Amarisolide monohydrate, a 2-(β-glu­cosyl)­neoclerodane

The absolute configuration of the neoclerodane glycoside amarisolide, presented here as the monohydrate, C₂₆H₃₆O₉·H₂O, has been determined by association with the known configuration of the glucose moiety. Its structure was established as 2β-(O-β-D-gluco­pyran­osyl)­neocleroda-3,13(16),14-trien-15,16-epoxy-18,19-olide. Extensive hydrogen bonding among the hydroxyl groups of the sugar moiety forms layers which are interconnected by water mol­ecules.

S1. Comment

In the course of our phytochemical investigation of the Salvia genus (Maldonado et al., 1992; Ortega et al., 1995), we have investigated S. amarissima Ort. (Family Labiatae, section Uricae subgenus Calosphace). From an acetone extract of the aerial parts of this plant we isolated the new diterpenoid glycoside amarisolide, (I), this being the first report of the occurrence of this type of glycoside in a Salvia species. \sch

A spectroscopic study of the title compound (Fig. 1) revealed it to be a glucosyl derivative of a trans-neo-clerodane diterpene, and led to the establishment of its relative configuration (Maldonado et al., 1996). We here confirm that finding and report the absolute configuration of this compound.

Although the absolute configuration could not be determined from the diffraction data alone, it was established by the known configuration of the β-D-glucose moiety attached at C2 and shows that the molecule is comprised of a tricyclic skeleton with the six-membered rings trans-fused [τ_1,10,5,4 = -39.4 (3)° and τ_9,10,5,6 = 61.8 (3)°]. The six-membered sugar ring exhibits torsion angles of -63.1 (3) to 61.8 (3)°, which are close to the ideal value of 56° for the chair conformation (Bucourt & Hainaut, 1965). The deviations may result from the extensive hydrogen-bonding network involving the sugar hydroxyl groups. The cyclohexene and cyclohexane rings exhibit intermediate conformations between half-chair and sofa for the former and a slightly distorted chair for the later [Cremer and Pople (1975) parameters: ϕ = 344.1 (5)°, θ = 52.3 (4)° Q_T = 0.531 (3) Å and ϕ = 349 (3)°, θ = 6.5 (4)° Q_T = 0.577 (4) Å, respectively]. The five-membered lactone ring adopts an envelope conformation [ϕ = 288.7 (6)°, q₂ = 0.401 (4) Å] with C5 as a flap. Both methyl groups are α-oriented, while the sugar moiety at C2 and the fully extended [τ_9,11,12,13 = -170.8 (3)°] side chain are β-oriented.

The packing scheme may be described as follows: layers of glycoside molecules approximately parallel to the [5 0 3] plane are formed by hydrogen bonding among the hydroxyl groups O3'-H3'A, O4'-H4'A and O6'-H6' of the sugar moiety with the corresponding oxygen atoms O2', O6' and O4', respectively, of symmetry-related molecules. Water molecules interconnect these layers with three hydrogen bonds acting as donor towards the lactone carbonyl atom O4 and the hydroxyl atom O3', while the water atom O5 acts as acceptor for the hydrogen atom from the hydroxyl group O2'-H2'A (Table 1).

S2. Experimental

The dried and finely powdered aerial parts of S. amarissima were extracted with acetone at room temperature. The extract was subjected to a partition between methanol and hexane. The methanolic extract was fractionated over a celite column using mixtures of hexane: ethyl acetate: acetone of increasing polarity. The fractions eluted with ethyl acetate: acetone 9:1 (A) and 4:1 (B) contained the title compound. Fractions A and B were combined, discoloured with activated charcoal and crystallized from methanol-water to obtain the title compound, m.p. 393–405 K. The anhydrous form melts at 479–481 K.

