research communications
β-hydroxyroyleanone isolated from Taxodium ascendens (B.)
of 7aSchool of Pharmaceutical Sciences, South-Central University for Nationalities, Wuhan 430074, People's Republic of China, and bCollege of Chemistry and Life Science, Qinghai University for Nationalities, Xining 810007, People's Republic of China
*Correspondence e-mail: xzyang@mail.scuec.edu.cn, mxhmxh02@163.com
The title compound, C20H28O4 [systematic name: (4bS,8aS,10S)-3,10-dihydroxy-2-isopropyl-4b,8,8-trimethyl-4b,5,6,7,8,8a,9,10-octahydrophenanthrene-1,4-dione], is an abietane-type diterpene, which was isolated from Taxodium ascendens (B.). The compound crystallizes in the P21, but it was not possible to determine the of the molecule in the crystal by The molecular structure is stabilized by two intramolecular O—H⋯O hydrogen bonds, enclosing S(5) and S(6) ring motifs. In the crystal, molecules are linked by O—H⋯O and C—H⋯O hydrogen bonds, forming chains along the [010] direction. The of the 10R stereoisomer of the title compound, isolated from the roots of Premna obtusifolia (Verbenaceae), has been reported. It crystallized in the P212121, and the was determined as (4bS,8aS,10R), by using Cu Kα radiation [Razak et al. (2010). Acta Cryst. E66, o1566–o1567].
CCDC reference: 1551129
1. Chemical context
Taxodium ascendens Brongn belongs to the Taxodiaceae species, which is native to the south-east of North America and has spread widely over southern China (Si et al., 2001). Previous chemical studies of Taxodium ascendens (B.) have described many diterpenes, such as 6,7-dehydroroyleanone, salvinolone and xanthoperol (Kusumoto et al., 2009; Gonzalez, 2015), and the have attracted much attention in recent years because of their diverse biological properties (Burmistrova et al., 2013; Tanaka, 2001), such as antibacterial (Yang et al., 2001), antioxidant (Kolak et al., 2009), antifungal (Topçu & Gören, 2007) and anticholinesterase activities (Topçu et al., 2013). A detailed phytochemical investigation of a petroleum ether extract of the pollen of Taxodium ascendens Brongn has been carried out and a series of have been isolated, including the title compound, 7β-hydroxyroyleanone. Herein, we present the of 7β-hydroxyroyleanone carried out in order to establish unambiguously the stereochemical features of this natural product.
2. Structural commentary
The molecular structure of the title compound is shown in Fig. 1. The structure contains two hydroxy groups, located at atoms C11 and C15, two ketone groups at C14 and C17, and two double bonds, C12=C13 and C15=C16. There are two intramolecular hydrogen bonds, viz. O2—H2⋯O1 and O4—H4⋯O3, which stabilize the molecular conformation. Ring A (atoms C1–C6) has a chair conformation [puckering parameters: amplitude (Q) = 0.552 (2) Å, θ = 4.9 (2)° and φ = 292 (3)°], while ring B (C1/C2/C10–C13) has an with atom C2 as the flap [puckering parameters: Q = 0.558 (2) Å, θ = 125.1 (2)° and φ = 256.2 (3)°]. Benzoquinone ring C (C12–C17) has a screw-boat conformation [puckering parameters: Q = 0.097 (2) Å, θ = 66.3 (12)° and φ = 29.7 (14)°]. The mean planes of the various rings are inclined to one another in the following manner: A/B = 22.97 (10)°, A/C = 34.52 (10)° and B/C = 12.84 (9)°.
The R stereoisomer of the title compound, isolated from the roots of Premna obtusifolia (Verbenaceae), has been reported twice (see §4, Database survey). It crystallized in the P212121, and the was determined as (4bS,8aS,10R) by using Cu Kα radiation (Razak et al., 2010). Comparing the two compounds indicates that the configuration of the three stereocentres in the title compound are (4bS,8aS,10S).
of the 103. Supramolecular features
In the crystal, two strong O—H⋯O hydrogen bonds, namely O2—H2A⋯O3i and O4—H4⋯O1ii, both approximately running along the b axis, are formed via the hydroxy group and the carbonyl groups (Fig. 2 and Table 1). Furthermore, a weak C11—H11⋯O1ii hydrogen bond occurs from a ring C atom to a carbonyl group, also running along the b-axis direction. These interactions result in the formation of chains propagating along the b-axis direction (Fig. 2 and Table 1).
