 (18) | C5—C12—C13—O2 | 102.7 (3) |
C3—C4—C5—C6 | 87.1 (2) | C1'—O3—C15—C6 | 170.8 (2) |
C14—C5—C6—C15 | −64.8 (3) | C7—C6—C15—O3 | −51.0 (3) |
C12—C5—C6—C15 | 170.5 (2) | C11—C6—C15—O3 | −167.16 (18) |
C4—C5—C6—C15 | 63.3 (2) | C5—C6—C15—O3 | 75.3 (2) |
C14—C5—C6—C7 | 61.2 (3) | C15—O3—C1'—O6 | −7.6 (4) |
C12—C5—C6—C7 | −63.5 (2) | C15—O3—C1'—C2' | 170.7 (2) |
C4—C5—C6—C7 | −170.71 (19) | O6—C1'—C2'—O7 | −13.8 (4) |
C14—C5—C6—C11 | −179.32 (19) | O3—C1'—C2'—O7 | 168.0 (2) |
C12—C5—C6—C11 | 56.0 (2) | O6—C1'—C2'—C3' | 106.9 (3) |
C4—C5—C6—C11 | −51.2 (2) | O3—C1'—C2'—C3' | −71.3 (3) |
C15—C6—C7—C8 | −53.9 (3) | O7—C2'—C3'—C12' | 54.8 (3) |
C11—C6—C7—C8 | 59.4 (3) | C1'—C2'—C3'—C12' | −66.6 (3) |
C5—C6—C7—C8 | 179.3 (2) | O7—C2'—C3'—C4' | −71.8 (3) |
C6—C7—C8—C9 | −44.4 (3) | C1'—C2'—C3'—C4' | 166.8 (3) |
C7—C8—C9—C10 | 14.6 (4) | C12'—C3'—C4'—C5' | 78.2 (4) |
C7—C8—C9—C16 | −166.1 (2) | C2'—C3'—C4'—C5' | −157.8 (3) |
C8—C9—C10—C11 | −1.4 (4) | C6'—O4—C5'—C4' | 179.0 (2) |
C16—C9—C10—C11 | 179.3 (2) | C3'—C4'—C5'—O4 | −64.7 (4) |
C2—O1—C11—C10 | 175.6 (2) | C5'—O4—C6'—C7' | −99.2 (3) |
C2—O1—C11—C6 | 51.9 (3) | C5'—O4—C6'—C13' | 137.6 (2) |
C9—C10—C11—O1 | −106.0 (3) | O4—C6'—C7'—C8' | 5.8 (4) |
C9—C10—C11—C6 | 17.6 (3) | C13'—C6'—C7'—C8' | 127.4 (3) |
C15—C6—C11—O1 | −166.89 (18) | C6'—C7'—C8'—C9' | 174.7 (2) |
C7—C6—C11—O1 | 74.9 (2) | C7'—C8'—C9'—C10' | −169.7 (3) |
C5—C6—C11—O1 | −46.7 (2) | C8'—C9'—C10'—C11' | −4.7 (4) |
C15—C6—C11—C10 | 73.4 (2) | C4—O5—C11'—O9 | −0.1 (3) |
C7—C6—C11—C10 | −44.8 (3) | C4—O5—C11'—C10' | 178.57 (19) |
C5—C6—C11—C10 | −166.4 (2) | C9'—C10'—C11'—O9 | −28.5 (4) |
C13—O2—C12—C2 | 117.4 (3) | C9'—C10'—C11'—O5 | 152.8 (2) |
C13—O2—C12—C5 | −119.9 (3) | O4—C6'—C13'—O8 | −68.1 (3) |
O1—C2—C12—O2 | −157.67 (19) | C7'—C6'—C13'—O8 | 167.6 (2) |
C3—C2—C12—O2 | 82.7 (2) | O4—C6'—C13'—C14' | 52.7 (3) |
O1—C2—C12—C13 | −87.6 (3) | C7'—C6'—C13'—C14' | −71.6 (3) |
C3—C2—C12—C13 | 152.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7···O8i | 0.84 | 1.94 | 2.761 (3) | 167 |
O8—H8···O2ii | 0.84 | 2.10 | 2.895 (3) | 158 |
C4—H4···O1iii | 1.00 | 2.55 | 3.467 (3) | 153 |
C13—H13B···O9iv | 0.99 | 2.65 | 3.490 (3) | 143 |
C7′—H7′···O6v | 0.95 | 2.62 | 3.473 (3) | 150 |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) −x+1, y+1/2, −z+3/2; (iii) x−1/2, −y+1/2, −z+1; (iv) x+1, y, z; (v) −x+1/2, −y+1, z+1/2. |
C29H40O9 | Dx = 1.222 Mg m−3 |
Mr = 532.61 | Cu Kα radiation, λ = 1.54180 Å |
Orthorhombic, P212121 | Cell parameters from 3458 reflections |
a = 9.302 (3) Å | θ = 4.3–72.7° |
b = 15.412 (6) Å | µ = 0.74 mm−1 |
c = 20.191 (8) Å | T = 293 K |
V = 2894.6 (19) Å3 | Block, colourless |
Z = 4 | 0.47 × 0.47 × 0.24 mm |
F(000) = 1144 |
