Natural diterpenoid ludongnin, octa­hydro-5′-hydroxy-7a-methyl-8′-methyl­ene­spiro­[isobenzo­furan-4(1H),4′(3′H)-[1H-7,9a]­methano­cyclo­hepta­[c]­pyran]-1′,3,9′(3aH,4′aH)-trione

The asymmetric unit of ludongnin consists of two mol­ecules of C₂₀H₂₄O₆. The hydroxyl group of each mol­ecule participates in a hydrogen bond with the carbonyl oxy­gen of the δ-lactone moiety of a translationally related mol­ecule, thus giving rise to the two symmetry-independent sets of infinite chains in the crystal, one of which is stretched along the c and another along the a axis of the crystal.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.038
• wR factor = 0.081
• Data-to-parameter ratio = 7.3

checkCIF results

No syntax errors found



ADDSYM reports no extra symmetry


 Alert Level C:



STRVAL_01
         From the CIF: _refine_ls_abs_structure_Flack   -0.400
         From the CIF: _refine_ls_abs_structure_Flack_su    1.100
           Alert C Flack parameter is too small

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           26.00
         From the CIF: _reflns_number_total               3474
         Count of symmetry unique reflns         3478
         Completeness (_total/calc)             99.88%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured         0
         Fraction of Friedel pairs measured     0.000
         Are heavy atom types Z>Si present           no
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

The diterpenoid ludongnin, (I), has been previously isolated from Rabdosia rubescens Hara (Ruan et al., 1986; Sun et al., 1988; Zheng et al., 1984, 1986) and its structure was established from the spectral and chemical evidence. Recently, it was for the first time isolated from Rabdosia var lophanthoides Hara, and its structure was confirmed by the X-ray diffraction study (Fig. 1).

In both molecules, the B ring adopts a chair, whereas the D ring shows a boat conformation. The isobenzofuran ring system couples orthogonally to the methanocyclohepta[c]pyran moiety through a spiro C atom. The differences in the geometrical parameters between two independent molecules are in fact inessential; the most notable discrepancies, as one would expect, have to do with the values of the torsion angles: C12—C13—C16—C17 - 92.1 (5), C12'-C13'-C16'-C17' -100.1 (5), C14—C13—C16—C17 151.1 (4) and C14'-C13'-C16'-C17' 143.5 (4)°.

The hydroxyl group of each of the independent molecules participates in the hydrogen bond with the carbonyl oxygen of the δ-lactone moiety of the same molecule as transformed by the c or a translation [O···O 2.824 (4) and 2.856 (3) Å, respectively]. Thus, two independent molecules give rise to two sets of infinite chains in the crystal, one of which is stretched along the z and another along the x axis of the crystal (Fig. 2).

S2. Experimental

2 kg of dried powder of the whole herb of Rabdosia var lophanthoides were soaked three times with 95% EtOH at room temperature. The ethanolic extracts were evaporated under reduced pressure, the residue was successively fractioned with petroleum ether, EtOAc and n-BuOH. The residue of EtOAc fraction was subjected to column chromatography over silica gel. The column was eluted with a petroleum ether–EtOAc mixture; the acetone–chloroform mixture was used for recrystallization of the title compound. Its purity was checked by ¹H NMR spectroscopy. α₁₂^D - 138° (c = 1, pyridine); UVλ_max (95%EtOH): 230 nm (ε 7130). Crystals suitable for X-ray structure analysis were obtained by slow evaporation from an aqueous solution containing chloroform and methanol in a 1:1 ratio at room temperature.

S3. Refinement

H atoms were placed in geometrically calculated positions and included in the final refinement in the riding-model approximation with the displacement parameters U_iso set equal to 1.2U_eq of the corresponding carrier atom. As one would expect, both independent molecules have the same configuration. Lack of the anomalous scatterers and, hence, high s.u. of the Flack parameter, -0.4 (11), do not permit to make unambiguous assignment of the absolute configuration of the title compound.

Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Siemens, 1991); software used to prepare material for publication: SHELXTL97.

Figures

	Fig. 1. One of the independent molecules of the title compound, shown with 50% probability displacement ellipsoids.
	Fig. 2. The crystal-packing diagram for the title compound viewed down the c axis. H atoms have been omitted for clarity.

octahydro-5'-hydroxy-7a-methyl-8'- methylene-spiro [isobenzofuran-4 (1H), 4' (3'H) - [1H-7, 9a] methanocyclohepta[c]pyran] -1', 3, 9' (3aH, 4'aH) -trione

Crystal data

C20H24O6	Dx = 1.368 Mg m^−3
Mr = 360.39	Melting point = 538–540 K
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.2397 (13) Å	Cell parameters from 18 reflections
b = 36.724 (8) Å	θ = 3.1–14.2°
c = 7.304 (2) Å	µ = 0.10 mm^−1
β = 115.69 (2)°	T = 291 K
V = 1749.9 (7) Å^3	Prism, colorless
Z = 4	0.52 × 0.44 × 0.42 mm
F(000) = 768