4. Database survey
A search of the Cambridge Structural Database (CSD, Version 5.27, last update February 2017; Groom et al., 2016) for the octahydrophenanthrene-1,4-dione skeleton revealed 14 entries. These include two reports of a compound similar to the title compound, but with no hydroxy group in position 10, i.e. CSD refcodes HACGUN (Eugster et al., 1993) and HACGUN01 (Fun et al., 2011), and two reports of the stereoisomer of the title compound, with the hydroxy group in position 10 having an R configuration, i.e. QICLIX (Chen et al., 2000) and QICLIX01 (Razak et al., 2010).
5. Isolation and crystallization
The title compound was isolated from the pollen of Taxodium ascendens, collected in Wuhan, China, in April 2013 (SC0123). The air-dried pollen (1.8 kg) was extracted with 95% ethanol and then partitioned successively with petroleum ether (PE), ethyl acetate (EtOAc) and n-butyl alcohol (n-BuOH) to give a PE extract (80 g), an EtOAc extract (120 g) and a n-BuOH extract (100 g). The PE extract (80 g) was subjected to normal-phase silica-gel (300–400 mesh) with a gradient solvent system of petroleum ether–acetone (1.0–0.1 v/v, containing 0.1% formic acid) to give eight major fractions, denoted F1–F8. Fraction F4 (6 g) was sequentially subjected to normal-phase silica-gel (300–400 mesh) with an isocratic elution (petroleum ether–acetone, 2:1 v/v, containing 0.1% formic acid) to give three major fractions, denoted F4.1, F4.2 and F4.3. Fraction F4.3 was purified by semipreparative HPLC (CNCH3/H2O, 10:90→100:0, 40 min, containing 0.1% formic acid in both phase), to give an orange solid, which was recrystallized from the mixed solvents of CH2Cl2–MeOH (5:2 v/v), affording orange block-like crystals suitable for X-ray The 1H and 13C NMR data of 7β-hydroxyroyleanone have been reported elsewhere (Chang & Zhu, 2001).
6. Refinement
Crystal data, data collection and structure . The H atoms were positioned with idealized geometry and refined using a riding model, with O—H = 0.82 Å and C—H = 0.94–0.98 Å, and with Uiso(H) = 1.5Ueq(O,C) for hydroxy and methyl groups, and 1.2Ueq(C) for other H atoms.
details are summarized in Table 2Supporting information
CCDC reference: 1551129
https://doi.org/10.1107/S2056989017011987/su5382sup1.cif
contains datablocks I, Global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017011987/su5382Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989017011987/su5382Isup3.cdx
Supporting information file. DOI: https://doi.org/10.1107/S2056989017011987/su5382Isup4.cml
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).C20H28O4 | F(000) = 360 |
Mr = 332.42 | Dx = 1.252 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.2570 (18) Å | Cell parameters from 5396 reflections |
