Crystal structure and Hirshfeld surface analysis of 2-oxo-13-epi-manoyl oxide isolated from Sideritis perfoliata.

The title compound, C20H32O2 (systematic name: 3-ethenyl-3,4a,7,7,10a-penta-methyl-dodeca-hydro-9H-benzo[f]chromen-9-one), was isolated from Sideritis perfoliata. In the crystal, mol-ecules pack in helical supra-molecular chains along the 21 screw axis running parallel to the a axis, bound by C-H⋯O hydrogen bonds. These chains are efficiently inter-locked in the other two unit-cell directions via van der Waals inter-actions. Hirshfeld surface analysis shows that van der Waals inter-actions constitute the major contribution to the inter-molecular inter-actions, with H⋯H contacts accounting for 86.0% of the surface.

Chemical context

The genus Sideritis belonging to the Lamiaceae family is represented by more than 150 species, distributed in tropical regions. Most of the species are found in the Mediterranean region. This genus is represented by 54 species in Turkey flora, 40 of which are endemic (Davis, 1982 ▸). Sideritis species have traditionally been used as herbal teas, flavouring agents and therapeutics (Danesi et al., 2013 ▸). Sideritis species include flavonoids, terpenes, iridoids, coumarins, lignanes and sterols that are responsible constituents for their pharmacological properties (González-Burgos et al., 2011 ▸). Sideritis species have been reported to exhibit considerable biological activities such as anti­oxidant (Demirtas et al., 2011 ▸), anti­proliferative (Demirtas et al., 2009 ▸), and anti­microbial (Yiğit Hanoğlu et al., 2017 ▸) effects. The crystal structure of 2-β-hy­droxy­manoyl oxide isolated from Sideritis perfoliata has been reported on by our group (Çelik et al., 2016 ▸). Herein, we report on the crystal structure of 2-oxo-13-epi-manoyl oxide, also isolated from S. perfoliata.

Structural commentary

As shown in Fig. 1 ▸, the junction between the two cyclo­hexane rings A (C8–C13) and B (C4–C9) is trans, and the junction for the tetra­hydro­pyran ring C (O1/C1–C5) is also trans. The six-membered carbon rings A and B possess chair conformations [puckering parameters: Q T = 0.528 (7) Å, θ = 172.6 (8)°, φ = 255 (6)° for ring A and Q T = 0.578 (6) Å, θ = 2.1 (6)°, φ = 261 (16)° for ring B]. The tetra­hydro­pyran ring has a slightly twisted boat conformation [puckering parameters: Q(2) = 0.411 (6) Å and φ(2) = 81.4 (8)°].

Figure 1

The mol­ecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 30% probability level.

Supra­molecular features

In the crystal, mol­ecules pack in helical supra­molecular C(11) chains along the 21 screw axis running parallel to the a axis, bound by C—H⋯O hydrogen bonds (Fig. 2 ▸ and Table 1 ▸). The chains are efficiently inter­locked in the other two unit-cell directions via van der Waals inter­actions. Between the chains there are narrow channels which also run along the [100] direction.

Figure 2

A view along the a axis of the crystal packing of the title compound. H atoms not involved in these inter­actions have been omitted for clarity.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18—H18A⋯O2i	0.93	2.59	3.501 (9)	167

Symmetry code: (i) .

Database survey

A search of the Cambridge Structural Database (CSD, V5.39, last update February 2018; Groom et al., 2016 ▸), for 3-ethenyl-3-methyl­dodeca­hydro-1H-naphtho­[2,1-b]pyran structures, gave 28 hits, all of which present the same basic structural motif as described herein for the title compound. The closest related compound is 2-β-hy­droxy­manoyl oxide [systematic name: 3,4a,7,7,10a-penta­methyl-3-vinyl­dodeca­hydro-1H-benzo[f]chromen- 9-ol] also isolated from Sideritis perfoliata (UVEVOI; Çelik et al., 2016 ▸ ). Other compounds include, Forskolin G (systematic name: 1α-hy­droxy-6β,7β-diacet­oxy-8,13-ep­oxy­labd-14-en-11-one; CSD refcode ADATUV; Shan et al., 2006 ▸), lα,5β-di­hydroxy­manoyl oxide, a novel diterpene from Satureja gilliesii (RASXUE; Manríquez et al., 1997 ▸), 4a-hy­droxy-18-normanoyl oxide (GAPZUT; Ybarra et al., 2005 ▸), jhanol (GAQBAC; Ybarra et al., 2005 ▸), 1R,11S-dihy­droxy-8R,13R-ep­oxy­labd-14-ene (LUDTOU; Stavri et al., 2009 ▸) and (−)-paniculatol (NEJHAL; Briand et al., 1997 ▸).

