(1R,4S,8R,9S,12S,13S,14R,16S,19R)-19-Acet­oxy-14-hydr­oxy-7,7-dimethyl-17-methyl­ene-2,18-dioxo-3,10-dioxapenta­cyclo­[14.2.1.0^1,13.0^4,12.0^8,12]nona­dec-9-yl acetate

The title compound, C₂₄H₃₀O₉, was prepared from the natural diterpenoid macrocalyxin J and is built from five fused rings. Cyclo­hexane ring A adopts a chair conformation, ring B exists in a screw-boat conformation and ring C adopts a boat conformation. The five-membered ring D adopts an envelope conformation, while ring E adopts a twist conformation. The crystal structure displays inter­molecular O—H...O hydrogen bonds, which link mol­ecules to form a chain parallel to the a axis. The absolute configuration was deduced from the chirality of macrocalyxin A, which was isolated from the same plant (i.e. Rabdosia macrocalyx) as macrocalyxin J. One of the carbonyl O atoms is disordered over two sites, with refined site occupancies of 0.794 (12):0.206 (12).

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.044
• wR factor = 0.064
• Data-to-parameter ratio = 7.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       7.64
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.77 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.33 Ratio
PLAT301_ALERT_3_C Main Residue  Disorder .........................       3.00 Perc.
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5
PLAT414_ALERT_2_C Short Intra D-H..H-X       H2     ..  H4      ..       1.94 Ang.

Alert level G
REFLT03_ALERT_4_G 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.
           From the CIF: _diffrn_reflns_theta_max           25.01
           From the CIF: _reflns_number_total               2324
           Count of symmetry unique reflns         2326
           Completeness (_total/calc)             99.91%
           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
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C1     ...          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4     ...          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C8     ...          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C9     ...          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C12    ...          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C13    ...          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C14    ...          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C16    ...          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C19    ...          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
  10 ALERT level G = General alerts; check

  10 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Since the natural diterpenoid Macrocalyxin J exhibits cytotoxicity in vitro against cultures of Hela cells (Shi et al., 2007), I have derived the title compound from it.

The molecule is built up from five fused rings, three six membered and two five membered rings. Some geometrical features of these rings were investigated using PLATON (Spek, 2003).

Cyclohexane ring A (C4—C8/C12) adopts a chair conformation with puckering parameters (Cremer & Pople, 1975) Q = 0.542 (4) Å, and θ= 161.5 (3) and ϕ = 285.9 (12) °, ring B (O3/C2/C1/C13/C12/C4) exists in a screw-boat conformation (Q = 0.631 (3) Å, θ = 112.5 (3) and ϕ = 90.5 (3) °), ring C (C1/C13—C16/C19) adopt the boat conformation (Q = 0.847 (4) Å, θ = 81.0 (3) and ϕ = 292.0 (2) °). The two five-membered rings, ring D (C1/C18/C17/C16/C19) adopts an envelope conformation with puckering parameters Q2 = 0.472 (4) Å, and ϕ2 = 147.2 (5)° (envelope on C19), the ring E (O10/C9/C8/C12/C11) adopts a twisted conformation with puckering parameters Q2 = 0.368 (3) Å, and ϕ2 = 268.6 (5)° (twisted on C8 and C12).

Intermolecular O—H···O hydrogen bond is present and link molecules to form a chain parallel to the a axis.

Since the title compound was prepared from Macrocalyxin J, which was isolated from the same plant (i.e. Rabdosia macrocalyx) as Macrocalyxin A, the configuration can be deduced from the known chirality of the Macrocalyxin A (Shi et al., 2003),and thus Fig. 1 represents the correct absolute configuration.

Related literature

For related literature, see: Cremer & Pople (1975); Shi et al. (2003, 2007).

S2. Experimental

Macrocalyxin J (50 mg; isolated from Rabdosia macrocalyx) was dissolved in a mixture of pyridine (1.5 ml) and Ac₂O (1.5 ml) and the solution was stirred for 3 h at room temperature. MeOH (5 ml) was then added to the mixture and the solution was concentrated in vacuo to give a residue that was purified by column chromatography to give the title compound (I).