SuperNova (Cu) X-ray Source diffractometer | 4285 reflections with I > 2σ(I) |
Radiation source: micro-focus sealed X-ray tube | Rint = 0.073 |
Absorption correction: analytical CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. | θmax = 72.9°, θmin = 3.6° |
Tmin = 0.775, Tmax = 0.878 | h = −6→11 |
6984 measured reflections | k = −16→18 |
5037 independent reflections | l = −24→24 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.086 | w = 1/[σ2(Fo2) + (0.2P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.265 | (Δ/σ)max < 0.001 |
S = 1.05 | Δρmax = 0.34 e Å−3 |
5037 reflections | Δρmin = −0.34 e Å−3 |
349 parameters | Absolute structure: Classical Flack method preferred over Parsons because s.u. lower. |
0 restraints | Absolute structure parameter: 0.4 (4) |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.1160 (4) | 0.2734 (3) | 0.4876 (2) | 0.0489 (9) | |
O5 | 0.4444 (4) | 0.3442 (2) | 0.33576 (19) | 0.0459 (8) | |
O9 | 0.6291 (4) | 0.4150 (3) | 0.3838 (2) | 0.0552 (10) | |
O8 | 1.0280 (6) | 0.8042 (3) | 0.2920 (3) | 0.0711 (13) | |
H40 | 0.996908 | 0.836900 | 0.263394 | 0.107* | |
O4 | 0.8192 (5) | 0.6918 (3) | 0.3550 (2) | 0.0588 (11) | |
O6 | 0.6101 (7) | 0.4992 (4) | 0.6056 (3) | 0.0914 (19) | |
O3 | 0.4451 (4) | 0.5178 (2) | 0.5267 (2) | 0.0470 (8) | |
O7 | 0.6931 (6) | 0.6700 (4) | 0.5946 (3) | 0.0780 (16) | |
H39 | 0.654210 | 0.670235 | 0.631038 | 0.117* | |
O2 | 0.1010 (4) | 0.3816 (3) | 0.3259 (2) | 0.0552 (10) | |
C5 | 0.2667 (5) | 0.4062 (3) | 0.4991 (2) | 0.0374 (10) | |
C10 | 0.2299 (5) | 0.3139 (3) | 0.5240 (3) | 0.0410 (10) | |
H10 | 0.316100 | 0.277728 | 0.519881 | 0.049* | |
C9 | 0.1829 (6) | 0.3130 (4) | 0.5960 (3) | 0.0489 (12) | |
H9 | 0.185959 | 0.260368 | 0.618428 | 0.059* | |
C8 | 0.1381 (6) | 0.3814 (5) | 0.6287 (3) | 0.0545 (14) | |
C7 | 0.1345 (7) | 0.4703 (5) | 0.5984 (3) | 0.0614 (16) | |
H7 | 0.212397 | 0.504623 | 0.616696 | 0.074* | |
H8 | 0.044767 | 0.498355 | 0.610164 | 0.074* | |
C6 | 0.1486 (6) | 0.4680 (4) | 0.5230 (3) | 0.0510 (13) | |
H6 | 0.169475 | 0.526086 | 0.507177 | 0.061* | |
H5 | 0.057494 | 0.450213 | 0.504050 | 0.061* | |
C15 | 0.0923 (9) | 0.3768 (6) | 0.7001 (4) | 0.078 (2) | |
H18 | 0.106251 | 0.318860 | 0.716334 | 0.117* | |
H19 | −0.007506 | 0.392031 | 0.703596 | 0.117* | |
H20 | 0.148797 | 0.416494 | 0.725830 | 0.117* | |
C4 | 0.2781 (5) | 0.4043 (3) | 0.4206 (3) | 0.0370 (9) | |
C3 | 0.3811 (5) | 0.3291 (3) | 0.4010 (3) | 0.0410 (10) | |
H4 | 0.456412 | 0.321639 | 0.434432 | 0.049* | |
C2 | 0.2894 (6) | 0.2480 (3) | 0.3958 (3) | 0.0495 (12) | |
H3 | 0.325979 | 0.203022 | 0.424943 | 0.059* | |
H2 | 0.289369 | 0.226140 | 0.350788 | 0.059* | |
C1 | 0.1377 (5) | 0.2748 (4) | 0.4166 (3) | 0.0464 (12) | |