In the title compound (P212121, Z = 4), the mol­ecules pack in helical supra­molecular chains along the 21 screw axis running parallel to the a axis, bound by one C—H⋯O hydrogen bond. These chains are efficiently inter­locked in the other two unit-cell directions via van der Waals inter­actions. In the similar compound UVEVOI (P212121, Z = 8), the asymmetric unit contains two independent mol­ecules. Inter­molecular O—H⋯O hydrogen bonds connect adjacent mol­ecules, forming C(6) helical chains located around a 21 screw axis running along the a-axis direction. The crystal packing of these chains is governed only by van der Waals inter­actions. The two asymmetric mol­ecules lead to pseudo-41 symmetry in space group P212121. The crystal structure of the other similar compound UDATUV (P21, Z = 4) is stabilized by inter­molecular O—H⋯O and C—H⋯O hydrogen bonds, which link the mol­ecules into networks approximately parallel to the (110) plane. In the crystal structure of the compound RASXUE (P21, Z = 4), no inter­molecular hydrogen-bonding inter­actions were detected, but the O—H⋯O or C—H⋯O inter­actions are possible hydrogen bonds. In GAPZUT (P21, Z = 6), there are three independent mol­ecules in the asymmetric unit. In the crystal, there is no classical hydrogen bonding·The mol­ecular packing is stabilized by van der Waals inter­actions and no π–π or C—H⋯π inter­actions are observed. In GAQBAC (P21, Z = 2), mol­ecules are connected by O—H⋯O hydrogen bonds into chains propagating along the c-axis direction. Here too, no π–π or C—H⋯π inter­actions are observed. In LUDTOU (P21, Z = 4), the structure contains a water mol­ecule. In the crystal, mol­ecules are connected via O—H⋯O hydrogen bonds involving the water mol­ecules, forming a three-dimensional framework. Again no π–π or C—H⋯π inter­actions are observed.

Hirshfeld surface analysis

A large range of properties of inter­molecular close contacts of a structure can be visualized on the Hirshfeld surface with the program CrystalExplorer (Wolff et al., 2012 ▸), including d e and d i, which represent the distances from a point on the Hirshfeld surface to the nearest atoms outside (external) and inside (inter­nal) the surface, respectively.

Inter­molecular distance information on the surface can be condensed into a two-dimensional histogram of d e and d i, which is a unique identifier for mol­ecules in a crystal structure, and is known as a fingerprint plot (Rohl et al., 2008 ▸). Instead of plotting d e and d i on the Hirshfeld surface, contact distances are normalized in CrystalExplorer using the van der Waals radius of the appropriate inter­nal (r i vdw) and external (r e vdw) atom of the surface:

d norm= (d i-r i vdw)/r i vdw+(d e-r e vdw)/r vdw.