Data collection

Siemens P4 diffractometer	Rint = 0.017
Radiation source: normal-focus sealed tube	θmax = 26.0°, θmin = 2.2°
Graphite monochromator	h = 0→8
ω scans	k = 0→45
3894 measured reflections	l = −9→8
3474 independent reflections	3 standard reflections every 97 reflections
2512 reflections with I > 2σ(I)	intensity decay: 3.6%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.038	w = 1/[σ^2(Fo^2) + (0.0428P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.081	(Δ/σ)max = 0.001
S = 0.91	Δρmax = 0.17 e Å^−3
3474 reflections	Δρmin = −0.14 e Å^−3
474 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0135 (12)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.4 (11)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic)

treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.3281 (4)	0.21845 (8)	0.3993 (4)	0.0600 (7)
H1A	0.3138	0.2270	0.2902	0.090*
O2	0.6199 (4)	0.25371 (7)	1.1879 (3)	0.0514 (7)
O3	0.1614 (4)	0.24262 (8)	0.9923 (4)	0.0585 (7)
O4	0.0682 (3)	0.26942 (7)	0.7008 (4)	0.0479 (6)
O5	0.3429 (5)	0.38238 (7)	0.8393 (5)	0.0696 (8)
O6	0.0656 (4)	0.35278 (8)	0.6352 (5)	0.0805 (10)
C1	0.3685 (5)	0.30797 (10)	0.4311 (5)	0.0439 (9)
H1B	0.3496	0.2888	0.3333	0.053*
H1C	0.2632	0.3262	0.3653	0.053*
C2	0.5779 (6)	0.32529 (10)	0.4931 (5)	0.0502 (9)
H2A	0.6835	0.3070	0.5546	0.060*
H2B	0.5878	0.3346	0.3734	0.060*
C3	0.6129 (6)	0.35612 (10)	0.6426 (6)	0.0508 (10)
H3A	0.5105	0.3749	0.5790	0.061*
H3B	0.7467	0.3668	0.6781	0.061*
C4	0.6011 (5)	0.34284 (9)	0.8365 (5)	0.0429 (9)
C5	0.4000 (5)	0.32149 (9)	0.7821 (5)	0.0375 (8)
H5A	0.4122	0.3093	0.9061	0.045*
C6	0.2460 (7)	0.35231 (10)	0.7390 (7)	0.0535 (10)
C7	0.2028 (5)	0.24993 (10)	0.8529 (5)	0.0408 (8)
C8	0.3906 (5)	0.23568 (9)	0.8393 (4)	0.0339 (7)
C9	0.4739 (5)	0.25749 (9)	0.7041 (4)	0.0330 (7)
H9A	0.6088	0.2666	0.7991	0.040*
C10	0.3422 (5)	0.29189 (9)	0.6134 (5)	0.0336 (7)
C11	0.5155 (6)	0.23190 (9)	0.5589 (5)	0.0421 (8)
H11A	0.5906	0.2455	0.4972	0.051*
C12	0.6456 (6)	0.19966 (10)	0.6745 (5)	0.0516 (10)
H12A	0.7875	0.2074	0.7439	0.062*
H12B	0.6374	0.1808	0.5781	0.062*
C13	0.5798 (5)	0.18343 (9)	0.8314 (5)	0.0473 (9)
H13A	0.5937	0.1569	0.8375	0.057*
C14	0.3601 (5)	0.19488 (9)	0.7802 (5)	0.0428 (8)
H14A	0.3053	0.1815	0.8602	0.051*
H14B	0.2707	0.1916	0.6369	0.051*
C15	0.5757 (5)	0.23262 (9)	1.0485 (5)	0.0373 (8)
C16	0.6929 (5)	0.20013 (10)	1.0379 (5)	0.0457 (9)
C17	0.8627 (6)	0.18976 (12)	1.1911 (7)	0.0714 (13)
H17A	0.9138	0.2029	1.3119	0.086*
H17B	0.9321	0.1693	1.1790	0.086*
C18	0.8024 (6)	0.32473 (11)	0.9816 (6)	0.0596 (11)
H18A	0.9047	0.3431	1.0455	0.089*
H18B	0.8477	0.3084	0.9066	0.089*
H18C	0.7809	0.3113	1.0836	0.089*
C19	0.5605 (7)	0.37542 (11)	0.9432 (7)	0.0649 (12)
H19A	0.6004	0.3699	1.0853	0.078*
H19B	0.6373	0.3965	0.9347	0.078*
C20	0.1186 (5)	0.27993 (10)	0.5349 (5)	0.0440 (9)
H20A	0.0298	0.2997	0.4590	0.053*
H20B	0.0939	0.2595	0.4433	0.053*
O1'	−0.3955 (3)	0.58886 (7)	0.1686 (4)	0.0527 (7)
H1'A	−0.5010	0.5770	0.1377	0.079*