Crystals suitable for X-ray structure analysis were obtained by slow evaporation from a solution of methanol at room temperature.

S3. Refinement

H atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.96 Å (CH₃), 0.97 Å (CH₂) and 0.98(CH) and with the temperature factors U_iso= 1.5 U_eq(CH₃) and 1.2 U_eq(CH₂, CH).

In the absence of significant anomalous scattering, the absolute configuration could not be reliably determined from the X-ray analyses. The Friedel pairs were merged and any references to the Flack parameter was removed.

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. Perspective view of the title compound, shown with 30% probability displacement ellipsoids.
	Fig. 2. Partial packing view of the title compound showing the formation of a chain parallel through O—H···O hydrogen bonding interactions. H atoms not involved in hydrogen bonds have been omitted for clarity. Symmetry codes: (i) x - 1,y,z; (ii) x + 1,y,z.
	Fig. 3. The formation of the title compound.

(1R,4S,8R,9S,12S,13S,14R, 16S,19R)-19-acetoxy-14-hydroxy-7,7-dimethyl-17-methylene- 2,18-dioxo-3,10-dioxapentacyclo[14.2.1.0^1,13.0^4,12.0^8,12]nonadec-9-yl acetate

Crystal data

C24H30O9	F(000) = 984
Mr = 462.48	Dx = 1.350 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1637 reflections
a = 7.5188 (6) Å	θ = 2.5–18.6°
b = 9.7993 (13) Å	µ = 0.10 mm^−1
c = 30.876 (3) Å	T = 298 K
V = 2274.9 (4) Å^3	Needle, colorless
Z = 4	0.40 × 0.18 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2324 independent reflections
Radiation source: fine-focus sealed tube	1579 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
ϕ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −8→8
Tmin = 0.960, Tmax = 0.983	k = −11→11
10274 measured reflections	l = −36→20

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.064	w = 1/[σ^2(Fo^2) + (0.0113P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.16	(Δ/σ)max = 0.001
2324 reflections	Δρmax = 0.18 e Å^−3
304 parameters	Δρmin = −0.14 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0023 (3)