For the title compound, the three-dimensional Hirshfeld surface mapped over d is given in Fig. 3 ▸. Contacts with distances equal to the sum of the van der Waals radii are shown in white, and contacts with distances shorter than or longer than the related sum values are shown in red (highlighted contacts) or blue, respectively. Two-dimensional finger print plots showing the occurrence of the various inter­molecular contacts are presented in Fig. 4 ▸ a–d. The H⋯H inter­actions appear in the middle of the scattered points in the two-dimensional fingerprint plots with an overall contribution to the Hirshfeld surface of 86.0% (Fig. 4 ▸ b). The contribution from the H⋯O/O⋯H contacts, corresponding to C—H⋯O inter­actions, is represented by a pair of sharp spikes characteristic of a strong hydrogen-bond inter­action (12.6%) (Fig. 4 ▸ c). The contribution of the other inter­molecular contacts to the Hirshfeld surfaces is H⋯C/C⋯H (1.4%) (Fig. 4 ▸ d). The large number of H⋯H, H⋯O/O⋯H and H⋯C/C⋯H inter­actions suggest that van der Waals inter­actions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015 ▸). A view of the Hirshfeld surface of the title complex plotted over the shape-index is given in Fig. 5 ▸.

Figure 3

View of the three-dimensional Hirshfeld surface of the title compound mapped with d norm.

Figure 4

The two-dimensional fingerprint plots of the title compound, showing (a) all inter­actions, and delineated into (b) H⋯H, (c) H⋯O and (d) H⋯C inter­actions [d e and d i represent the distances from a point on the Hirshfeld surface to the nearest atoms outside (external) and inside (inter­nal) the surface, respectively].

Figure 5

Hirshfeld surface of the title complex plotted over the shape-index.

Synthesis and crystallization

The floral parts of Sideritis perfoliata (100 g) were extracted with EtOAc (3 × 1.0 L). After removal of the solvent in vacuo, the extract (4.0 g) was subjected to Sephadex LH-20 column chromatography using methanol as the mobile phase at 0.5 ml/min flow rate. According to TLC basis the 6–8th fractions were combined (1.2 g) and separated over silica gel column chromatography using a hexa­ne/EtOAc (6/4) mixture. Fractions 2–4 were combined to give 2-oxo-13-epi-manoyl oxide (60 mg). After removal of the solvent, a white amorphous powder was obtained. The solid was dissolved in acetone and left to stand at room temperature for 12 h. On slow evaporation of the solvent, colourless block-like crystals were obtained.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms: C—H = 0.93–0.97 Å with U iso(H) = 1.5U eq(C-meth­yl) and 1.2U eq(C) for other H atoms. As the title compound is a weak anomalous scatterer, the value of the Flack parameter of −1.1 (10) is meaningless.

Table 2

Experimental details

Crystal data
Chemical formula	C20H32O2
M r	304.46
Crystal system, space group	Orthorhombic, P212121
Temperature (K)	296
a, b, c (Å)	7.803 (2), 9.242 (3), 24.952 (7)
V (Å3)	1799.4 (9)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.07
Crystal size (mm)	0.12 × 0.11 × 0.09
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007 ▸)
T min, T max	0.596, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	11666, 3530, 2120
R int	0.097
(sin θ/λ)max (Å−1)	0.626
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.096, 0.186, 1.27
No. of reflections	3530
No. of parameters	204
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.21, −0.25

Computer programs: APEX2 and SAINT (Bruker, 2007 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018005807/su5431sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018005807/su5431Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989018005807/su5431Isup3.cml

CCDC reference: 1837011

Additional supporting information: crystallographic information; 3D view; checkCIF report

C20H32O2	F(000) = 672
Mr = 304.46	Dx = 1.124 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6426 reflections
a = 7.803 (2) Å	θ = 3.1–26.4°
b = 9.242 (3) Å	µ = 0.07 mm−1
c = 24.952 (7) Å	T = 296 K
V = 1799.4 (9) Å3	Block, colourless
Z = 4	0.12 × 0.11 × 0.09 mm

Bruker APEXII CCD diffractometer	2120 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.097
Absorption correction: multi-scan (SADABS; Bruker, 2007)	θmax = 26.4°, θmin = 3.1°
Tmin = 0.596, Tmax = 0.745	h = −8→9
11666 measured reflections	k = −11→11
3530 independent reflections	l = −30→31