b = 7.6151 (13) Å | θ = 2.4–31.8° |
c = 11.503 (2) Å | µ = 0.09 mm−1 |
β = 101.110 (3)° | T = 296 K |
V = 881.6 (3) Å3 | Block, orange |
Z = 2 | 0.15 × 0.12 × 0.10 mm |
Bruker APEXII CCD diffractometer | Rint = 0.024 |
φ and ω scans | θmax = 26.0°, θmin = 1.8° |
6669 measured reflections | h = −12→12 |
3463 independent reflections | k = −9→8 |
3163 reflections with I > 2σ(I) | l = −14→14 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.030 | w = 1/[σ2(Fo2) + (0.0415P)2 + 0.1205P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.083 | (Δ/σ)max = 0.018 |
S = 1.03 | Δρmax = 0.18 e Å−3 |
3319 reflections | Δρmin = −0.11 e Å−3 |
225 parameters | Extinction correction: (SHELXL2014; Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.042 (5) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack x determined using 1341 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.2 (3) |
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 | ||
C1 | 0.18336 (18) | 0.9032 (3) | 0.38131 (16) | 0.0325 (4) | |
C2 | 0.12043 (19) | 1.0797 (3) | 0.33060 (16) | 0.0330 (4) | |
H2 | 0.0708 | 1.1210 | 0.3901 | 0.040* | |
C3 | 0.0151 (2) | 1.0710 (3) | 0.21358 (18) | 0.0436 (5) | |
C4 | −0.0879 (2) | 0.9310 (4) | 0.2287 (2) | 0.0558 (6) | |
H4A | −0.1416 | 0.9755 | 0.2830 | 0.067* | |
H4B | −0.1464 | 0.9124 | 0.1527 | 0.067* | |
C5 | −0.0293 (2) | 0.7561 (3) | 0.2744 (2) | 0.0552 (6) | |
H5A | 0.0162 | 0.7042 | 0.2163 | 0.066* | |
H5B | −0.1003 | 0.6773 | 0.2852 | 0.066* | |
C6 | 0.0680 (2) | 0.7766 (3) | 0.3915 (2) | 0.0449 (5) | |
H6A | 0.1043 | 0.6625 | 0.4175 | 0.054* | |
H6B | 0.0210 | 0.8209 | 0.4509 | 0.054* | |
C7 | 0.2771 (2) | 0.8148 (3) | 0.30881 (19) | 0.0468 (5) | |
H7A | 0.3432 | 0.8976 | 0.2954 | 0.070* | |
H7B | 0.2267 | 0.7760 | 0.2341 | 0.070* | |
H7C | 0.3198 | 0.7158 | 0.3519 | 0.070* | |
C8 | 0.0733 (3) | 1.0359 (5) | 0.1025 (2) | 0.0652 (7) | |
H8A | 0.1034 | 0.9164 | 0.1032 | 0.098* | |
H8B | 0.1467 | 1.1137 | 0.1015 | 0.098* | |
H8C | 0.0061 | 1.0555 | 0.0331 | 0.098* | |
C9 | −0.0575 (3) | 1.2484 (4) | 0.1956 (3) | 0.0632 (7) | |
H9A | 0.0009 | 1.3358 | 0.1739 | 0.095* | |
H9B | −0.0841 | 1.2826 | 0.2679 | 0.095* | |
H9C | −0.1347 | 1.2376 | 0.1338 | 0.095* | |
C10 | 0.2287 (2) | 1.2171 (3) | 0.33153 (17) | 0.0393 (4) | |
H10A | 0.2976 | 1.1703 | 0.2932 | 0.047* | |
H10B | 0.1914 | 1.3204 | 0.2881 | 0.047* | |
C11 | 0.28762 (18) | 1.2668 (2) | 0.45820 (17) | 0.0329 (4) | |
H11 | 0.2280 | 1.3501 | 0.4866 | 0.040* | |
C12 | 0.30669 (18) | 1.1084 (2) | 0.53977 (16) | 0.0304 (4) | |
C13 | 0.26614 (18) | 0.9456 (2) | 0.50399 (16) | 0.0304 (4) | |
C14 | 0.3121 (2) | 0.8004 (3) | 0.58809 (17) | 0.0346 (4) | |
C15 | 0.38257 (19) | 0.8399 (3) | 0.71053 (17) | 0.0354 (4) | |