S3. Refinement

Hydrogen atoms of hydroxyl groups in the sugar moiety as well as those of the water molecule were refined in a restrained fashion. The isotropic temperature factor for all the H atoms in the structure was given as: U_iso = 1.2U_eq of parent atom. Diffraction data wre collected for one quarter of the sphere plus several hundred Friedel opposites. Since the refinement of the Flack parameter -0.4 (12) (Flack, 1983) was not useful in assigning the absolute configuration, it was instead assigned by internal reference based on the stereochemistry of the sugar moiety. Amarisolide was resistant to hydrolysis under acidic or basic conditions. Nevertheless, the aglycone was obtained by fungal action of Fusarium moniliforme, which is known to use the sugar moieties of glucosides as a carbon source (García et al., 1979). The absolute configuration was therefore assigned to agree with the known chirality of the glucosyl moiety at C2.

Computing details

Data collection: XSCANS (Siemens, 1993); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXLTL/PC (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. Displacement ellipsoid plot of (I). Ellipsoids are shown at 50% probability while H atoms are represented by spheres of arbitrary size.

2β-O-β-D-glucopyranosyl neo-cleroda-2,13 (16),14-trien-15,16-epoxy- 18,19-olide

Crystal data

C26H36O9·H2O	F(000) = 1096
Mr = 510.56	Dx = 1.332 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
a = 16.997 (2) Å	Cell parameters from 41 reflections
b = 8.441 (1) Å	θ = 5.0–12.5°
c = 17.763 (1) Å	µ = 0.10 mm^−1
β = 92.57 (1)°	T = 293 K
V = 2545.9 (4) Å^3	Prism, colorless
Z = 4	0.60 × 0.50 × 0.20 mm

Data collection

Siemens P4/PC diffractometer	Rint = 0.037
Radiation source: fine-focus sealed tube	θmax = 30.0°, θmin = 1.5°
Graphite monochromator	h = 0→23
ω:2θ scans	k = 0→11
8034 measured reflections	l = −24→24
7373 independent reflections	3 standard reflections every 97 reflections
4762 reflections with I > 2σ(I)	intensity decay: 3%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.062	Only H-atom coordinates refined
wR(F^2) = 0.143	w = 1/[σ^2(Fo^2) + (0.0463P)^2 + 0.124P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.017
7373 reflections	Δρmax = 0.23 e Å^−3
439 parameters	Δρmin = −0.20 e Å^−3
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0076 (7)