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.096	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.186	H-atom parameters constrained
S = 1.27	w = 1/[σ2(Fo2) + (0.0079P)2 + 2.0609P] where P = (Fo2 + 2Fc2)/3
3530 reflections	(Δ/σ)max < 0.001
204 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > 2sigma(F2) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
O1	0.2335 (5)	0.8443 (5)	0.71085 (15)	0.0343 (16)
O2	0.3930 (9)	0.4214 (6)	0.47206 (19)	0.083 (3)
C1	0.0977 (8)	0.9360 (7)	0.6904 (2)	0.034 (2)
C2	0.0185 (8)	0.8669 (7)	0.6406 (2)	0.037 (2)
C3	0.1511 (8)	0.8173 (7)	0.5996 (2)	0.034 (2)
C4	0.2784 (8)	0.7152 (6)	0.6273 (2)	0.0247 (19)
C5	0.3660 (8)	0.7939 (6)	0.6745 (2)	0.0257 (19)
C6	0.4657 (8)	0.6837 (7)	0.7072 (2)	0.036 (2)
C7	0.5901 (8)	0.5959 (7)	0.6731 (2)	0.035 (2)
C8	0.4971 (9)	0.5188 (7)	0.6269 (2)	0.0310 (19)
C9	0.4001 (9)	0.6277 (6)	0.5902 (2)	0.0303 (19)
C10	0.2898 (10)	0.5375 (8)	0.5505 (2)	0.044 (3)
C11	0.3961 (11)	0.4285 (8)	0.5206 (3)	0.050 (3)
C12	0.4981 (10)	0.3273 (7)	0.5547 (3)	0.051 (3)
C13	0.6085 (9)	0.4010 (7)	0.5985 (3)	0.038 (2)
C14	0.6582 (10)	0.2831 (8)	0.6390 (3)	0.056 (3)
C15	0.7747 (11)	0.4588 (9)	0.5732 (3)	0.067 (3)
C16	0.4820 (9)	0.9208 (7)	0.6596 (3)	0.040 (2)
C17	0.1589 (9)	1.0879 (7)	0.6821 (3)	0.039 (2)
C18	0.1195 (10)	1.1772 (8)	0.6434 (3)	0.050 (3)
C19	−0.0318 (10)	0.9399 (8)	0.7360 (3)	0.059 (3)
C20	0.5154 (11)	0.7268 (7)	0.5559 (3)	0.049 (3)
H2A	−0.04990	0.78430	0.65140	0.0440*
H2B	−0.05760	0.93630	0.62370	0.0440*
H3A	0.21130	0.90030	0.58510	0.0410*
H3B	0.09470	0.76740	0.57030	0.0410*
H4	0.20610	0.64180	0.64440	0.0300*
H6A	0.38570	0.61840	0.72450	0.0430*
H6B	0.52920	0.73360	0.73500	0.0430*
H7A	0.64680	0.52460	0.69540	0.0420*
H7B	0.67720	0.65970	0.65850	0.0420*
H8	0.40580	0.46380	0.64450	0.0370*
H10A	0.20050	0.48750	0.57030	0.0530*
H10B	0.23500	0.60210	0.52520	0.0530*
H12A	0.57310	0.27130	0.53160	0.0610*
H12B	0.41990	0.26020	0.57190	0.0610*
H14A	0.55750	0.25030	0.65750	0.0840*
H14B	0.73820	0.32210	0.66440	0.0840*
H14C	0.70990	0.20330	0.62040	0.0840*
H15A	0.83750	0.51340	0.59950	0.1000*
H15B	0.74710	0.52010	0.54340	0.1000*
H15C	0.84340	0.37910	0.56110	0.1000*
H16A	0.42730	0.97830	0.63240	0.0600*
H16B	0.58910	0.88470	0.64610	0.0600*
H16C	0.50240	0.97930	0.69070	0.0600*
H17	0.23470	1.12310	0.70770	0.0470*
H18A	0.04430	1.14840	0.61660	0.0600*
H18B	0.16670	1.26960	0.64280	0.0600*
H19A	−0.07240	0.84370	0.74300	0.0890*
H19B	−0.12660	1.00050	0.72610	0.0890*
H19C	0.02180	0.97810	0.76760	0.0890*
H20A	0.44920	0.80690	0.54280	0.0740*
H20B	0.56040	0.67290	0.52620	0.0740*
H20C	0.60830	0.76240	0.57740	0.0740*