C16 | 0.40798 (19) | 1.0040 (3) | 0.75146 (17) | 0.0347 (4) | |
C17 | 0.36998 (17) | 1.1471 (3) | 0.66582 (17) | 0.0319 (4) | |
C18 | 0.4710 (2) | 1.0503 (3) | 0.87781 (17) | 0.0434 (5) | |
H18 | 0.4779 | 1.1785 | 0.8825 | 0.052* | |
C19 | 0.3826 (3) | 0.9924 (4) | 0.9633 (2) | 0.0596 (7) | |
H19A | 0.2956 | 1.0422 | 0.9390 | 0.089* | |
H19B | 0.4203 | 1.0321 | 1.0418 | 0.089* | |
H19C | 0.3761 | 0.8667 | 0.9629 | 0.089* | |
C20 | 0.6116 (2) | 0.9766 (4) | 0.9132 (2) | 0.0596 (7) | |
H20A | 0.6080 | 0.8506 | 0.9140 | 0.089* | |
H20B | 0.6511 | 1.0186 | 0.9907 | 0.089* | |
H20C | 0.6640 | 1.0143 | 0.8571 | 0.089* | |
O1 | 0.29606 (19) | 0.6460 (2) | 0.56208 (14) | 0.0538 (4) | |
O2 | 0.41656 (17) | 0.6964 (2) | 0.77776 (13) | 0.0485 (4) | |
H2A | 0.3912 | 0.6082 | 0.7391 | 0.073* | |
O3 | 0.38668 (15) | 1.30061 (19) | 0.69666 (13) | 0.0441 (4) | |
O4 | 0.41202 (14) | 1.3502 (2) | 0.45960 (14) | 0.0458 (4) | |
H4 | 0.4286 | 1.4170 | 0.5165 | 0.069* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0336 (9) | 0.0310 (10) | 0.0314 (9) | 0.0013 (7) | 0.0025 (7) | −0.0020 (7) |
C2 | 0.0350 (9) | 0.0332 (10) | 0.0304 (8) | 0.0038 (8) | 0.0052 (7) | 0.0013 (7) |
C3 | 0.0406 (11) | 0.0488 (13) | 0.0373 (10) | 0.0060 (9) | −0.0025 (8) | 0.0032 (9) |
C4 | 0.0404 (11) | 0.0618 (17) | 0.0577 (14) | −0.0007 (11) | −0.0090 (10) | 0.0018 (12) |
C5 | 0.0486 (13) | 0.0476 (15) | 0.0628 (14) | −0.0103 (10) | −0.0057 (11) | −0.0022 (11) |
C6 | 0.0455 (11) | 0.0353 (12) | 0.0499 (12) | −0.0063 (9) | −0.0008 (9) | 0.0018 (9) |
C7 | 0.0472 (12) | 0.0483 (14) | 0.0435 (11) | 0.0137 (10) | 0.0048 (9) | −0.0089 (10) |
C8 | 0.0711 (16) | 0.087 (2) | 0.0342 (11) | 0.0040 (15) | 0.0019 (10) | −0.0009 (13) |
C9 | 0.0588 (15) | 0.0589 (18) | 0.0639 (15) | 0.0147 (12) | −0.0083 (12) | 0.0115 (13) |
C10 | 0.0454 (11) | 0.0375 (11) | 0.0343 (9) | −0.0008 (9) | 0.0059 (8) | 0.0086 (9) |
C11 | 0.0348 (9) | 0.0251 (10) | 0.0386 (9) | 0.0002 (7) | 0.0062 (7) | 0.0025 (7) |
C12 | 0.0296 (8) | 0.0283 (10) | 0.0331 (9) | 0.0036 (7) | 0.0057 (7) | 0.0015 (7) |
C13 | 0.0319 (9) | 0.0274 (10) | 0.0312 (9) | 0.0035 (7) | 0.0042 (7) | −0.0006 (7) |
C14 | 0.0409 (10) | 0.0244 (10) | 0.0370 (9) | 0.0001 (8) | 0.0038 (7) | 0.0002 (8) |
C15 | 0.0421 (10) | 0.0280 (10) | 0.0343 (9) | 0.0038 (8) | 0.0030 (8) | 0.0053 (7) |
C16 | 0.0376 (9) | 0.0330 (11) | 0.0315 (9) | −0.0003 (8) | 0.0017 (7) | 0.0000 (8) |
C17 | 0.0303 (8) | 0.0276 (10) | 0.0374 (9) | 0.0008 (7) | 0.0058 (7) | −0.0008 (8) |
C18 | 0.0539 (12) | 0.0355 (11) | 0.0351 (10) | −0.0038 (9) | −0.0058 (8) | −0.0008 (9) |
C19 | 0.0685 (16) | 0.0722 (19) | 0.0364 (11) | −0.0044 (13) | 0.0059 (10) | −0.0088 (11) |
C20 | 0.0518 (13) | 0.0643 (17) | 0.0538 (13) | −0.0058 (12) | −0.0119 (11) | 0.0043 (12) |