H1 | 0.064181 | 0.241008 | 0.393355 | 0.056* | |
C11 | 0.1364 (5) | 0.3678 (4) | 0.3957 (3) | 0.0440 (11) | |
C12 | 0.0054 (6) | 0.4163 (5) | 0.3763 (3) | 0.0589 (15) | |
H12 | −0.086756 | 0.387974 | 0.382581 | 0.071* | |
H11 | 0.004807 | 0.478567 | 0.383133 | 0.071* | |
C13 | 0.3143 (6) | 0.4929 (3) | 0.3906 (3) | 0.0467 (11) | |
H13 | 0.410265 | 0.509081 | 0.402971 | 0.070* | |
H14 | 0.247744 | 0.535526 | 0.406821 | 0.070* | |
H15 | 0.307528 | 0.489630 | 0.343241 | 0.070* | |
C26 | 0.5702 (6) | 0.3883 (3) | 0.3352 (3) | 0.0471 (12) | |
C25 | 0.6222 (7) | 0.3981 (4) | 0.2658 (3) | 0.0539 (13) | |
H31 | 0.598031 | 0.355482 | 0.235147 | 0.065* | |
C24 | 0.7018 (6) | 0.4650 (4) | 0.2455 (3) | 0.0556 (13) | |
H30 | 0.734023 | 0.462248 | 0.201998 | 0.067* | |
C23 | 0.7443 (6) | 0.5408 (4) | 0.2820 (3) | 0.0512 (12) | |
H29 | 0.727688 | 0.542171 | 0.327450 | 0.061* | |
C22 | 0.8056 (6) | 0.6081 (4) | 0.2540 (3) | 0.0523 (12) | |
H28 | 0.828538 | 0.602330 | 0.209401 | 0.063* | |
C21 | 0.8430 (7) | 0.6929 (4) | 0.2853 (3) | 0.0523 (13) | |
H27 | 0.782251 | 0.738141 | 0.265737 | 0.063* | |
C28 | 1.0009 (7) | 0.7169 (4) | 0.2733 (3) | 0.0571 (14) | |
H35 | 1.022230 | 0.710209 | 0.226072 | 0.068* | |
C29 | 1.1011 (7) | 0.6590 (5) | 0.3124 (4) | 0.0708 (19) | |
H36 | 1.197581 | 0.680668 | 0.308900 | 0.106* | |
H38 | 1.096988 | 0.601105 | 0.295030 | 0.106* | |
H37 | 1.072340 | 0.658622 | 0.358053 | 0.106* | |
C20 | 0.6981 (9) | 0.7363 (5) | 0.3781 (4) | 0.077 (2) | |
H26 | 0.612231 | 0.712286 | 0.357938 | 0.092* | |
H25 | 0.704638 | 0.796976 | 0.365662 | 0.092* | |
C19 | 0.6872 (9) | 0.7289 (4) | 0.4530 (4) | 0.073 (2) | |
H24 | 0.773092 | 0.753899 | 0.472527 | 0.088* | |
H23 | 0.605803 | 0.763021 | 0.467929 | 0.088* | |
C18 | 0.6703 (6) | 0.6377 (4) | 0.4784 (3) | 0.0517 (13) | |
H22 | 0.606637 | 0.606921 | 0.447720 | 0.062* | |
C17 | 0.5983 (6) | 0.6359 (4) | 0.5475 (3) | 0.0520 (13) | |
H21 | 0.511966 | 0.672257 | 0.546192 | 0.062* | |
C16 | 0.5547 (7) | 0.5449 (4) | 0.5645 (3) | 0.0527 (13) | |
C14 | 0.4109 (5) | 0.4275 (3) | 0.5324 (3) | 0.0414 (10) | |
H16 | 0.406303 | 0.411712 | 0.578824 | 0.050* | |
H17 | 0.486538 | 0.393422 | 0.511897 | 0.050* | |
C27 | 0.8125 (8) | 0.5867 (6) | 0.4818 (4) | 0.078 (2) | |
H34 | 0.873613 | 0.611882 | 0.514942 | 0.117* | |
H33 | 0.859594 | 0.589071 | 0.439554 | 0.117* | |
H32 | 0.792810 | 0.527350 | 0.493052 | 0.117* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0333 (16) | 0.073 (2) | 0.040 (2) | −0.0189 (16) | 0.0039 (17) | −0.0017 (17) |
O5 | 0.0357 (16) | 0.0644 (17) | 0.0375 (19) | −0.0007 (16) | 0.0033 (16) | 0.0029 (16) |
O9 | 0.0357 (17) | 0.081 (2) | 0.049 (2) | −0.0155 (18) | −0.0011 (19) | 0.0094 (19) |