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
C1	−0.11391 (19)	0.8218 (4)	0.72558 (19)	0.0348 (7)
H1A	−0.093 (2)	0.721 (5)	0.726 (2)	0.042*
H1B	−0.165 (2)	0.821 (5)	0.701 (2)	0.042*
O1	0.01980 (11)	0.9002 (5)	0.71008 (11)	0.0319 (4)
C2	−0.05927 (18)	0.9216 (5)	0.67860 (17)	0.0325 (6)
H2	−0.065 (2)	0.883 (5)	0.629 (2)	0.039*
C3	−0.08540 (18)	1.0927 (5)	0.67841 (18)	0.0331 (6)
H3	−0.079 (2)	1.153 (5)	0.637 (2)	0.040*
C4	−0.12961 (17)	1.1475 (5)	0.73207 (18)	0.0319 (6)
C5	−0.15668 (16)	1.0596 (5)	0.80000 (16)	0.0289 (6)
C6	−0.1352 (2)	1.1448 (5)	0.87479 (19)	0.0358 (6)
H6A	−0.159 (2)	1.243 (5)	0.872 (2)	0.043*
H6B	−0.080 (2)	1.152 (5)	0.881 (2)	0.043*
C7	−0.1626 (2)	1.0471 (6)	0.9408 (2)	0.0415 (7)
H7A	−0.148 (2)	1.087 (5)	0.987 (2)	0.050*
H7B	−0.219 (3)	1.044 (5)	0.943 (2)	0.050*
C8	−0.13108 (19)	0.8771 (6)	0.94405 (18)	0.0368 (7)
H8	−0.073 (2)	0.882 (5)	0.952 (2)	0.044*
C9	−0.14606 (17)	0.7859 (5)	0.86838 (18)	0.0329 (6)
C10	−0.11778 (16)	0.8949 (5)	0.80456 (16)	0.0279 (5)
H10	−0.064 (2)	0.917 (4)	0.8216 (19)	0.034*
C11	−0.09875 (19)	0.6282 (5)	0.8697 (2)	0.0391 (7)
H11A	−0.112 (2)	0.570 (5)	0.820 (2)	0.047*
H11B	−0.116 (2)	0.567 (5)	0.910 (2)	0.047*
C12	−0.0086 (2)	0.6386 (6)	0.8778 (3)	0.0450 (8)
H12A	0.009 (3)	0.710 (6)	0.849 (3)	0.054*
H12B	0.014 (2)	0.675 (5)	0.932 (3)	0.054*
C13	0.02846 (19)	0.4789 (6)	0.8653 (2)	0.0386 (7)
C14	0.0578 (2)	0.3792 (6)	0.9171 (2)	0.0446 (8)
H14	0.065 (2)	0.378 (5)	0.970 (3)	0.053*
O2	0.08138 (15)	0.2392 (5)	0.88526 (17)	0.0537 (7)
C15	0.0662 (2)	0.2569 (7)	0.8106 (3)	0.0589 (11)
H15	0.079 (3)	0.177 (6)	0.778 (3)	0.071*
C16	0.0343 (2)	0.3982 (7)	0.7958 (2)	0.0541 (10)
H16	0.013 (3)	0.442 (6)	0.752 (3)	0.065*
C17	−0.1642 (3)	0.7952 (8)	1.0130 (3)	0.0592 (11)
H17A	−0.151 (3)	0.852 (6)	1.058 (3)	0.071*
H17B	−0.143 (3)	0.690 (6)	1.019 (3)	0.071*
H17C	−0.221 (3)	0.799 (6)	1.004 (3)	0.071*
C18	−0.18463 (19)	1.2830 (6)	0.7201 (2)	0.0403 (7)
O3	−0.25275 (14)	1.2418 (5)	0.75057 (16)	0.0505 (7)
O4	−0.17743 (16)	1.4068 (5)	0.68721 (17)	0.0535 (7)
C19	−0.24644 (19)	1.0798 (6)	0.7824 (2)	0.0415 (8)