O2'	0.3896 (3)	0.54835 (7)	0.4384 (3)	0.0478 (6)
O3'	0.1919 (4)	0.56283 (8)	−0.0129 (4)	0.0552 (7)
O4'	−0.1052 (3)	0.53694 (7)	−0.1068 (3)	0.0463 (6)
O5'	0.0239 (5)	0.42278 (7)	0.1509 (4)	0.0660 (8)
O6'	−0.1798 (5)	0.45366 (8)	−0.1190 (4)	0.0742 (9)
C1'	−0.3756 (5)	0.49813 (10)	0.1919 (5)	0.0405 (8)
H1'B	−0.4719	0.5176	0.1758	0.049*
H1'C	−0.4449	0.4803	0.0861	0.049*
C2'	−0.3138 (5)	0.48014 (9)	0.3990 (5)	0.0449 (9)
H2'A	−0.2480	0.4979	0.5059	0.054*
H2'B	−0.4350	0.4712	0.4092	0.054*
C3'	−0.1683 (5)	0.44896 (9)	0.4252 (5)	0.0449 (9)
H3'A	−0.2368	0.4310	0.3203	0.054*
H3'B	−0.1330	0.4375	0.5558	0.054*
C4'	0.0288 (5)	0.46125 (9)	0.4137 (5)	0.0427 (8)
C5'	−0.0268 (5)	0.48378 (9)	0.2165 (5)	0.0366 (8)
H5'A	0.0991	0.4958	0.2294	0.044*
C6'	−0.0730 (6)	0.45338 (10)	0.0600 (6)	0.0513 (10)
C7'	0.0517 (5)	0.55599 (9)	0.0281 (5)	0.0400 (8)
C8'	0.0432 (4)	0.56942 (9)	0.2179 (4)	0.0327 (7)
C9'	−0.0943 (4)	0.54763 (8)	0.3002 (5)	0.0318 (7)
H9'A	0.0014	0.5378	0.4321	0.038*
C10'	−0.1931 (5)	0.51372 (8)	0.1640 (5)	0.0319 (7)
C11'	−0.2352 (5)	0.57350 (9)	0.3464 (5)	0.0404 (8)
H11B	−0.2980	0.5598	0.4200	0.048*
C12'	−0.1095 (5)	0.60452 (9)	0.4824 (6)	0.0463 (9)
H12C	−0.0376	0.5956	0.6205	0.056*
H12D	−0.2021	0.6236	0.4825	0.056*
C13'	0.0478 (5)	0.62090 (9)	0.4159 (5)	0.0422 (8)
H13B	0.0567	0.6474	0.4337	0.051*
C14'	−0.0106 (5)	0.61039 (9)	0.1943 (5)	0.0406 (8)
H14C	0.0700	0.6237	0.1396	0.049*
H14D	−0.1552	0.6144	0.1088	0.049*
C15'	0.2536 (5)	0.57060 (9)	0.3983 (5)	0.0360 (7)
C16'	0.2567 (5)	0.60343 (10)	0.5193 (5)	0.0439 (9)
C17'	0.4243 (6)	0.61465 (11)	0.6755 (6)	0.0631 (11)
H17C	0.5464	0.6019	0.7136	0.076*
H17D	0.4202	0.6353	0.7474	0.076*
C18'	0.1781 (6)	0.47852 (11)	0.6149 (5)	0.0597 (11)
H18D	0.2360	0.4599	0.7160	0.090*
H18E	0.1060	0.4958	0.6587	0.090*
H18F	0.2857	0.4907	0.5958	0.090*
C19'	0.1308 (6)	0.42868 (11)	0.3676 (6)	0.0606 (11)
H19C	0.2747	0.4336	0.4071	0.073*
H19D	0.1200	0.4074	0.4408	0.073*
C20'	−0.2718 (5)	0.52686 (10)	−0.0559 (5)	0.0436 (9)
H20C	−0.3524	0.5077	−0.1468	0.052*
H20D	−0.3607	0.5477	−0.0760	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0748 (19)	0.0685 (18)	0.0303 (13)	−0.0124 (15)	0.0169 (14)	−0.0058 (13)
O2	0.0602 (16)	0.0631 (17)	0.0293 (13)	−0.0091 (14)	0.0180 (12)	−0.0050 (13)
O3	0.0533 (16)	0.083 (2)	0.0500 (15)	−0.0010 (14)	0.0324 (13)	0.0143 (14)
O4	0.0352 (13)	0.0572 (16)	0.0518 (14)	0.0037 (12)	0.0194 (12)	0.0180 (12)
O5	0.077 (2)	0.0399 (16)	0.107 (2)	0.0044 (15)	0.054 (2)	−0.0053 (16)
O6	0.0490 (18)	0.0619 (19)	0.136 (3)	0.0156 (16)	0.0452 (19)	0.017 (2)
C1	0.052 (2)	0.047 (2)	0.0352 (19)	0.0036 (18)	0.0210 (17)	0.0121 (16)
C2	0.057 (2)	0.054 (2)	0.051 (2)	0.0043 (19)	0.033 (2)	0.0153 (19)
C3	0.045 (2)	0.046 (2)	0.067 (3)	0.0016 (18)	0.030 (2)	0.014 (2)
C4	0.044 (2)	0.0344 (19)	0.048 (2)	−0.0049 (16)	0.0175 (18)	0.0012 (16)
C5	0.0406 (19)	0.0372 (19)	0.0410 (19)	0.0003 (16)	0.0237 (16)	0.0070 (15)
C6	0.058 (3)	0.037 (2)	0.085 (3)	0.005 (2)	0.049 (2)	0.010 (2)