O1 | 0.0789 (11) | 0.0247 (8) | 0.0491 (9) | 0.0005 (8) | −0.0098 (8) | −0.0004 (7) |
O2 | 0.0687 (10) | 0.0291 (8) | 0.0405 (8) | 0.0007 (7) | −0.0074 (7) | 0.0059 (6) |
O3 | 0.0557 (9) | 0.0269 (8) | 0.0456 (8) | −0.0017 (6) | −0.0004 (7) | −0.0048 (6) |
O4 | 0.0443 (8) | 0.0421 (9) | 0.0517 (8) | −0.0115 (7) | 0.0111 (6) | 0.0015 (7) |
C1—C13 | 1.535 (2) | C10—C11 | 1.514 (3) |
C1—C7 | 1.543 (3) | C10—H10A | 0.9700 |
C1—C6 | 1.547 (3) | C10—H10B | 0.9700 |
C1—C2 | 1.555 (3) | C11—O4 | 1.423 (2) |
C2—C10 | 1.525 (3) | C11—C12 | 1.517 (3) |
C2—C3 | 1.556 (3) | C11—H11 | 0.9800 |
C2—H2 | 0.9800 | C12—C13 | 1.347 (3) |
C3—C4 | 1.534 (4) | C12—C17 | 1.499 (3) |
C3—C8 | 1.534 (3) | C13—C14 | 1.485 (3) |
C3—C9 | 1.538 (4) | C14—O1 | 1.217 (3) |
C4—C5 | 1.514 (4) | C14—C15 | 1.485 (3) |
C4—H4A | 0.9700 | C15—C16 | 1.343 (3) |
C4—H4B | 0.9700 | C15—O2 | 1.345 (2) |
C5—C6 | 1.522 (3) | C16—C17 | 1.470 (3) |
C5—H5A | 0.9700 | C16—C18 | 1.514 (3) |
C5—H5B | 0.9700 | C17—O3 | 1.224 (2) |
C6—H6A | 0.9700 | C18—C19 | 1.526 (3) |
C6—H6B | 0.9700 | C18—C20 | 1.527 (3) |
C7—H7A | 0.9600 | C18—H18 | 0.9800 |
C7—H7B | 0.9600 | C19—H19A | 0.9600 |
C7—H7C | 0.9600 | C19—H19B | 0.9600 |
C8—H8A | 0.9600 | C19—H19C | 0.9600 |
C8—H8B | 0.9600 | C20—H20A | 0.9600 |
C8—H8C | 0.9600 | C20—H20B | 0.9600 |
C9—H9A | 0.9600 | C20—H20C | 0.9600 |
C9—H9B | 0.9600 | O2—H2A | 0.8200 |
C9—H9C | 0.9600 | O4—H4 | 0.8200 |
C13—C1—C7 | 107.26 (15) | H9A—C9—H9C | 109.5 |
C13—C1—C6 | 110.93 (16) | H9B—C9—H9C | 109.5 |
C7—C1—C6 | 109.52 (18) | C11—C10—C2 | 109.46 (15) |
C13—C1—C2 | 106.21 (15) | C11—C10—H10A | 109.8 |
C7—C1—C2 | 115.53 (17) | C2—C10—H10A | 109.8 |
C6—C1—C2 | 107.36 (15) | C11—C10—H10B | 109.8 |
C10—C2—C1 | 109.97 (15) | C2—C10—H10B | 109.8 |
C10—C2—C3 | 114.73 (16) | H10A—C10—H10B | 108.2 |
C1—C2—C3 | 117.15 (16) | O4—C11—C10 | 108.25 (15) |
C10—C2—H2 | 104.5 | O4—C11—C12 | 109.85 (15) |
C1—C2—H2 | 104.5 | C10—C11—C12 | 112.14 (16) |
C3—C2—H2 | 104.5 | O4—C11—H11 | 108.9 |
C4—C3—C8 | 111.1 (2) | C10—C11—H11 | 108.9 |
C4—C3—C9 | 107.4 (2) | C12—C11—H11 | 108.8 |
C8—C3—C9 | 107.3 (2) | C13—C12—C17 | 121.81 (17) |
C4—C3—C2 | 108.08 (18) | C13—C12—C11 | 123.18 (16) |
C8—C3—C2 | 114.31 (18) | C17—C12—C11 | 114.97 (16) |
C9—C3—C2 | 108.44 (19) | C12—C13—C14 | 116.48 (16) |
C5—C4—C3 | 114.45 (19) | C12—C13—C1 | 123.93 (17) |
C5—C4—H4A | 108.6 | C14—C13—C1 | 119.50 (16) |
C3—C4—H4A | 108.6 | O1—C14—C13 | 123.26 (19) |
C5—C4—H4B | 108.6 | O1—C14—C15 | 116.57 (18) |
C3—C4—H4B | 108.6 | C13—C14—C15 | 120.16 (17) |
H4A—C4—H4B | 107.6 | C16—C15—O2 | 122.88 (17) |
C4—C5—C6 | 111.5 (2) | C16—C15—C14 | 123.19 (18) |
C4—C5—H5A | 109.3 | O2—C15—C14 | 113.92 (17) |
C6—C5—H5A | 109.3 | C15—C16—C17 | 116.50 (17) |