H19A	−0.281 (2)	1.081 (5)	0.827 (2)	0.050*
H19B	−0.267 (2)	1.004 (5)	0.746 (2)	0.050*
C20	−0.2330 (2)	0.7394 (6)	0.8554 (3)	0.0470 (8)
H20A	−0.245 (3)	0.653 (6)	0.891 (3)	0.056*
H20B	−0.268 (3)	0.835 (5)	0.859 (2)	0.056*
H20C	−0.242 (3)	0.693 (5)	0.806 (3)	0.056*
C1'	0.08205 (17)	0.9169 (5)	0.66194 (16)	0.0284 (6)
H1'	0.131 (2)	0.907 (4)	0.692 (2)	0.034*
O1'	0.07877 (13)	1.0727 (4)	0.63111 (12)	0.0317 (5)
C2'	0.08243 (17)	0.7950 (5)	0.59811 (17)	0.0280 (6)
H2'	0.038 (2)	0.808 (4)	0.565 (2)	0.034*
O2'	0.08767 (15)	0.6400 (5)	0.62838 (15)	0.0404 (5)
H2'A	0.043 (2)	0.608 (5)	0.626 (2)	0.049*
C3'	0.15345 (17)	0.8274 (5)	0.55074 (17)	0.0284 (6)
H3'	0.205 (2)	0.808 (4)	0.578 (2)	0.034*
O3'	0.15344 (15)	0.7251 (5)	0.48691 (14)	0.0397 (5)
H3'A	0.194 (2)	0.668 (5)	0.496 (2)	0.048*
C4'	0.15037 (18)	0.9984 (5)	0.52306 (17)	0.0299 (6)
H4'	0.100 (2)	1.007 (5)	0.488 (2)	0.036*
O4'	0.21887 (17)	1.0369 (5)	0.48350 (16)	0.0479 (7)
H4'A	0.224 (3)	0.973 (5)	0.456 (2)	0.057*
C5'	0.14655 (18)	1.1116 (5)	0.58916 (17)	0.0288 (6)
H5'	0.191 (2)	1.095 (4)	0.619 (2)	0.035*
C6'	0.1390 (2)	1.2835 (5)	0.5646 (2)	0.0374 (7)
H6'A	0.081 (2)	1.310 (5)	0.555 (2)	0.045*
H6'B	0.163 (2)	1.298 (5)	0.515 (2)	0.045*
O6'	0.18419 (15)	1.3826 (5)	0.61404 (15)	0.0439 (6)
H6'	0.161 (2)	1.472 (5)	0.620 (2)	0.053*
O5	0.44562 (18)	1.0097 (5)	0.5972 (2)	0.0594 (8)
H5A	0.427 (3)	1.068 (6)	0.571 (3)	0.071*
H5B	0.417 (3)	0.965 (6)	0.618 (3)	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0323 (15)	0.0314 (15)	0.0410 (17)	−0.0021 (12)	0.0033 (13)	−0.0042 (13)
O1	0.0291 (9)	0.0391 (11)	0.0278 (10)	0.0048 (9)	0.0040 (8)	0.0014 (9)
C2	0.0335 (14)	0.0387 (16)	0.0254 (13)	0.0030 (12)	0.0034 (11)	−0.0043 (12)
C3	0.0329 (15)	0.0350 (15)	0.0314 (14)	0.0042 (12)	0.0016 (12)	0.0068 (13)
C4	0.0297 (13)	0.0278 (13)	0.0381 (16)	0.0022 (12)	0.0002 (12)	0.0049 (13)
C5	0.0250 (12)	0.0283 (13)	0.0337 (14)	0.0010 (10)	0.0049 (11)	−0.0005 (12)
C6	0.0381 (16)	0.0298 (14)	0.0402 (17)	0.0004 (13)	0.0082 (13)	−0.0041 (14)
C7	0.0411 (18)	0.0473 (18)	0.0370 (17)	0.0010 (15)	0.0125 (14)	−0.0056 (15)