O8 | 0.080 (3) | 0.070 (2) | 0.063 (3) | −0.017 (2) | −0.023 (3) | 0.018 (2) |
O4 | 0.052 (2) | 0.084 (2) | 0.041 (2) | 0.014 (2) | 0.0078 (19) | 0.0072 (19) |
O6 | 0.094 (4) | 0.101 (4) | 0.079 (4) | −0.041 (3) | −0.053 (4) | 0.024 (3) |
O3 | 0.0348 (15) | 0.0587 (17) | 0.048 (2) | −0.0084 (15) | −0.0088 (18) | −0.0012 (16) |
O7 | 0.070 (3) | 0.106 (3) | 0.058 (3) | −0.044 (3) | 0.018 (3) | −0.033 (3) |
O2 | 0.0410 (19) | 0.087 (2) | 0.038 (2) | −0.0024 (18) | −0.0140 (18) | 0.0003 (19) |
C5 | 0.0241 (18) | 0.055 (2) | 0.033 (2) | 0.0005 (18) | −0.005 (2) | −0.0008 (18) |
C10 | 0.030 (2) | 0.057 (2) | 0.036 (3) | −0.0048 (19) | 0.003 (2) | 0.002 (2) |
C9 | 0.036 (2) | 0.075 (3) | 0.036 (3) | −0.011 (2) | 0.000 (2) | 0.007 (2) |
C8 | 0.033 (2) | 0.089 (4) | 0.041 (3) | −0.003 (3) | 0.005 (2) | 0.000 (3) |
C7 | 0.049 (3) | 0.084 (4) | 0.050 (3) | 0.015 (3) | 0.004 (3) | −0.016 (3) |
C6 | 0.036 (2) | 0.073 (3) | 0.044 (3) | 0.007 (2) | −0.002 (3) | −0.006 (2) |
C15 | 0.073 (4) | 0.119 (6) | 0.042 (3) | −0.005 (4) | 0.012 (4) | −0.005 (4) |
C4 | 0.0248 (18) | 0.053 (2) | 0.033 (2) | −0.0032 (17) | −0.005 (2) | 0.0018 (19) |
C3 | 0.030 (2) | 0.060 (2) | 0.033 (2) | −0.0010 (19) | 0.004 (2) | 0.0060 (19) |
C2 | 0.046 (3) | 0.056 (2) | 0.047 (3) | −0.005 (2) | 0.010 (3) | −0.002 (2) |
C1 | 0.031 (2) | 0.069 (3) | 0.040 (3) | −0.018 (2) | 0.002 (2) | −0.004 (2) |
C11 | 0.028 (2) | 0.071 (3) | 0.033 (2) | −0.005 (2) | −0.007 (2) | −0.003 (2) |
C12 | 0.031 (2) | 0.093 (4) | 0.052 (3) | 0.012 (3) | −0.014 (3) | −0.004 (3) |
C13 | 0.039 (2) | 0.056 (2) | 0.046 (3) | 0.000 (2) | −0.007 (2) | 0.006 (2) |
C26 | 0.035 (2) | 0.057 (2) | 0.049 (3) | 0.001 (2) | 0.009 (3) | 0.003 (2) |
C25 | 0.052 (3) | 0.066 (2) | 0.044 (3) | −0.005 (2) | 0.014 (3) | 0.000 (2) |
C24 | 0.051 (3) | 0.073 (3) | 0.042 (3) | 0.000 (3) | 0.010 (3) | 0.005 (3) |
C23 | 0.041 (3) | 0.069 (3) | 0.043 (3) | −0.002 (2) | 0.004 (3) | 0.009 (2) |
C22 | 0.046 (3) | 0.071 (3) | 0.040 (3) | −0.004 (2) | 0.000 (3) | 0.010 (2) |
C21 | 0.050 (3) | 0.068 (3) | 0.039 (3) | 0.002 (3) | 0.002 (3) | 0.010 (2) |
C28 | 0.060 (3) | 0.068 (3) | 0.044 (3) | −0.014 (3) | 0.007 (3) | 0.010 (2) |
C29 | 0.051 (3) | 0.080 (4) | 0.081 (5) | 0.004 (3) | 0.005 (4) | 0.008 (4) |
C20 | 0.073 (5) | 0.080 (4) | 0.078 (5) | 0.015 (4) | 0.025 (4) | 0.017 (4) |
C19 | 0.074 (4) | 0.067 (3) | 0.078 (5) | −0.003 (3) | 0.038 (4) | −0.009 (3) |
C18 | 0.041 (3) | 0.065 (3) | 0.049 (3) | −0.002 (2) | 0.010 (3) | −0.006 (2) |
C17 | 0.043 (3) | 0.064 (3) | 0.049 (3) | −0.013 (2) | 0.009 (3) | −0.012 (2) |
C16 | 0.047 (3) | 0.072 (3) | 0.039 (3) | −0.016 (3) | −0.006 (3) | −0.004 (2) |
C14 | 0.028 (2) | 0.056 (2) | 0.040 (3) | 0.0003 (18) | −0.008 (2) | 0.002 (2) |