C4—C5—H5B | 109.3 | C15—C16—C18 | 124.83 (19) |
C6—C5—H5B | 109.3 | C17—C16—C18 | 118.67 (18) |
H5A—C5—H5B | 108.0 | O3—C17—C16 | 120.63 (18) |
C5—C6—C1 | 112.19 (18) | O3—C17—C12 | 118.58 (17) |
C5—C6—H6A | 109.2 | C16—C17—C12 | 120.78 (17) |
C1—C6—H6A | 109.2 | C16—C18—C19 | 110.77 (18) |
C5—C6—H6B | 109.2 | C16—C18—C20 | 112.1 (2) |
C1—C6—H6B | 109.2 | C19—C18—C20 | 111.7 (2) |
H6A—C6—H6B | 107.9 | C16—C18—H18 | 107.3 |
C1—C7—H7A | 109.5 | C19—C18—H18 | 107.3 |
C1—C7—H7B | 109.5 | C20—C18—H18 | 107.3 |
H7A—C7—H7B | 109.5 | C18—C19—H19A | 109.5 |
C1—C7—H7C | 109.5 | C18—C19—H19B | 109.5 |
H7A—C7—H7C | 109.5 | H19A—C19—H19B | 109.5 |
H7B—C7—H7C | 109.5 | C18—C19—H19C | 109.5 |
C3—C8—H8A | 109.5 | H19A—C19—H19C | 109.5 |
C3—C8—H8B | 109.5 | H19B—C19—H19C | 109.5 |
H8A—C8—H8B | 109.5 | C18—C20—H20A | 109.5 |
C3—C8—H8C | 109.5 | C18—C20—H20B | 109.5 |
H8A—C8—H8C | 109.5 | H20A—C20—H20B | 109.5 |
H8B—C8—H8C | 109.5 | C18—C20—H20C | 109.5 |
C3—C9—H9A | 109.5 | H20A—C20—H20C | 109.5 |
C3—C9—H9B | 109.5 | H20B—C20—H20C | 109.5 |
H9A—C9—H9B | 109.5 | C15—O2—H2A | 109.5 |
C3—C9—H9C | 109.5 | C11—O4—H4 | 109.5 |
C13—C1—C2—C10 | 54.86 (19) | C11—C12—C13—C1 | −6.7 (3) |
C7—C1—C2—C10 | −63.9 (2) | C7—C1—C13—C12 | 105.6 (2) |
C6—C1—C2—C10 | 173.59 (16) | C6—C1—C13—C12 | −134.8 (2) |
C13—C1—C2—C3 | −171.78 (16) | C2—C1—C13—C12 | −18.5 (2) |
C7—C1—C2—C3 | 69.5 (2) | C7—C1—C13—C14 | −70.9 (2) |
C6—C1—C2—C3 | −53.1 (2) | C6—C1—C13—C14 | 48.6 (2) |
C10—C2—C3—C4 | −178.36 (19) | C2—C1—C13—C14 | 164.98 (16) |
C1—C2—C3—C4 | 50.4 (2) | C12—C13—C14—O1 | −171.2 (2) |
C10—C2—C3—C8 | 57.4 (3) | C1—C13—C14—O1 | 5.6 (3) |
C1—C2—C3—C8 | −73.8 (3) | C12—C13—C14—C15 | 8.3 (3) |
C10—C2—C3—C9 | −62.3 (2) | C1—C13—C14—C15 | −174.92 (17) |
C1—C2—C3—C9 | 166.5 (2) | O1—C14—C15—C16 | 179.6 (2) |
C8—C3—C4—C5 | 76.0 (3) | C13—C14—C15—C16 | 0.1 (3) |
C9—C3—C4—C5 | −166.9 (2) | O1—C14—C15—O2 | −1.6 (3) |
C2—C3—C4—C5 | −50.1 (3) | C13—C14—C15—O2 | 178.92 (17) |
C3—C4—C5—C6 | 56.2 (3) | O2—C15—C16—C17 | 177.42 (18) |
C4—C5—C6—C1 | −58.2 (3) | C14—C15—C16—C17 | −3.9 (3) |
C13—C1—C6—C5 | 170.39 (19) | O2—C15—C16—C18 | −3.1 (3) |
C7—C1—C6—C5 | −71.4 (2) | C14—C15—C16—C18 | 175.61 (19) |
C2—C1—C6—C5 | 54.8 (2) | C15—C16—C17—O3 | 178.2 (2) |
C1—C2—C10—C11 | −68.9 (2) | C18—C16—C17—O3 | −1.4 (3) |
C3—C2—C10—C11 | 156.51 (17) | C15—C16—C17—C12 | −0.2 (3) |
C2—C10—C11—O4 | 162.26 (16) | C18—C16—C17—C12 | −179.73 (17) |
C2—C10—C11—C12 | 40.9 (2) | C13—C12—C17—O3 | −169.35 (19) |
O4—C11—C12—C13 | −125.08 (19) | C11—C12—C17—O3 | 8.4 (2) |
C10—C11—C12—C13 | −4.7 (3) | C13—C12—C17—C16 | 9.0 (3) |
O4—C11—C12—C17 | 57.2 (2) | C11—C12—C17—C16 | −173.16 (16) |
C10—C11—C12—C17 | 177.58 (16) | C15—C16—C18—C19 | −63.3 (3) |