C8	0.0329 (15)	0.0439 (18)	0.0343 (15)	0.0029 (13)	0.0086 (12)	0.0047 (14)
C9	0.0263 (13)	0.0324 (14)	0.0404 (16)	−0.0031 (11)	0.0056 (11)	0.0034 (13)
C10	0.0229 (12)	0.0277 (13)	0.0332 (14)	−0.0019 (10)	0.0019 (10)	−0.0013 (12)
C11	0.0350 (15)	0.0315 (15)	0.051 (2)	0.0017 (13)	0.0064 (14)	0.0071 (15)
C12	0.0333 (16)	0.0337 (16)	0.067 (3)	0.0013 (14)	−0.0034 (16)	0.0014 (17)
C13	0.0317 (15)	0.0404 (17)	0.0440 (18)	0.0003 (13)	0.0053 (13)	0.0015 (14)
C14	0.0452 (18)	0.047 (2)	0.0421 (18)	0.0094 (15)	0.0050 (15)	−0.0020 (16)
O2	0.0432 (13)	0.0437 (14)	0.0743 (19)	0.0119 (12)	0.0034 (13)	−0.0013 (14)
C15	0.045 (2)	0.066 (3)	0.066 (3)	0.0082 (19)	0.0021 (18)	−0.027 (2)
C16	0.051 (2)	0.073 (3)	0.0381 (18)	0.004 (2)	0.0014 (16)	−0.002 (2)
C17	0.064 (3)	0.067 (3)	0.048 (2)	0.010 (2)	0.020 (2)	0.018 (2)
C18	0.0356 (15)	0.0400 (17)	0.0453 (19)	0.0076 (14)	0.0027 (13)	0.0019 (15)
O3	0.0311 (11)	0.0497 (14)	0.0709 (18)	0.0123 (11)	0.0049 (11)	0.0092 (14)
O4	0.0505 (14)	0.0426 (14)	0.0675 (17)	0.0100 (12)	0.0040 (13)	0.0159 (14)
C19	0.0297 (15)	0.0389 (17)	0.056 (2)	0.0052 (13)	0.0025 (14)	0.0040 (16)
C20	0.0281 (14)	0.047 (2)	0.066 (2)	−0.0101 (14)	0.0073 (15)	0.0078 (19)
C1'	0.0302 (13)	0.0276 (13)	0.0276 (13)	0.0036 (11)	0.0039 (11)	0.0006 (11)
O1'	0.0351 (11)	0.0228 (9)	0.0381 (11)	0.0032 (8)	0.0095 (9)	−0.0012 (9)
C2'	0.0301 (13)	0.0241 (13)	0.0302 (14)	0.0031 (11)	0.0059 (11)	−0.0006 (11)
O2'	0.0417 (12)	0.0243 (10)	0.0563 (15)	0.0031 (10)	0.0134 (11)	0.0039 (10)
C3'	0.0290 (13)	0.0239 (13)	0.0328 (14)	−0.0004 (10)	0.0055 (11)	−0.0056 (11)
O3'	0.0451 (12)	0.0343 (11)	0.0402 (13)	0.0049 (10)	0.0084 (10)	−0.0120 (10)
C4'	0.0352 (15)	0.0223 (12)	0.0330 (15)	−0.0031 (11)	0.0092 (12)	−0.0002 (11)
O4'	0.0547 (15)	0.0369 (13)	0.0545 (16)	−0.0077 (11)	0.0302 (12)	−0.0103 (11)
C5'	0.0315 (14)	0.0224 (13)	0.0327 (14)	0.0022 (10)	0.0036 (11)	−0.0025 (11)
C6'	0.0472 (18)	0.0231 (14)	0.0423 (18)	0.0008 (13)	0.0051 (15)	0.0038 (13)
O6'	0.0483 (14)	0.0228 (10)	0.0610 (16)	−0.0004 (10)	0.0063 (11)	−0.0073 (11)
O5	0.0452 (16)	0.0571 (19)	0.076 (2)	−0.0060 (13)	0.0001 (14)	0.0126 (16)