	U11	U22	U33	U12	U13	U23
O1	0.032 (3)	0.044 (3)	0.027 (2)	0.010 (2)	0.0025 (19)	0.000 (2)
O2	0.132 (6)	0.082 (4)	0.035 (3)	−0.004 (4)	0.005 (3)	−0.019 (3)
C1	0.025 (4)	0.040 (4)	0.038 (3)	0.001 (3)	0.002 (3)	0.001 (3)
C2	0.025 (4)	0.039 (4)	0.047 (4)	−0.002 (3)	−0.005 (3)	0.000 (3)
C3	0.032 (4)	0.040 (4)	0.030 (3)	0.003 (3)	−0.014 (3)	0.000 (3)
C4	0.022 (3)	0.031 (4)	0.021 (3)	−0.010 (3)	−0.002 (3)	0.000 (3)
C5	0.023 (3)	0.027 (4)	0.027 (3)	0.002 (3)	−0.003 (3)	−0.006 (3)
C6	0.039 (4)	0.041 (4)	0.028 (3)	0.007 (4)	−0.011 (3)	−0.003 (3)
C7	0.025 (4)	0.038 (4)	0.043 (4)	0.004 (3)	−0.007 (3)	−0.003 (3)
C8	0.030 (4)	0.030 (3)	0.033 (3)	0.003 (3)	0.008 (3)	0.000 (3)
C9	0.041 (4)	0.028 (3)	0.022 (3)	−0.005 (3)	0.001 (3)	−0.002 (3)
C10	0.051 (5)	0.046 (5)	0.035 (4)	0.000 (4)	−0.010 (3)	−0.002 (3)
C11	0.066 (5)	0.042 (4)	0.042 (4)	−0.010 (4)	0.004 (4)	−0.017 (4)
C12	0.058 (5)	0.040 (4)	0.054 (4)	0.000 (4)	0.010 (4)	−0.016 (4)
C13	0.033 (4)	0.033 (4)	0.049 (4)	−0.003 (3)	0.007 (3)	−0.004 (3)
C14	0.056 (5)	0.037 (4)	0.076 (6)	0.016 (4)	0.004 (4)	−0.002 (4)
C15	0.052 (5)	0.063 (6)	0.086 (6)	0.004 (5)	0.029 (5)	−0.011 (5)
C16	0.031 (4)	0.035 (4)	0.055 (4)	−0.005 (4)	0.000 (3)	−0.007 (3)
C17	0.034 (4)	0.035 (4)	0.048 (4)	0.006 (3)	−0.003 (3)	−0.005 (4)
C18	0.043 (5)	0.039 (4)	0.068 (5)	0.001 (4)	0.004 (4)	0.000 (4)
C19	0.053 (5)	0.068 (5)	0.057 (5)	0.017 (5)	0.024 (4)	0.005 (4)
C20	0.070 (6)	0.040 (4)	0.038 (4)	0.004 (4)	0.024 (4)	0.004 (3)