C27 | 0.060 (4) | 0.113 (5) | 0.060 (4) | 0.028 (4) | 0.016 (4) | 0.009 (4) |
O1—C10 | 1.433 (6) | C2—H2 | 0.9700 |
O1—C1 | 1.447 (7) | C1—C11 | 1.494 (8) |
O5—C26 | 1.354 (7) | C1—H1 | 0.9800 |
O5—C3 | 1.461 (6) | C11—C12 | 1.482 (7) |
O9—C26 | 1.196 (7) | C12—H12 | 0.9700 |
O8—C28 | 1.420 (7) | C12—H11 | 0.9700 |
O8—H40 | 0.8200 | C13—H13 | 0.9600 |
O4—C20 | 1.400 (9) | C13—H14 | 0.9600 |
O4—C21 | 1.424 (7) | C13—H15 | 0.9600 |
O6—C16 | 1.205 (8) | C26—C25 | 1.490 (8) |
O3—C16 | 1.341 (7) | C25—C24 | 1.334 (9) |
O3—C14 | 1.432 (6) | C25—H31 | 0.9300 |
O7—C17 | 1.399 (8) | C24—C23 | 1.436 (9) |
O7—H39 | 0.8200 | C24—H30 | 0.9300 |
O2—C12 | 1.454 (8) | C23—C22 | 1.313 (8) |
O2—C11 | 1.463 (6) | C23—H29 | 0.9300 |
C5—C6 | 1.533 (7) | C22—C21 | 1.493 (9) |
C5—C14 | 1.536 (6) | C22—H28 | 0.9300 |
C5—C10 | 1.549 (7) | C21—C28 | 1.534 (9) |
C5—C4 | 1.587 (7) | C21—H27 | 0.9800 |
C10—C9 | 1.517 (7) | C28—C29 | 1.511 (10) |
C10—H10 | 0.9800 | C28—H35 | 0.9800 |
C9—C8 | 1.312 (9) | C29—H36 | 0.9600 |
C9—H9 | 0.9300 | C29—H38 | 0.9600 |
C8—C7 | 1.500 (10) | C29—H37 | 0.9600 |
C8—C15 | 1.504 (9) | C20—C19 | 1.520 (11) |
C7—C6 | 1.528 (9) | C20—H26 | 0.9700 |
C7—H7 | 0.9700 | C20—H25 | 0.9700 |
C7—H8 | 0.9700 | C19—C18 | 1.504 (9) |
C6—H6 | 0.9700 | C19—H24 | 0.9700 |
C6—H5 | 0.9700 | C19—H23 | 0.9700 |
C15—H18 | 0.9600 | C18—C27 | 1.540 (9) |
C15—H19 | 0.9600 | C18—C17 | 1.547 (9) |
C15—H20 | 0.9600 | C18—H22 | 0.9800 |
C4—C11 | 1.519 (6) | C17—C16 | 1.499 (8) |
C4—C13 | 1.531 (6) | C17—H21 | 0.9800 |
C4—C3 | 1.556 (7) | C14—H16 | 0.9700 |
C3—C2 | 1.517 (7) | C14—H17 | 0.9700 |
C3—H4 | 0.9800 | C27—H34 | 0.9600 |
C2—C1 | 1.529 (7) | C27—H33 | 0.9600 |
C2—H3 | 0.9700 | C27—H32 | 0.9600 |
C10—O1—C1 | 113.5 (3) | C4—C13—H13 | 109.5 |
C26—O5—C3 | 115.8 (4) | C4—C13—H14 | 109.5 |
C28—O8—H40 | 109.5 | H13—C13—H14 | 109.5 |
C20—O4—C21 | 116.7 (5) | C4—C13—H15 | 109.5 |
C16—O3—C14 | 115.2 (4) | H13—C13—H15 | 109.5 |
C17—O7—H39 | 109.5 | H14—C13—H15 | 109.5 |
C12—O2—C11 | 61.1 (3) | O9—C26—O5 | 124.2 (5) |
C6—C5—C14 | 110.8 (4) | O9—C26—C25 | 126.0 (5) |
C6—C5—C10 | 108.0 (4) | O5—C26—C25 | 109.8 (5) |
C14—C5—C10 | 104.3 (4) | C24—C25—C26 | 123.1 (6) |
C6—C5—C4 | 112.0 (4) | C24—C25—H31 | 118.4 |
C14—C5—C4 | 112.5 (4) | C26—C25—H31 | 118.4 |
C10—C5—C4 | 108.8 (4) | C25—C24—C23 | 128.6 (6) |
O1—C10—C9 | 106.0 (4) | C25—C24—H30 | 115.7 |
O1—C10—C5 | 113.4 (4) | C23—C24—H30 | 115.7 |
C9—C10—C5 | 112.6 (4) | C22—C23—C24 | 122.8 (6) |
O1—C10—H10 | 108.3 | C22—C23—H29 | 118.6 |
C9—C10—H10 | 108.3 | C24—C23—H29 | 118.6 |
C5—C10—H10 | 108.3 | C23—C22—C21 | 127.7 (6) |
C8—C9—C10 | 124.5 (5) | C23—C22—H28 | 116.2 |
C8—C9—H9 | 117.7 | C21—C22—H28 | 116.2 |