Geometric parameters (Å, º)

C1—C2	1.529 (4)	C15—C16	1.332 (7)
C1—C10	1.537 (4)	C15—H15	0.92 (5)
C1—H1A	0.92 (4)	C16—H16	0.92 (5)
C1—H1B	0.95 (4)	C17—H17A	0.94 (5)
O1—C1'	1.397 (3)	C17—H17B	0.96 (5)
O1—C2	1.444 (4)	C17—H17C	0.97 (5)
C2—C3	1.511 (4)	C18—O4	1.206 (4)
C2—H2	0.93 (4)	C18—O3	1.346 (4)
C3—C4	1.323 (4)	O3—C19	1.482 (5)
C3—H3	0.90 (4)	C19—H19A	1.01 (4)
C4—C18	1.487 (4)	C19—H19B	0.96 (4)
C4—C5	1.506 (4)	C20—H20A	0.99 (5)
C5—C10	1.540 (4)	C20—H20B	1.00 (5)
C5—C6	1.540 (4)	C20—H20C	0.97 (5)
C5—C19	1.553 (4)	C1'—O1'	1.425 (3)
C6—C7	1.523 (5)	C1'—C2'	1.531 (4)
C6—H6A	0.93 (4)	C1'—H1'	0.98 (4)
C6—H6B	0.94 (4)	O1'—C5'	1.438 (3)
C7—C8	1.532 (5)	C2'—O2'	1.416 (4)
C7—H7A	0.91 (4)	C2'—C3'	1.527 (4)
C7—H7B	0.96 (4)	C2'—H2'	0.95 (4)
C8—C17	1.534 (5)	O2'—H2'A	0.80 (4)
C8—C9	1.560 (5)	C3'—O3'	1.425 (4)
C8—H8	0.99 (4)	C3'—C4'	1.526 (4)
C9—C20	1.537 (4)	C3'—H3'	0.99 (4)
C9—C10	1.553 (4)	O3'—H3'A	0.85 (3)
C9—C11	1.554 (4)	C4'—O4'	1.424 (4)
C10—H10	0.98 (4)	C4'—C5'	1.517 (4)
C11—C12	1.535 (5)	C4'—H4'	1.05 (4)
C11—H11A	1.03 (4)	O4'—H4'A	0.74 (4)
C11—H11B	0.93 (4)	C5'—C6'	1.519 (4)
C12—C13	1.508 (5)	C5'—H5'	0.91 (4)
C12—H12A	0.86 (5)	C6'—O6'	1.415 (4)
C12—H12B	1.06 (5)	C6'—H6'A	1.01 (4)
C13—C14	1.327 (5)	C6'—H6'B	0.99 (4)
C13—C16	1.418 (5)	O6'—H6'	0.86 (4)
C14—O2	1.378 (5)	O5—H5A	0.73 (4)
C14—H14	0.95 (4)	O5—H5B	0.72 (4)
O2—C15	1.349 (5)
C2—C1—C10	109.2 (2)	O2—C14—H14	112 (3)
C2—C1—H1A	106 (2)	C15—O2—C14	105.2 (3)
C10—C1—H1A	113 (2)	C16—C15—O2	110.5 (4)
C2—C1—H1B	109 (2)	C16—C15—H15	130 (3)
C10—C1—H1B	110 (2)	O2—C15—H15	119 (3)
H1A—C1—H1B	110 (3)	C15—C16—C13	107.6 (4)
C1'—O1—C2	117.9 (2)	C15—C16—H16	132 (3)
O1—C2—C3	112.9 (3)	C13—C16—H16	120 (3)
O1—C2—C1	107.3 (3)	C8—C17—H17A	111 (3)
C3—C2—C1	110.0 (2)	C8—C17—H17B	111 (3)
O1—C2—H2	112 (2)	H17A—C17—H17B	107 (4)
C3—C2—H2	108 (2)	C8—C17—H17C	105 (3)
C1—C2—H2	106 (2)	H17A—C17—H17C	109 (4)
C4—C3—C2	120.6 (3)	H17B—C17—H17C	114 (4)
C4—C3—H3	119 (2)	O4—C18—O3	121.8 (3)
C2—C3—H3	120 (2)	O4—C18—C4	131.2 (3)
C3—C4—C18	122.6 (3)	O3—C18—C4	106.9 (3)
C3—C4—C5	127.5 (3)	C18—O3—C19	110.1 (3)
C18—C4—C5	106.3 (3)	O3—C19—C5	103.4 (3)
C4—C5—C10	109.9 (2)	O3—C19—H19A	105 (2)
C4—C5—C6	113.1 (3)	C5—C19—H19A	116 (2)
C10—C5—C6	107.0 (2)	O3—C19—H19B	110 (3)
C4—C5—C19	96.8 (2)	C5—C19—H19B	113 (3)
C10—C5—C19	121.7 (3)	H19A—C19—H19B	109 (3)