C7	0.0369 (19)	0.044 (2)	0.0406 (19)	−0.0105 (17)	0.0163 (17)	0.0026 (17)
C8	0.0353 (18)	0.0375 (17)	0.0287 (16)	−0.0019 (15)	0.0136 (15)	0.0080 (14)
C9	0.0325 (17)	0.0403 (19)	0.0261 (16)	−0.0039 (15)	0.0125 (14)	0.0015 (14)
C10	0.0287 (17)	0.0387 (18)	0.0300 (18)	0.0019 (15)	0.0096 (15)	0.0053 (14)
C11	0.052 (2)	0.042 (2)	0.0359 (18)	−0.0039 (18)	0.0219 (17)	−0.0026 (16)
C12	0.059 (2)	0.044 (2)	0.054 (2)	0.0054 (19)	0.027 (2)	−0.0071 (18)
C13	0.051 (2)	0.0302 (19)	0.056 (2)	0.0018 (17)	0.0183 (19)	0.0008 (16)
C14	0.045 (2)	0.0371 (19)	0.0415 (19)	−0.0080 (17)	0.0139 (16)	0.0028 (16)
C15	0.038 (2)	0.0417 (19)	0.0315 (18)	−0.0102 (16)	0.0147 (15)	0.0059 (16)
C16	0.043 (2)	0.042 (2)	0.046 (2)	−0.0008 (17)	0.0135 (18)	0.0128 (17)
C17	0.058 (3)	0.060 (3)	0.071 (3)	0.006 (2)	0.005 (2)	0.017 (2)
C18	0.050 (2)	0.052 (2)	0.059 (2)	−0.011 (2)	0.007 (2)	−0.001 (2)
C19	0.081 (3)	0.045 (2)	0.071 (3)	−0.008 (2)	0.035 (3)	−0.008 (2)
C20	0.040 (2)	0.049 (2)	0.039 (2)	0.0025 (17)	0.0137 (17)	0.0127 (17)
O1'	0.0290 (13)	0.0479 (15)	0.0725 (18)	0.0016 (11)	0.0138 (13)	0.0106 (13)
O2'	0.0318 (13)	0.0583 (16)	0.0522 (15)	0.0030 (13)	0.0171 (12)	0.0036 (13)
O3'	0.0458 (15)	0.082 (2)	0.0449 (14)	−0.0119 (14)	0.0262 (12)	0.0014 (14)
O4'	0.0484 (14)	0.0579 (16)	0.0319 (12)	−0.0129 (13)	0.0168 (11)	0.0010 (11)
O5'	0.099 (2)	0.0388 (15)	0.076 (2)	0.0060 (15)	0.0525 (18)	−0.0044 (15)
O6'	0.123 (3)	0.0601 (18)	0.0429 (16)	−0.0122 (19)	0.0390 (18)	−0.0123 (14)
C1'	0.0336 (18)	0.0372 (18)	0.046 (2)	−0.0055 (16)	0.0130 (16)	−0.0008 (16)
C2'	0.049 (2)	0.042 (2)	0.054 (2)	−0.0097 (18)	0.0333 (19)	−0.0002 (17)
C3'	0.063 (2)	0.0356 (19)	0.040 (2)	−0.0060 (18)	0.0262 (18)	0.0029 (15)
C4'	0.047 (2)	0.0353 (19)	0.044 (2)	−0.0023 (17)	0.0178 (18)	0.0042 (16)
C5'	0.0383 (19)	0.0343 (18)	0.0414 (19)	−0.0041 (15)	0.0214 (16)	−0.0005 (15)
C6'	0.071 (3)	0.036 (2)	0.061 (3)	−0.008 (2)	0.042 (2)	−0.0043 (19)
C7'	0.0353 (19)	0.045 (2)	0.0391 (19)	−0.0038 (16)	0.0158 (17)	0.0084 (16)
C8'	0.0291 (17)	0.0338 (17)	0.0347 (17)	−0.0040 (15)	0.0136 (14)	0.0015 (15)
C9'	0.0275 (16)	0.0315 (17)	0.0368 (17)	−0.0020 (14)	0.0144 (14)	0.0043 (14)
C10'	0.0301 (17)	0.0323 (17)	0.0322 (17)	−0.0023 (14)	0.0125 (14)	0.0026 (14)
C11'	0.0353 (18)	0.0374 (19)	0.051 (2)	0.0007 (16)	0.0213 (17)	0.0038 (17)
C12'	0.047 (2)	0.0371 (19)	0.058 (2)	−0.0004 (17)	0.0250 (19)	−0.0022 (18)
C13'	0.041 (2)	0.0291 (17)	0.054 (2)	−0.0029 (15)	0.0178 (18)	−0.0007 (16)
C14'	0.0357 (18)	0.0378 (19)	0.046 (2)	−0.0049 (16)	0.0158 (16)	0.0096 (16)
C15'	0.0270 (17)	0.0389 (18)	0.0454 (19)	0.0005 (16)	0.0189 (15)	0.0068 (16)
C16'	0.040 (2)	0.042 (2)	0.042 (2)	−0.0050 (17)	0.0112 (17)	−0.0020 (16)
C17'	0.062 (3)	0.049 (2)	0.057 (2)	0.004 (2)	0.005 (2)	−0.006 (2)
C18'	0.064 (3)	0.050 (2)	0.044 (2)	0.002 (2)	0.004 (2)	0.0097 (19)
C19'	0.061 (3)	0.045 (2)	0.074 (3)	0.013 (2)	0.028 (2)	0.008 (2)
C20'	0.0348 (18)	0.053 (2)	0.0358 (18)	−0.0054 (17)	0.0087 (15)	0.0053 (17)