O1—C1	1.450 (7)	C4—H4	0.9800
O1—C5	1.452 (7)	C6—H6A	0.9700
O2—C11	1.213 (9)	C6—H6B	0.9700
C1—C2	1.528 (8)	C7—H7A	0.9700
C1—C17	1.497 (9)	C7—H7B	0.9700
C1—C19	1.522 (9)	C8—H8	0.9800
C2—C3	1.526 (8)	C10—H10A	0.9700
C3—C4	1.535 (8)	C10—H10B	0.9700
C4—C5	1.544 (8)	C12—H12A	0.9700
C4—C9	1.553 (8)	C12—H12B	0.9700
C5—C6	1.519 (8)	C14—H14A	0.9600
C5—C16	1.527 (9)	C14—H14B	0.9600
C6—C7	1.525 (8)	C14—H14C	0.9600
C7—C8	1.537 (8)	C15—H15A	0.9600
C8—C9	1.557 (8)	C15—H15B	0.9600
C8—C13	1.563 (9)	C15—H15C	0.9600
C9—C10	1.555 (9)	C16—H16A	0.9600
C9—C20	1.543 (10)	C16—H16B	0.9600
C10—C11	1.503 (10)	C16—H16C	0.9600
C11—C12	1.494 (11)	C17—H17	0.9300
C12—C13	1.549 (10)	C18—H18A	0.9300
C13—C14	1.536 (10)	C18—H18B	0.9300
C13—C15	1.538 (11)	C19—H19A	0.9600
C17—C18	1.307 (10)	C19—H19B	0.9600
C2—H2A	0.9700	C19—H19C	0.9600
C2—H2B	0.9700	C20—H20A	0.9600
C3—H3A	0.9700	C20—H20B	0.9600
C3—H3B	0.9700	C20—H20C	0.9600
C1—O1—C5	119.2 (4)	C7—C6—H6A	109.00
O1—C1—C2	109.7 (5)	C7—C6—H6B	109.00
O1—C1—C17	111.3 (5)	H6A—C6—H6B	108.00
O1—C1—C19	103.7 (5)	C6—C7—H7A	109.00
C2—C1—C17	114.1 (5)	C6—C7—H7B	109.00
C2—C1—C19	110.5 (5)	C8—C7—H7A	109.00
C17—C1—C19	107.0 (5)	C8—C7—H7B	109.00
C1—C2—C3	113.4 (5)	H7A—C7—H7B	108.00
C2—C3—C4	108.8 (4)	C7—C8—H8	104.00
C3—C4—C5	109.9 (5)	C9—C8—H8	104.00
C3—C4—C9	116.6 (4)	C13—C8—H8	104.00
C5—C4—C9	115.4 (5)	C9—C10—H10A	109.00
O1—C5—C4	108.2 (5)	C9—C10—H10B	109.00
O1—C5—C6	104.1 (4)	C11—C10—H10A	109.00
O1—C5—C16	109.1 (5)	C11—C10—H10B	109.00
C4—C5—C6	108.7 (5)	H10A—C10—H10B	108.00
C4—C5—C16	116.0 (5)	C11—C12—H12A	108.00
C6—C5—C16	110.0 (5)	C11—C12—H12B	108.00
C5—C6—C7	112.5 (4)	C13—C12—H12A	109.00
C6—C7—C8	111.4 (5)	C13—C12—H12B	109.00
C7—C8—C9	111.8 (5)	H12A—C12—H12B	108.00
C7—C8—C13	113.6 (6)	C13—C14—H14A	109.00
C9—C8—C13	117.0 (5)	C13—C14—H14B	109.00
C4—C9—C8	106.5 (4)	C13—C14—H14C	109.00
C4—C9—C10	108.7 (5)	H14A—C14—H14B	109.00
C4—C9—C20	112.2 (5)	H14A—C14—H14C	109.00
C8—C9—C10	107.3 (5)	H14B—C14—H14C	110.00
C8—C9—C20	115.2 (6)	C13—C15—H15A	109.00
C10—C9—C20	106.7 (5)	C13—C15—H15B	110.00
C9—C10—C11	111.7 (6)	C13—C15—H15C	109.00
O2—C11—C10	121.4 (7)	H15A—C15—H15B	109.00
O2—C11—C12	123.1 (7)	H15A—C15—H15C	109.00
C10—C11—C12	115.5 (6)	H15B—C15—H15C	110.00
C11—C12—C13	115.0 (6)	C5—C16—H16A	109.00