C6—C5—C19	108.3 (3)	C9—C20—H20A	109 (3)
C7—C6—C5	110.0 (3)	C9—C20—H20B	110 (3)
C7—C6—H6A	112 (2)	H20A—C20—H20B	114 (3)
C5—C6—H6A	107 (2)	C9—C20—H20C	111 (3)
C7—C6—H6B	107 (3)	H20A—C20—H20C	105 (4)
C5—C6—H6B	109 (2)	H20B—C20—H20C	109 (4)
H6A—C6—H6B	112 (4)	O1—C1'—O1'	108.1 (2)
C6—C7—C8	114.7 (3)	O1—C1'—C2'	114.5 (2)
C6—C7—H7A	114 (3)	O1'—C1'—C2'	109.7 (2)
C8—C7—H7A	104 (3)	O1—C1'—H1'	108 (2)
C6—C7—H7B	112 (2)	O1'—C1'—H1'	108 (2)
C8—C7—H7B	108 (3)	C2'—C1'—H1'	109 (2)
H7A—C7—H7B	103 (3)	C1'—O1'—C5'	113.1 (2)
C7—C8—C17	108.2 (3)	O2'—C2'—C3'	109.7 (2)
C7—C8—C9	112.7 (3)	O2'—C2'—C1'	110.0 (2)
C17—C8—C9	114.4 (3)	C3'—C2'—C1'	108.5 (2)
C7—C8—H8	108 (2)	O2'—C2'—H2'	112 (2)
C17—C8—H8	107 (2)	C3'—C2'—H2'	106 (2)
C9—C8—H8	106 (2)	C1'—C2'—H2'	111 (2)
C20—C9—C10	111.6 (3)	C2'—O2'—H2'A	104 (3)
C20—C9—C11	106.1 (3)	O3'—C3'—C4'	108.6 (2)
C10—C9—C11	109.9 (2)	O3'—C3'—C2'	111.0 (2)
C20—C9—C8	111.9 (3)	C4'—C3'—C2'	109.3 (2)
C10—C9—C8	107.0 (2)	O3'—C3'—H3'	105 (2)
C11—C9—C8	110.2 (3)	C4'—C3'—H3'	109 (2)
C1—C10—C5	110.5 (2)	C2'—C3'—H3'	114 (2)
C1—C10—C9	117.1 (2)	C3'—O3'—H3'A	103 (3)
C5—C10—C9	115.3 (2)	O4'—C4'—C5'	107.6 (2)
C1—C10—H10	107 (2)	O4'—C4'—C3'	111.0 (3)
C5—C10—H10	104 (2)	C5'—C4'—C3'	110.4 (2)
C9—C10—H10	102 (2)	O4'—C4'—H4'	111 (2)
C12—C11—C9	117.8 (3)	C5'—C4'—H4'	111 (2)
C12—C11—H11A	107 (2)	C3'—C4'—H4'	106 (2)
C9—C11—H11A	108 (2)	C4'—O4'—H4'A	107 (4)
C12—C11—H11B	108 (2)	O1'—C5'—C4'	108.7 (2)
C9—C11—H11B	108 (3)	O1'—C5'—C6'	107.9 (2)
H11A—C11—H11B	109 (3)	C4'—C5'—C6'	112.7 (3)
C13—C12—C11	110.9 (3)	O1'—C5'—H5'	109 (2)
C13—C12—H12A	112 (3)	C4'—C5'—H5'	107 (2)
C11—C12—H12A	111 (3)	C6'—C5'—H5'	112 (2)
C13—C12—H12B	104 (2)	O6'—C6'—C5'	110.5 (3)
C11—C12—H12B	115 (2)	O6'—C6'—H6'A	118 (2)
H12A—C12—H12B	102 (4)	C5'—C6'—H6'A	109 (2)
C14—C13—C16	105.0 (3)	O6'—C6'—H6'B	104 (2)
C14—C13—C12	127.7 (4)	C5'—C6'—H6'B	110 (2)
C16—C13—C12	127.1 (4)	H6'A—C6'—H6'B	106 (3)
C13—C14—O2	111.6 (3)	C6'—O6'—H6'	111 (3)
C13—C14—H14	136 (3)	H5A—O5—H5B	113 (6)
C1'—O1—C2—C3	−86.6 (3)	C11—C12—C13—C14	−101.9 (4)
C1'—O1—C2—C1	152.1 (2)	C11—C12—C13—C16	73.1 (5)
C10—C1—C2—O1	68.9 (3)	C16—C13—C14—O2	−0.5 (4)
C10—C1—C2—C3	−54.2 (3)	C12—C13—C14—O2	175.4 (3)
O1—C2—C3—C4	−98.4 (3)	C13—C14—O2—C15	0.7 (4)
C1—C2—C3—C4	21.4 (4)	C14—O2—C15—C16	−0.6 (5)