Geometric parameters (Å, º)

O1—C11	1.439 (4)	O1'—C11'	1.430 (4)
O1—H1A	0.8200	O1'—H1'A	0.8200
O2—C15	1.207 (4)	O2'—C15'	1.213 (4)
O3—C7	1.210 (4)	O3'—C7'	1.204 (4)
O4—C7	1.326 (4)	O4'—C7'	1.334 (4)
O4—C20	1.461 (4)	O4'—C20'	1.456 (4)
O5—C6	1.343 (5)	O5'—C6'	1.339 (5)
O5—C19	1.444 (5)	O5'—C19'	1.445 (4)
O6—C6	1.193 (5)	O6'—C6'	1.196 (5)
C1—C2	1.521 (5)	C1'—C2'	1.529 (5)
C1—C10	1.542 (4)	C1'—C10'	1.532 (4)
C1—H1B	0.9700	C1'—H1'B	0.9700
C1—H1C	0.9700	C1'—H1'C	0.9700
C2—C3	1.516 (5)	C2'—C3'	1.511 (5)
C2—H2A	0.9700	C2'—H2'A	0.9700
C2—H2B	0.9700	C2'—H2'B	0.9700
C3—C4	1.535 (5)	C3'—C4'	1.533 (5)
C3—H3A	0.9700	C3'—H3'A	0.9700
C3—H3B	0.9700	C3'—H3'B	0.9700
C4—C19	1.524 (5)	C4'—C19'	1.519 (5)
C4—C18	1.533 (5)	C4'—C18'	1.534 (5)
C4—C5	1.546 (5)	C4'—C5'	1.556 (5)
C5—C6	1.523 (5)	C5'—C6'	1.527 (5)
C5—C10	1.558 (5)	C5'—C10'	1.551 (4)
C5—H5A	0.9800	C5'—H5'A	0.9800
C7—C8	1.499 (5)	C7'—C8'	1.497 (5)
C8—C15	1.539 (4)	C8'—C15'	1.523 (4)
C8—C14	1.549 (5)	C8'—C14'	1.545 (5)
C8—C9	1.581 (4)	C8'—C9'	1.585 (4)
C9—C11	1.541 (4)	C9'—C11'	1.535 (4)
C9—C10	1.548 (4)	C9'—C10'	1.560 (4)
C9—H9A	0.9800	C9'—H9'A	0.9800
C10—C20	1.528 (4)	C10'—C20'	1.531 (4)
C11—C12	1.521 (5)	C11'—C12'	1.526 (5)
C11—H11A	0.9800	C11'—H11B	0.9800
C12—C13	1.539 (5)	C12'—C13'	1.541 (5)
C12—H12A	0.9700	C12'—H12C	0.9700
C12—H12B	0.9700	C12'—H12D	0.9700
C13—C16	1.500 (5)	C13'—C16'	1.510 (5)
C13—C14	1.527 (5)	C13'—C14'	1.534 (5)
C13—H13A	0.9800	C13'—H13B	0.9800
C14—H14A	0.9700	C14'—H14C	0.9700
C14—H14B	0.9700	C14'—H14D	0.9700
C15—C16	1.486 (5)	C15'—C16'	1.489 (5)
C16—C17	1.310 (5)	C16'—C17'	1.320 (5)
C17—H17A	0.9300	C17'—H17C	0.9300
C17—H17B	0.9300	C17'—H17D	0.9300
C18—H18A	0.9600	C18'—H18D	0.9600
C18—H18B	0.9600	C18'—H18E	0.9600
C18—H18C	0.9600	C18'—H18F	0.9600
C19—H19A	0.9700	C19'—H19C	0.9700
C19—H19B	0.9700	C19'—H19D	0.9700
C20—H20A	0.9700	C20'—H20C	0.9700
C20—H20B	0.9700	C20'—H20D	0.9700
C11—O1—H1A	109.5	C11'—O1'—H1'A	109.5
C7—O4—C20	118.7 (3)	C7'—O4'—C20'	118.6 (3)
C6—O5—C19	109.5 (3)	C6'—O5'—C19'	109.5 (3)
C2—C1—C10	112.5 (3)	C2'—C1'—C10'	113.2 (3)
C2—C1—H1B	109.1	C2'—C1'—H1'B	108.9
C10—C1—H1B	109.1	C10'—C1'—H1'B	108.9
C2—C1—H1C	109.1	C2'—C1'—H1'C	108.9
C10—C1—H1C	109.1	C10'—C1'—H1'C	108.9
H1B—C1—H1C	107.8	H1'B—C1'—H1'C	107.8
C3—C2—C1	111.2 (3)	C3'—C2'—C1'	110.0 (3)
C3—C2—H2A	109.4	C3'—C2'—H2'A	109.7
C1—C2—H2A	109.4	C1'—C2'—H2'A	109.7
C3—C2—H2B	109.4	C3'—C2'—H2'B	109.7
C1—C2—H2B	109.4	C1'—C2'—H2'B	109.7
H2A—C2—H2B	108.0	H2'A—C2'—H2'B	108.2
C2—C3—C4	111.6 (3)	C2'—C3'—C4'	112.6 (3)
C2—C3—H3A	109.3	C2'—C3'—H3'A	109.1
C4—C3—H3A	109.3	C4'—C3'—H3'A	109.1
C2—C3—H3B	109.3	C2'—C3'—H3'B	109.1
C4—C3—H3B	109.3	C4'—C3'—H3'B	109.1
H3A—C3—H3B	108.0	H3'A—C3'—H3'B	107.8