C17—C12—C13—C14 | −12.5 (3) | C17—C16—C18—C19 | 116.2 (2) |
C11—C12—C13—C14 | 169.93 (16) | C15—C16—C18—C20 | 62.2 (3) |
C17—C12—C13—C1 | 170.90 (16) | C17—C16—C18—C20 | −118.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O1 | 0.82 | 2.10 | 2.579 (2) | 117 |
O4—H4···O3 | 0.82 | 2.37 | 2.814 (2) | 115 |
O2—H2A···O3i | 0.82 | 2.39 | 3.153 (2) | 155 |
O4—H4···O1ii | 0.82 | 2.33 | 2.901 (2) | 127 |
C11—H11···O1ii | 0.98 | 2.47 | 3.120 (2) | 124 |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z. |
Funding information
Funding for this research was provided by: Natural Science Foundation of Qinghai Province (grant No. 2016-ZJ-908); National Natural Science Foundation of China grant (grant No. 81573561).
References
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Burmistrova, O., Simoes, M. F., Rijo, P., Quintana, J., Bermejo, J. & Estevez, F. (2013). J. Nat. Prod. 76, 1413–1423. Web of Science CrossRef CAS PubMed
Chang, J. & Zhu, N. S. (2001). Nat. Prod. Res. Dev. 13, 27–29. CAS
Chen, X., Liao, R.-A., Weng, L.-H., Xie, Q.-L. & Deng, F.-J. (2000). Chin. J. Struct. Chem. 19, 122–125. CAS
Eugster, C. H., Ruedi, P., Tanudjaja, T., Bieri, J. H., Prewo, R. & Linden, A. (1993). Private communication. CCDC, Cambridge, England.
Fun, H.-K., Chantrapromma, S., Salae, A. W., Razak, I. A. & Karalai, C. (2011). Acta Cryst. E67, o1032–o1033. Web of Science CSD CrossRef IUCr Journals
Gonzalez, M. A. (2015). Nat. Prod. Rep. 32, 684–704. Web of Science CAS PubMed
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals
Kolak, U., Kabouche, A., Öztürk, M., Kabouche, Z., Topçu, G. & Ulubelen, A. (2009). Phytochem. Anal. 20, 320–327. Web of Science CrossRef PubMed CAS
Kusumoto, N., Ashitani, T., Hayasaka, Y., Murayama, T., Ogiyama, K. & Takahashi, K. (2009). J. Chem. Ecol. 35, 635–642. Web of Science CrossRef PubMed CAS
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals
Razak, I. A., Salae, A. W., Chantrapromma, S., Karalai, C. & Fun, H.-K. (2010). Acta Cryst. E66, o1566–o1567. Web of Science CSD CrossRef IUCr Journals
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals
Si, Y., Zhang, C.-K., Yao, X.-H. & Tu, Z.-B. (2001). J. Wuhan Bot. Res. 19, 517–520.
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals
Tanaka, R. (2001). Bioorg. Med. Chem. 9, 1911–1921. Web of Science CrossRef PubMed
Topçu, G. & Gören, A. C. (2007). Rec. Nat. Prod. 1, 1–16.
Topçu, G., Kolak, U., Ozturk, M., Boga, M., Hatipoglu, S. D., Bahadori, F., Culhaoglu, B. & Dirmenci, T. (2013). Nat. Prod. J, 3, 3–9.
Yang, Z., Kitano, Y., Chiba, K., Shibata, N., Kurokawa, H., Doi, Y., Arakawa, Y. & Tada, M. (2001). Bioorg. Med. Chem. 9, 347–356. Web of Science CrossRef PubMed CAS
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