C10—C9—H9 | 117.7 | O4—C21—C22 | 111.8 (5) |
C9—C8—C7 | 122.4 (5) | O4—C21—C28 | 107.9 (5) |
C9—C8—C15 | 122.3 (7) | C22—C21—C28 | 111.5 (5) |
C7—C8—C15 | 115.3 (6) | O4—C21—H27 | 108.5 |
C8—C7—C6 | 112.6 (5) | C22—C21—H27 | 108.5 |
C8—C7—H7 | 109.1 | C28—C21—H27 | 108.5 |
C6—C7—H7 | 109.1 | O8—C28—C29 | 108.1 (6) |
C8—C7—H8 | 109.1 | O8—C28—C21 | 110.8 (6) |
C6—C7—H8 | 109.1 | C29—C28—C21 | 111.5 (5) |
H7—C7—H8 | 107.8 | O8—C28—H35 | 108.8 |
C7—C6—C5 | 113.0 (5) | C29—C28—H35 | 108.8 |
C7—C6—H6 | 109.0 | C21—C28—H35 | 108.8 |
C5—C6—H6 | 109.0 | C28—C29—H36 | 109.5 |
C7—C6—H5 | 109.0 | C28—C29—H38 | 109.5 |
C5—C6—H5 | 109.0 | H36—C29—H38 | 109.5 |
H6—C6—H5 | 107.8 | C28—C29—H37 | 109.5 |
C8—C15—H18 | 109.5 | H36—C29—H37 | 109.5 |
C8—C15—H19 | 109.5 | H38—C29—H37 | 109.5 |
H18—C15—H19 | 109.5 | O4—C20—C19 | 110.4 (7) |
C8—C15—H20 | 109.5 | O4—C20—H26 | 109.6 |
H18—C15—H20 | 109.5 | C19—C20—H26 | 109.6 |
H19—C15—H20 | 109.5 | O4—C20—H25 | 109.6 |
C11—C4—C13 | 112.9 (4) | C19—C20—H25 | 109.6 |
C11—C4—C3 | 100.0 (4) | H26—C20—H25 | 108.1 |
C13—C4—C3 | 115.3 (4) | C18—C19—C20 | 114.6 (6) |
C11—C4—C5 | 106.3 (4) | C18—C19—H24 | 108.6 |
C13—C4—C5 | 113.2 (4) | C20—C19—H24 | 108.6 |
C3—C4—C5 | 108.0 (4) | C18—C19—H23 | 108.6 |
O5—C3—C2 | 107.2 (4) | C20—C19—H23 | 108.6 |
O5—C3—C4 | 111.1 (4) | H24—C19—H23 | 107.6 |
C2—C3—C4 | 106.6 (4) | C19—C18—C27 | 113.7 (6) |
O5—C3—H4 | 110.6 | C19—C18—C17 | 111.7 (5) |
C2—C3—H4 | 110.6 | C27—C18—C17 | 108.8 (5) |
C4—C3—H4 | 110.6 | C19—C18—H22 | 107.5 |
C3—C2—C1 | 106.1 (4) | C27—C18—H22 | 107.5 |
C3—C2—H3 | 110.5 | C17—C18—H22 | 107.5 |
C1—C2—H3 | 110.5 | O7—C17—C16 | 111.5 (6) |
C3—C2—H2 | 110.5 | O7—C17—C18 | 109.4 (5) |
C1—C2—H2 | 110.5 | C16—C17—C18 | 109.9 (5) |
H3—C2—H2 | 108.7 | O7—C17—H21 | 108.7 |
O1—C1—C11 | 107.1 (4) | C16—C17—H21 | 108.7 |
O1—C1—C2 | 113.3 (5) | C18—C17—H21 | 108.7 |
C11—C1—C2 | 100.9 (4) | O6—C16—O3 | 122.4 (6) |
O1—C1—H1 | 111.6 | O6—C16—C17 | 126.1 (5) |
C11—C1—H1 | 111.6 | O3—C16—C17 | 111.5 (5) |
C2—C1—H1 | 111.6 | O3—C14—C5 | 111.5 (4) |
O2—C11—C12 | 59.2 (4) | O3—C14—H16 | 109.3 |
O2—C11—C1 | 114.5 (4) | C5—C14—H16 | 109.3 |
C12—C11—C1 | 124.4 (5) | O3—C14—H17 | 109.3 |
O2—C11—C4 | 117.5 (4) | C5—C14—H17 | 109.3 |
C12—C11—C4 | 127.9 (5) | H16—C14—H17 | 108.0 |
C1—C11—C4 | 104.7 (4) | C18—C27—H34 | 109.5 |
O2—C12—C11 | 59.8 (3) | C18—C27—H33 | 109.5 |
O2—C12—H12 | 117.8 | H34—C27—H33 | 109.5 |
C11—C12—H12 | 117.8 | C18—C27—H32 | 109.5 |
O2—C12—H11 | 117.8 | H34—C27—H32 | 109.5 |
C11—C12—H11 | 117.8 | H33—C27—H32 | 109.5 |
H12—C12—H11 | 114.9 | ||
C1—O1—C10—C9 | 175.3 (4) | O1—C1—C11—C4 | 72.6 (5) |
C1—O1—C10—C5 | 51.3 (6) | C2—C1—C11—C4 | −46.2 (5) |
C6—C5—C10—O1 | 75.4 (5) | C13—C4—C11—O2 | 38.3 (6) |