C19—C4—C18	108.9 (3)	C19'—C4'—C3'	109.5 (3)
C19—C4—C3	108.8 (3)	C19'—C4'—C18'	109.2 (3)
C18—C4—C3	111.0 (3)	C3'—C4'—C18'	110.8 (3)
C19—C4—C5	99.2 (3)	C19'—C4'—C5'	99.7 (3)
C18—C4—C5	117.7 (3)	C3'—C4'—C5'	109.5 (3)
C3—C4—C5	110.3 (3)	C18'—C4'—C5'	117.3 (3)
C6—C5—C4	101.5 (3)	C6'—C5'—C10'	116.0 (3)
C6—C5—C10	115.7 (3)	C6'—C5'—C4'	100.9 (3)
C4—C5—C10	117.2 (3)	C10'—C5'—C4'	117.9 (3)
C6—C5—H5A	107.3	C6'—C5'—H5'A	107.1
C4—C5—H5A	107.3	C10'—C5'—H5'A	107.1
C10—C5—H5A	107.3	C4'—C5'—H5'A	107.1
O6—C6—O5	120.3 (4)	O6'—C6'—O5'	120.1 (4)
O6—C6—C5	130.1 (4)	O6'—C6'—C5'	129.8 (4)
O5—C6—C5	109.6 (3)	O5'—C6'—C5'	110.2 (3)
O3—C7—O4	117.7 (3)	O3'—C7'—O4'	117.7 (3)
O3—C7—C8	122.7 (3)	O3'—C7'—C8'	122.6 (3)
O4—C7—C8	119.5 (3)	O4'—C7'—C8'	119.6 (3)
C7—C8—C15	112.6 (3)	C7'—C8'—C15'	112.5 (3)
C7—C8—C14	109.4 (3)	C7'—C8'—C14'	109.1 (3)
C15—C8—C14	99.4 (3)	C15'—C8'—C14'	100.3 (3)
C7—C8—C9	117.8 (3)	C7'—C8'—C9'	118.0 (3)
C15—C8—C9	104.7 (2)	C15'—C8'—C9'	104.1 (2)
C14—C8—C9	111.3 (3)	C14'—C8'—C9'	111.4 (3)
C11—C9—C10	118.1 (2)	C11'—C9'—C10'	118.0 (2)
C11—C9—C8	111.2 (3)	C11'—C9'—C8'	110.9 (2)
C10—C9—C8	110.5 (2)	C10'—C9'—C8'	110.5 (2)
C11—C9—H9A	105.3	C11'—C9'—H9'A	105.4
C10—C9—H9A	105.3	C10'—C9'—H9'A	105.4
C8—C9—H9A	105.3	C8'—C9'—H9'A	105.4
C20—C10—C1	107.1 (2)	C20'—C10'—C1'	107.9 (2)
C20—C10—C9	106.4 (3)	C20'—C10'—C5'	112.3 (3)
C1—C10—C9	113.5 (3)	C1'—C10'—C5'	108.9 (3)
C20—C10—C5	112.0 (3)	C20'—C10'—C9'	106.1 (2)
C1—C10—C5	108.9 (3)	C1'—C10'—C9'	113.4 (3)
C9—C10—C5	109.1 (2)	C5'—C10'—C9'	108.4 (2)
O1—C11—C12	108.8 (3)	O1'—C11'—C12'	108.5 (3)
O1—C11—C9	111.7 (3)	O1'—C11'—C9'	113.5 (3)
C12—C11—C9	110.6 (3)	C12'—C11'—C9'	109.9 (3)
O1—C11—H11A	108.6	O1'—C11'—H11B	108.3
C12—C11—H11A	108.6	C12'—C11'—H11B	108.3
C9—C11—H11A	108.6	C9'—C11'—H11B	108.3
C11—C12—C13	113.5 (3)	C11'—C12'—C13'	113.6 (3)
C11—C12—H12A	108.9	C11'—C12'—H12C	108.9
C13—C12—H12A	108.9	C13'—C12'—H12C	108.9
C11—C12—H12B	108.9	C11'—C12'—H12D	108.9
C13—C12—H12B	108.9	C13'—C12'—H12D	108.9
H12A—C12—H12B	107.7	H12C—C12'—H12D	107.7
C16—C13—C14	101.0 (3)	C16'—C13'—C14'	100.3 (3)
C16—C13—C12	112.3 (3)	C16'—C13'—C12'	113.2 (3)
C14—C13—C12	109.7 (3)	C14'—C13'—C12'	109.3 (3)
C16—C13—H13A	111.1	C16'—C13'—H13B	111.2
C14—C13—H13A	111.1	C14'—C13'—H13B	111.2
C12—C13—H13A	111.1	C12'—C13'—H13B	111.2
C13—C14—C8	101.0 (3)	C13'—C14'—C8'	100.7 (2)
C13—C14—H14A	111.6	C13'—C14'—H14C	111.6
C8—C14—H14A	111.6	C8'—C14'—H14C	111.6
C13—C14—H14B	111.6	C13'—C14'—H14D	111.6
C8—C14—H14B	111.6	C8'—C14'—H14D	111.6
H14A—C14—H14B	109.4	H14C—C14'—H14D	109.4
O2—C15—C16	127.7 (3)	O2'—C15'—C16'	126.9 (3)
O2—C15—C8	126.1 (3)	O2'—C15'—C8'	126.3 (3)
C16—C15—C8	106.1 (3)	C16'—C15'—C8'	106.8 (3)