C8—C13—C12	108.5 (6)	C5—C16—H16B	110.00
C8—C13—C14	109.7 (6)	C5—C16—H16C	110.00
C8—C13—C15	114.4 (6)	H16A—C16—H16B	109.00
C12—C13—C14	107.0 (5)	H16A—C16—H16C	109.00
C12—C13—C15	109.4 (6)	H16B—C16—H16C	110.00
C14—C13—C15	107.7 (6)	C1—C17—H17	116.00
C1—C17—C18	128.3 (7)	C18—C17—H17	116.00
C1—C2—H2A	109.00	C17—C18—H18A	120.00
C1—C2—H2B	109.00	C17—C18—H18B	120.00
C3—C2—H2A	109.00	H18A—C18—H18B	120.00
C3—C2—H2B	109.00	C1—C19—H19A	109.00
H2A—C2—H2B	108.00	C1—C19—H19B	109.00
C2—C3—H3A	110.00	C1—C19—H19C	109.00
C2—C3—H3B	110.00	H19A—C19—H19B	109.00
C4—C3—H3A	110.00	H19A—C19—H19C	110.00
C4—C3—H3B	110.00	H19B—C19—H19C	109.00
H3A—C3—H3B	108.00	C9—C20—H20A	109.00
C3—C4—H4	104.00	C9—C20—H20B	109.00
C5—C4—H4	104.00	C9—C20—H20C	109.00
C9—C4—H4	105.00	H20A—C20—H20B	110.00
C5—C6—H6A	109.00	H20A—C20—H20C	109.00
C5—C6—H6B	109.00	H20B—C20—H20C	109.00
C5—O1—C1—C2	50.8 (7)	C4—C5—C6—C7	53.8 (7)
C5—O1—C1—C17	−76.5 (6)	C16—C5—C6—C7	−74.3 (6)
C5—O1—C1—C19	168.8 (5)	C5—C6—C7—C8	−56.6 (7)
C1—O1—C5—C6	−171.1 (5)	C6—C7—C8—C9	57.8 (7)
C1—O1—C5—C16	71.5 (6)	C6—C7—C8—C13	−167.1 (5)
C1—O1—C5—C4	−55.5 (6)	C7—C8—C9—C4	−55.5 (6)
C19—C1—C2—C3	−162.4 (5)	C7—C8—C9—C10	−171.7 (5)
C2—C1—C17—C18	17.1 (10)	C7—C8—C9—C20	69.6 (6)
C19—C1—C17—C18	−105.4 (8)	C13—C8—C9—C4	171.1 (5)
O1—C1—C17—C18	142.0 (7)	C13—C8—C9—C10	54.9 (7)
O1—C1—C2—C3	−48.8 (6)	C13—C8—C9—C20	−63.8 (7)
C17—C1—C2—C3	76.9 (7)	C7—C8—C13—C12	177.6 (5)
C1—C2—C3—C4	55.0 (7)	C7—C8—C13—C14	61.0 (7)
C2—C3—C4—C9	167.5 (5)	C7—C8—C13—C15	−60.1 (7)
C2—C3—C4—C5	−58.7 (6)	C9—C8—C13—C12	−49.9 (7)
C3—C4—C5—C6	169.8 (5)	C9—C8—C13—C14	−166.4 (6)
C9—C4—C5—C6	−55.9 (6)	C9—C8—C13—C15	72.5 (8)
C3—C4—C5—C16	−65.7 (7)	C4—C9—C10—C11	−168.9 (5)
C9—C4—C5—O1	−168.4 (4)	C8—C9—C10—C11	−54.1 (7)
C3—C4—C5—O1	57.3 (6)	C20—C9—C10—C11	69.9 (7)
C3—C4—C9—C20	60.6 (7)	C9—C10—C11—O2	−127.6 (8)
C5—C4—C9—C8	56.3 (6)	C9—C10—C11—C12	54.9 (8)
C5—C4—C9—C10	171.6 (5)	O2—C11—C12—C13	132.0 (8)
C5—C4—C9—C20	−70.7 (6)	C10—C11—C12—C13	−50.5 (9)
C9—C4—C5—C16	68.6 (6)	C11—C12—C13—C8	45.0 (8)
C3—C4—C9—C8	−172.5 (5)	C11—C12—C13—C14	163.2 (6)
C3—C4—C9—C10	−57.2 (6)	C11—C12—C13—C15	−80.4 (8)
O1—C5—C6—C7	168.9 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18A···O2i	0.93	2.59	3.501 (9)	167