C14—C5—C10—O1 | −166.6 (4) | C3—C4—C11—O2 | −84.8 (5) |
C4—C5—C10—O1 | −46.4 (5) | C5—C4—C11—O2 | 162.9 (4) |
C6—C5—C10—C9 | −44.8 (5) | C13—C4—C11—C12 | −32.7 (8) |
C14—C5—C10—C9 | 73.1 (5) | C3—C4—C11—C12 | −155.8 (6) |
C4—C5—C10—C9 | −166.6 (4) | C5—C4—C11—C12 | 92.0 (6) |
O1—C10—C9—C8 | −106.0 (6) | C13—C4—C11—C1 | 166.6 (4) |
C5—C10—C9—C8 | 18.4 (7) | C3—C4—C11—C1 | 43.5 (5) |
C10—C9—C8—C7 | −2.6 (9) | C5—C4—C11—C1 | −68.8 (5) |
C10—C9—C8—C15 | 179.8 (6) | C1—C11—C12—O2 | −100.1 (6) |
C9—C8—C7—C6 | 15.4 (8) | C4—C11—C12—O2 | 102.5 (6) |
C15—C8—C7—C6 | −166.9 (5) | C3—O5—C26—O9 | −0.5 (7) |
C8—C7—C6—C5 | −44.7 (7) | C3—O5—C26—C25 | 179.5 (4) |
C14—C5—C6—C7 | −54.1 (6) | O9—C26—C25—C24 | −29.4 (9) |
C10—C5—C6—C7 | 59.5 (6) | O5—C26—C25—C24 | 150.5 (6) |
C4—C5—C6—C7 | 179.4 (5) | C26—C25—C24—C23 | −4.5 (10) |
C6—C5—C4—C11 | −63.9 (5) | C25—C24—C23—C22 | −170.0 (7) |
C14—C5—C4—C11 | 170.5 (4) | C24—C23—C22—C21 | 174.3 (6) |
C10—C5—C4—C11 | 55.5 (5) | C20—O4—C21—C22 | −105.1 (6) |
C6—C5—C4—C13 | 60.6 (5) | C20—O4—C21—C28 | 131.9 (6) |
C14—C5—C4—C13 | −65.0 (5) | C23—C22—C21—O4 | 6.8 (9) |
C10—C5—C4—C13 | 180.0 (4) | C23—C22—C21—C28 | 127.7 (6) |
C6—C5—C4—C3 | −170.5 (4) | O4—C21—C28—O8 | −68.0 (6) |
C14—C5—C4—C3 | 64.0 (5) | C22—C21—C28—O8 | 168.8 (5) |
C10—C5—C4—C3 | −51.1 (5) | O4—C21—C28—C29 | 52.4 (7) |
C26—O5—C3—C2 | −153.7 (4) | C22—C21—C28—C29 | −70.7 (7) |
C26—O5—C3—C4 | 90.3 (5) | C21—O4—C20—C19 | 179.8 (6) |
C11—C4—C3—O5 | 92.9 (5) | O4—C20—C19—C18 | −61.6 (9) |
C13—C4—C3—O5 | −28.5 (6) | C20—C19—C18—C27 | 80.2 (9) |
C5—C4—C3—O5 | −156.2 (4) | C20—C19—C18—C17 | −156.2 (6) |
C11—C4—C3—C2 | −23.6 (5) | C19—C18—C17—O7 | −69.4 (8) |
C13—C4—C3—C2 | −145.0 (5) | C27—C18—C17—O7 | 57.0 (7) |
C5—C4—C3—C2 | 87.3 (5) | C19—C18—C17—C16 | 167.9 (6) |
O5—C3—C2—C1 | −122.6 (5) | C27—C18—C17—C16 | −65.8 (7) |
C4—C3—C2—C1 | −3.5 (6) | C14—O3—C16—O6 | −7.9 (9) |
C10—O1—C1—C11 | −64.0 (5) | C14—O3—C16—C17 | 170.8 (5) |
C10—O1—C1—C2 | 46.4 (6) | O7—C17—C16—O6 | −12.6 (9) |
C3—C2—C1—O1 | −84.4 (5) | C18—C17—C16—O6 | 109.0 (8) |
C3—C2—C1—C11 | 29.8 (6) | O7—C17—C16—O3 | 168.7 (5) |
C12—O2—C11—C1 | 116.8 (6) | C18—C17—C16—O3 | −69.7 (6) |
C12—O2—C11—C4 | −119.7 (6) | C16—O3—C14—C5 | 168.2 (4) |
O1—C1—C11—O2 | −157.3 (4) | C6—C5—C14—O3 | −50.8 (6) |
C2—C1—C11—O2 | 83.9 (5) | C10—C5—C14—O3 | −166.8 (4) |
O1—C1—C11—C12 | −89.1 (6) | C4—C5—C14—O3 | 75.4 (5) |
C2—C1—C11—C12 | 152.1 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O8—H40···O2i | 0.82 | 2.13 | 2.921 (6) | 161 |
O7—H39···O8ii | 0.82 | 1.99 | 2.785 (7) | 164 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x−1/2, −y+3/2, −z+1. |
Position (Scheme 1) | 1H NMR (J in Hz) | 13C NMR | COSY | HMBC | NOESY |