C17—C16—C15	122.3 (4)	C17'—C16'—C15'	122.5 (3)
C17—C16—C13	129.9 (4)	C17'—C16'—C13'	130.2 (4)
C15—C16—C13	107.8 (3)	C15'—C16'—C13'	107.1 (3)
C16—C17—H17A	120.0	C16'—C17'—H17C	120.0
C16—C17—H17B	120.0	C16'—C17'—H17D	120.0
H17A—C17—H17B	120.0	H17C—C17'—H17D	120.0
C4—C18—H18A	109.5	C4'—C18'—H18D	109.5
C4—C18—H18B	109.5	C4'—C18'—H18E	109.5
H18A—C18—H18B	109.5	H18D—C18'—H18E	109.5
C4—C18—H18C	109.5	C4'—C18'—H18F	109.5
H18A—C18—H18C	109.5	H18D—C18'—H18F	109.5
H18B—C18—H18C	109.5	H18E—C18'—H18F	109.5
O5—C19—C4	106.2 (3)	O5'—C19'—C4'	106.3 (3)
O5—C19—H19A	110.5	O5'—C19'—H19C	110.5
C4—C19—H19A	110.5	C4'—C19'—H19C	110.5
O5—C19—H19B	110.5	O5'—C19'—H19D	110.5
C4—C19—H19B	110.5	C4'—C19'—H19D	110.5
H19A—C19—H19B	108.7	H19C—C19'—H19D	108.7
O4—C20—C10	111.7 (2)	O4'—C20'—C10'	112.0 (2)
O4—C20—H20A	109.3	O4'—C20'—H20C	109.2
C10—C20—H20A	109.3	C10'—C20'—H20C	109.2
O4—C20—H20B	109.3	O4'—C20'—H20D	109.2
C10—C20—H20B	109.3	C10'—C20'—H20D	109.2
H20A—C20—H20B	107.9	H20C—C20'—H20D	107.9
C10—C1—C2—C3	−60.1 (4)	C10'—C1'—C2'—C3'	−60.3 (4)
C1—C2—C3—C4	59.7 (4)	C1'—C2'—C3'—C4'	60.1 (4)
C2—C3—C4—C19	−159.9 (3)	C2'—C3'—C4'—C19'	−160.4 (3)
C2—C3—C4—C18	80.3 (4)	C2'—C3'—C4'—C18'	79.0 (4)
C2—C3—C4—C5	−52.0 (4)	C2'—C3'—C4'—C5'	−52.0 (4)
C19—C4—C5—C6	34.6 (3)	C19'—C4'—C5'—C6'	33.8 (3)
C18—C4—C5—C6	151.7 (3)	C3'—C4'—C5'—C6'	−81.0 (3)
C3—C4—C5—C6	−79.5 (3)	C18'—C4'—C5'—C6'	151.5 (3)
C19—C4—C5—C10	161.6 (3)	C19'—C4'—C5'—C10'	161.2 (3)
C18—C4—C5—C10	−81.3 (4)	C3'—C4'—C5'—C10'	46.4 (4)
C3—C4—C5—C10	47.5 (4)	C18'—C4'—C5'—C10'	−81.1 (4)
C19—O5—C6—O6	−176.6 (4)	C19'—O5'—C6'—O6'	−176.0 (4)
C19—O5—C6—C5	3.3 (4)	C19'—O5'—C6'—C5'	2.8 (4)
C4—C5—C6—O6	154.6 (4)	C10'—C5'—C6'—O6'	25.8 (6)
C10—C5—C6—O6	26.6 (6)	C4'—C5'—C6'—O6'	154.4 (4)
C4—C5—C6—O5	−25.2 (4)	C10'—C5'—C6'—O5'	−152.8 (3)
C10—C5—C6—O5	−153.2 (3)	C4'—C5'—C6'—O5'	−24.2 (4)
C20—O4—C7—O3	177.4 (3)	C20'—O4'—C7'—O3'	177.1 (3)
C20—O4—C7—C8	−6.9 (5)	C20'—O4'—C7'—C8'	−5.7 (4)
O3—C7—C8—C15	−35.4 (5)	O3'—C7'—C8'—C15'	−35.5 (5)
O4—C7—C8—C15	149.1 (3)	O4'—C7'—C8'—C15'	147.4 (3)
O3—C7—C8—C14	74.1 (4)	O3'—C7'—C8'—C14'	74.8 (4)
O4—C7—C8—C14	−101.3 (3)	O4'—C7'—C8'—C14'	−102.2 (3)
O3—C7—C8—C9	−157.5 (3)	O3'—C7'—C8'—C9'	−156.8 (3)
O4—C7—C8—C9	27.1 (4)	O4'—C7'—C8'—C9'	26.1 (4)
C7—C8—C9—C11	−131.1 (3)	C7'—C8'—C9'—C11'	−130.7 (3)
C15—C8—C9—C11	102.9 (3)	C15'—C8'—C9'—C11'	103.8 (3)
C14—C8—C9—C11	−3.6 (4)	C14'—C8'—C9'—C11'	−3.4 (3)
C7—C8—C9—C10	2.1 (4)	C7'—C8'—C9'—C10'	2.2 (4)
C15—C8—C9—C10	−123.9 (3)	C15'—C8'—C9'—C10'	−123.3 (3)
C14—C8—C9—C10	129.6 (3)	C14'—C8'—C9'—C10'	129.5 (3)
C2—C1—C10—C20	172.9 (3)	C2'—C1'—C10'—C20'	173.6 (3)
C2—C1—C10—C9	−70.1 (4)	C2'—C1'—C10'—C5'	51.5 (4)
C2—C1—C10—C5	51.6 (4)	C2'—C1'—C10'—C9'	−69.3 (4)