C2—C3—C4—C18	−152.7 (3)	O2—C15—C16—C13	0.3 (5)
C2—C3—C4—C5	3.1 (5)	C14—C13—C16—C15	0.1 (5)
C3—C4—C5—C10	6.2 (4)	C12—C13—C16—C15	−175.8 (4)
C18—C4—C5—C10	165.2 (3)	C3—C4—C18—O4	−41.4 (6)
C3—C4—C5—C6	125.7 (3)	C5—C4—C18—O4	158.4 (4)
C18—C4—C5—C6	−75.4 (3)	C3—C4—C18—O3	135.0 (3)
C3—C4—C5—C19	−121.1 (4)	C5—C4—C18—O3	−25.2 (4)
C18—C4—C5—C19	37.9 (3)	O4—C18—O3—C19	176.0 (4)
C4—C5—C6—C7	−178.6 (3)	C4—C18—O3—C19	−0.8 (4)
C10—C5—C6—C7	−57.4 (3)	C18—O3—C19—C5	25.4 (4)
C19—C5—C6—C7	75.4 (3)	C4—C5—C19—O3	−37.3 (3)
C5—C6—C7—C8	55.8 (4)	C10—C5—C19—O3	−155.8 (3)
C6—C7—C8—C17	−179.7 (4)	C6—C5—C19—O3	79.8 (3)
C6—C7—C8—C9	−52.1 (4)	C2—O1—C1'—O1'	59.3 (3)
C7—C8—C9—C20	−73.5 (3)	C2—O1—C1'—C2'	−63.3 (3)
C17—C8—C9—C20	50.7 (4)	O1—C1'—O1'—C5'	171.5 (2)
C7—C8—C9—C10	49.1 (3)	C2'—C1'—O1'—C5'	−63.1 (3)
C17—C8—C9—C10	173.4 (3)	O1—C1'—C2'—O2'	−59.8 (3)
C7—C8—C9—C11	168.7 (3)	O1'—C1'—C2'—O2'	178.5 (2)
C17—C8—C9—C11	−67.1 (4)	O1—C1'—C2'—C3'	−179.8 (2)
C2—C1—C10—C5	65.2 (3)	O1'—C1'—C2'—C3'	58.6 (3)
C2—C1—C10—C9	−160.1 (2)	O2'—C2'—C3'—O3'	64.4 (3)
C4—C5—C10—C1	−39.4 (3)	C1'—C2'—C3'—O3'	−175.5 (2)
C6—C5—C10—C1	−162.6 (2)	O2'—C2'—C3'—C4'	−175.9 (3)
C19—C5—C10—C1	72.4 (3)	C1'—C2'—C3'—C4'	−55.8 (3)
C4—C5—C10—C9	−175.0 (2)	O3'—C3'—C4'—O4'	−63.3 (3)
C6—C5—C10—C9	61.8 (3)	C2'—C3'—C4'—O4'	175.5 (3)
C19—C5—C10—C9	−63.3 (4)	O3'—C3'—C4'—C5'	177.4 (2)
C20—C9—C10—C1	−66.7 (4)	C2'—C3'—C4'—C5'	56.3 (3)
C11—C9—C10—C1	50.8 (3)	C1'—O1'—C5'—C4'	61.8 (3)
C8—C9—C10—C1	170.5 (3)	C1'—O1'—C5'—C6'	−175.7 (2)
C20—C9—C10—C5	65.9 (4)	O4'—C4'—C5'—O1'	−178.7 (3)
C11—C9—C10—C5	−176.6 (3)	C3'—C4'—C5'—O1'	−57.4 (3)
C8—C9—C10—C5	−56.9 (3)	O4'—C4'—C5'—C6'	61.8 (3)
C20—C9—C11—C12	176.9 (3)	C3'—C4'—C5'—C6'	−176.9 (3)
C10—C9—C11—C12	56.0 (4)	O1'—C5'—C6'—O6'	98.5 (3)
C8—C9—C11—C12	−61.7 (4)	C4'—C5'—C6'—O6'	−141.5 (3)
C9—C11—C12—C13	−170.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2′—H2′A···O5^i	0.80 (4)	1.91 (4)	2.688 (4)	166 (4)
O3′—H3′A···O4′^ii	0.85 (3)	1.87 (4)	2.721 (4)	178 (4)
O4′—H4′A···O6′^ii	0.74 (4)	2.17 (4)	2.769 (3)	139 (5)
O6′—H6′···O2′^iii	0.86 (4)	1.90 (4)	2.741 (3)	166 (4)
O5—H5A···O3′^iv	0.73 (4)	2.14 (4)	2.854 (4)	165 (6)
O5—H5B···O4^v	0.72 (4)	2.13 (4)	2.826 (4)	162 (6)

Symmetry codes: (i) x−1/2, y−1/2, z; (ii) −x+1/2, y−1/2, −z+1; (iii) x, y+1, z; (iv) −x+1/2, y+1/2, −z+1; (v) x+1/2, y−1/2, z.