2 | 3.74 (d, 5.1) | 80.4 | 3b | 4, 5, 12 | 3', 13a |
3 | b: 2.14 (overlap by H-3') | 35.7 | 2, 4 | 2, 4 | |
a: 2.47 (dd, 8.2, 15.2) | 2, 5, 12 | ||||
4 | 5.84 (dd, 4.5, 8.2) | 76.0 | 3 | 2, 3, 5, 6, 12, 11' | 11 |
5 | Cq | 50.5 | |||
6 | Cq | 45.0 | |||
7 | 1.87 (m, 2H) | 21.3 | 8 | 6, 8, 9, 11 | 13, 14 |
8 | a: 1.93 (d, 8.0) | 28.7 | 7 | 6,7, 9, 10 | |
b: 1.98 (m) | |||||
9 | Cq | 141.7 | |||
10 | 5.41 (d, 5.4) | 119.7 | 11, 16 | 6, 8, 11, 16 | |
11 | 3.72 (br d, 5.4) | 68.5 | 10 | 7, 10, 15 | 4 |
12 | Cq | 66.4 | |||
13 | 2.86 (d, 4.0) | 48.5 | 2, 5, 12 | 14 | |
3.05 (d, 4.0) | |||||
14 | 0.81 (s) | 8.0 | , | 4, 5, 6, 12 | 2', 3', 15, 12' |
15 | 4.32 (d, 12.2) | 64.8 | 15 | 5, 6, 7, 1' | 14 |
4.46 (d, 12.2) | 5, 6, 7, 11, 1' | ||||
16 | 1.72 (s) | 23.3 | 10 | 8, 9, 10 | |
1' | CO | 175.6 | |||
2' | 4.04 (d, 4.0) | 76.7 | 3' | 1', 4', 12' | 14, 3', 12' |
3' | 2.08 (m | 37.7 | 2', 12' | 1', 2' | 14, 2' |
4' | 1.58 (m) | 34.9 | 4', 5' | 3', 5', 12' | |
1.73 (m) | 2', 3', 5' | ||||
5' | 3.50 (ddd, 5.2, 8.7, 9.1) | 70.9 | 4', 5' | 3', 4', 6' | |
3.58 (ddd, 5.2, 9.6, 9.8) | |||||
6' | 3.82 (m) | 84.6 | 7', 13' | 5', 7', 8', 14' | 8', 14' |
7' | 6.17 (dd, 3.0, 15.4) | 142.3 | 6', 8' | 6', 8', 9' | 13', 14' |
8' | 7.60 (ddt, 11.4, 15.4, 1.1) | 126.8 | 7', 9' | 6', 9', 10' | 14, 3', 10', 12' |
9' | 6.75 (t, 11.4) | 145.5 | 8', 10' | 7', 8', 11' | 7' |
10' | 5.76 (d, 11.2) | 117.9 | 9' | 8', 9', 11' | 14 |
11' | CO | 168.1 | |||
12' | 1.09 (d, 6.8) | 15.1 | 3' | 2', 3', 4' | 14, 2', 3', 8' |
13' | 3.69 (m) | 71.0 | 6', 14' | 6', 14' | 7', 8', 14' |
14' | 1.16 (d, 6.4) | 18.4 | 13' | 6', 13' | 6', 7', 8',13' |
Note: (a) the assignments were based on 1H–1H COSY, HSQC–DEPT and HMBC experiments and recorded in MeOD-d4. |
Acknowledgements
MAA acknowledges a joint graduate student scholarship from the Egyptian Ministry of Higher Education (Cultural Affairs and Missions Sector) and the Greek Ministry of Foreign Affairs (E1 sector). The authors also thank Assistant Professor Nikolaos Tsoureas (Department of Chemistry, National and Kapodistrian University of Athens) for his assistance with the measurement of the X-ray diffraction data at the Core Facilities of the National and Kapodistrian University of Athens, as well as Associate Professor Kostas Bethanis, Department of Science, Agricultural University of Athens, partner of the National Research Infrastructure `INSPIRED', for critical reading of the manuscript.
Funding information
Funding for this research was provided by: `INSPIRED' under the Action `Reinforcement of the Research and Innovation' (NSRF 2014–2020) (grant No. 5002550 to Evangelia Chrysina).
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