C11—C9—C10—C20	84.9 (3)	C6'—C5'—C10'—C20'	−45.6 (4)
C8—C9—C10—C20	−44.7 (3)	C4'—C5'—C10'—C20'	−165.3 (3)
C11—C9—C10—C1	−32.5 (4)	C6'—C5'—C10'—C1'	73.8 (3)
C8—C9—C10—C1	−162.1 (3)	C4'—C5'—C10'—C1'	−46.0 (4)
C11—C9—C10—C5	−154.1 (3)	C6'—C5'—C10'—C9'	−162.4 (3)
C8—C9—C10—C5	76.3 (3)	C4'—C5'—C10'—C9'	77.8 (3)
C6—C5—C10—C20	−45.3 (4)	C11'—C9'—C10'—C20'	84.9 (3)
C4—C5—C10—C20	−165.1 (3)	C8'—C9'—C10'—C20'	−44.2 (3)
C6—C5—C10—C1	72.9 (3)	C11'—C9'—C10'—C1'	−33.2 (4)
C4—C5—C10—C1	−46.9 (4)	C8'—C9'—C10'—C1'	−162.4 (3)
C6—C5—C10—C9	−162.8 (3)	C11'—C9'—C10'—C5'	−154.3 (3)
C4—C5—C10—C9	77.5 (3)	C8'—C9'—C10'—C5'	76.5 (3)
C10—C9—C11—O1	−58.3 (4)	C10'—C9'—C11'—O1'	−58.8 (4)
C8—C9—C11—O1	70.9 (3)	C8'—C9'—C11'—O1'	70.2 (3)
C10—C9—C11—C12	−179.6 (3)	C10'—C9'—C11'—C12'	179.5 (3)
C8—C9—C11—C12	−50.4 (4)	C8'—C9'—C11'—C12'	−51.5 (3)
O1—C11—C12—C13	−80.4 (4)	O1'—C11'—C12'—C13'	−80.3 (3)
C9—C11—C12—C13	42.6 (4)	C9'—C11'—C12'—C13'	44.4 (4)
C11—C12—C13—C16	−91.7 (4)	C11'—C12'—C13'—C16'	−92.5 (4)
C11—C12—C13—C14	19.7 (4)	C11'—C12'—C13'—C14'	18.4 (4)
C16—C13—C14—C8	46.6 (3)	C16'—C13'—C14'—C8'	47.6 (3)
C12—C13—C14—C8	−72.1 (3)	C12'—C13'—C14'—C8'	−71.6 (3)
C7—C8—C14—C13	−165.1 (3)	C7'—C8'—C14'—C13'	−164.7 (2)
C15—C8—C14—C13	−46.9 (3)	C15'—C8'—C14'—C13'	−46.3 (3)
C9—C8—C14—C13	62.9 (3)	C9'—C8'—C14'—C13'	63.4 (3)
C7—C8—C15—O2	−37.8 (4)	C7'—C8'—C15'—O2'	−38.8 (4)
C14—C8—C15—O2	−153.5 (3)	C14'—C8'—C15'—O2'	−154.6 (3)
C9—C8—C15—O2	91.4 (4)	C9'—C8'—C15'—O2'	90.1 (4)
C7—C8—C15—C16	145.6 (3)	C7'—C8'—C15'—C16'	143.3 (3)
C14—C8—C15—C16	29.9 (3)	C14'—C8'—C15'—C16'	27.6 (3)
C9—C8—C15—C16	−85.2 (3)	C9'—C8'—C15'—C16'	−87.8 (3)
O2—C15—C16—C17	2.7 (6)	O2'—C15'—C16'—C17'	9.2 (6)
C8—C15—C16—C17	179.2 (4)	C8'—C15'—C16'—C17'	−172.9 (3)
O2—C15—C16—C13	−178.0 (3)	O2'—C15'—C16'—C13'	−176.0 (3)
C8—C15—C16—C13	−1.5 (3)	C8'—C15'—C16'—C13'	1.9 (3)
C14—C13—C16—C17	151.1 (4)	C14'—C13'—C16'—C17'	143.5 (4)
C12—C13—C16—C17	−92.1 (5)	C12'—C13'—C16'—C17'	−100.1 (5)
C14—C13—C16—C15	−28.1 (3)	C14'—C13'—C16'—C15'	−30.7 (3)
C12—C13—C16—C15	88.7 (3)	C12'—C13'—C16'—C15'	85.6 (3)
C6—O5—C19—C4	20.8 (4)	C6'—O5'—C19'—C4'	20.9 (4)
C18—C4—C19—O5	−158.1 (3)	C3'—C4'—C19'—O5'	80.7 (3)
C3—C4—C19—O5	80.7 (4)	C18'—C4'—C19'—O5'	−157.8 (3)
C5—C4—C19—O5	−34.5 (4)	C5'—C4'—C19'—O5'	−34.2 (4)
C7—O4—C20—C10	−41.5 (4)	C7'—O4'—C20'—C10'	−42.5 (4)
C1—C10—C20—O4	−171.2 (3)	C1'—C10'—C20'—O4'	−171.0 (3)
C9—C10—C20—O4	67.2 (3)	C5'—C10'—C20'—O4'	−51.1 (4)
C5—C10—C20—O4	−51.8 (4)	C9'—C10'—C20'—O4'	67.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3^i	0.82	2.05	2.824 (4)	157
O1′—H1′A···O3′^ii	0.82	2.07	2.856 (3)	159

Symmetry codes: (i) x, y, z−1; (ii) x−1, y, z.