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	Occ. (<1)
O1	0.9266 (3)	0.3557 (3)	0.10199 (9)	0.0638 (8)
O2	0.2850 (3)	0.4305 (2)	0.17675 (7)	0.0576 (7)
H2	0.2533	0.5074	0.1697	0.086*
O3	0.7029 (3)	0.6822 (2)	0.15932 (7)	0.0493 (6)
O4	0.9468 (3)	0.5647 (2)	0.16904 (8)	0.0575 (7)
O5	0.8068 (3)	0.3360 (3)	0.21771 (8)	0.0585 (7)
O6	0.7301 (5)	0.5132 (4)	0.25961 (10)	0.0999 (12)
O7	0.3183 (3)	0.4234 (2)	0.03846 (7)	0.0540 (7)
O8	0.2005 (10)	0.4360 (5)	−0.0284 (2)	0.097 (2)	0.794 (12)
O8'	0.109 (4)	0.440 (2)	−0.0064 (7)	0.097 (2)	0.206 (12)
O10	0.5259 (3)	0.5940 (2)	0.03211 (7)	0.0536 (7)
C1	0.6912 (4)	0.4326 (3)	0.15109 (10)	0.0381 (8)
C2	0.7893 (5)	0.5633 (4)	0.16052 (10)	0.0440 (9)
C4	0.5137 (4)	0.6782 (3)	0.14912 (11)	0.0421 (9)
H4	0.4504	0.6345	0.1731	0.051*
C5	0.4536 (5)	0.8256 (3)	0.14586 (12)	0.0539 (11)
H5A	0.5275	0.8745	0.1253	0.065*
H5B	0.4640	0.8699	0.1738	0.065*
C6	0.2601 (5)	0.8270 (3)	0.13087 (11)	0.0517 (10)
H6A	0.1887	0.7737	0.1508	0.062*
H6B	0.2160	0.9201	0.1313	0.062*
C7	0.2398 (5)	0.7694 (3)	0.08555 (11)	0.0431 (10)
C8	0.3068 (4)	0.6184 (3)	0.08541 (10)	0.0359 (9)
H8	0.2158	0.5598	0.0985	0.043*
C9	0.3465 (5)	0.5686 (4)	0.04003 (10)	0.0439 (9)
H9	0.2714	0.6155	0.0188	0.053*
C11	0.6174 (5)	0.6268 (3)	0.07161 (11)	0.0464 (10)
H11A	0.6495	0.7226	0.0722	0.056*
H11B	0.7248	0.5727	0.0743	0.056*
C12	0.4870 (4)	0.5935 (3)	0.10847 (10)	0.0346 (8)
C13	0.5188 (4)	0.4418 (3)	0.12135 (10)	0.0367 (9)
H13	0.5496	0.3946	0.0944	0.044*
C14	0.3617 (5)	0.3632 (3)	0.14031 (11)	0.0463 (10)
H14	0.2702	0.3557	0.1178	0.056*
C15	0.4184 (5)	0.2188 (3)	0.15317 (12)	0.0558 (11)
H15A	0.4182	0.1616	0.1275	0.067*
H15B	0.3314	0.1819	0.1732	0.067*
C16	0.6038 (5)	0.2121 (4)	0.17436 (12)	0.0521 (10)
H16	0.6077	0.1417	0.1969	0.062*
C17	0.7514 (5)	0.1926 (4)	0.14214 (12)	0.0527 (11)
C18	0.8119 (5)	0.3301 (4)	0.12811 (12)	0.0481 (10)
C19	0.6474 (5)	0.3517 (3)	0.19292 (11)	0.0475 (10)
H19	0.5493	0.3914	0.2096	0.057*
C20	0.8287 (5)	0.0804 (4)	0.12796 (13)	0.0759 (13)
H20A	0.9235	0.0861	0.1087	0.091*
H20B	0.7884	−0.0045	0.1372	0.091*
C21	0.0411 (4)	0.7654 (3)	0.07380 (12)	0.0554 (11)
H21A	−0.0225	0.7145	0.0954	0.083*
H21B	0.0264	0.7225	0.0461	0.083*
H21C	−0.0046	0.8568	0.0726	0.083*
C22	0.3306 (5)	0.8651 (3)	0.05231 (12)	0.0629 (12)
H22A	0.3085	0.8322	0.0235	0.094*
H22B	0.4564	0.8669	0.0576	0.094*
H22C	0.2832	0.9556	0.0552	0.094*
C23	0.8354 (7)	0.4277 (6)	0.24981 (14)	0.0762 (14)
C24	1.0157 (6)	0.4049 (5)	0.26971 (12)	0.0957 (17)
H24A	1.1059	0.4180	0.2481	0.143*
H24B	1.0227	0.3135	0.2808	0.143*
H24C	1.0334	0.4687	0.2929	0.143*
C25	0.2385 (6)	0.3704 (4)	0.00398 (15)	0.0697 (13)
C26	0.2193 (6)	0.2209 (4)	0.00810 (14)	0.0904 (16)
H26A	0.1868	0.1829	−0.0194	0.136*
H26B	0.1286	0.2006	0.0290	0.136*
H26C	0.3302	0.1822	0.0174	0.136*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0483 (18)	0.0726 (19)	0.0705 (18)	0.0063 (15)	0.0176 (15)	0.0007 (16)
O2	0.0565 (17)	0.0549 (15)	0.0616 (15)	0.0084 (14)	0.0072 (14)	0.0112 (15)
O3	0.0370 (16)	0.0476 (15)	0.0633 (16)	−0.0001 (13)	−0.0105 (13)	−0.0090 (13)
O4	0.0351 (16)	0.0637 (16)	0.0737 (18)	−0.0027 (14)	−0.0131 (14)	0.0023 (16)
O5	0.0530 (18)	0.0747 (19)	0.0478 (16)	0.0041 (16)	−0.0117 (14)	0.0042 (15)
O6	0.087 (3)	0.131 (3)	0.082 (2)	0.002 (2)	0.000 (2)	−0.038 (2)
O7	0.0669 (19)	0.0443 (15)	0.0508 (16)	−0.0013 (15)	−0.0141 (14)	−0.0079 (14)
O8	0.149 (6)	0.086 (2)	0.055 (4)	0.010 (3)	−0.040 (4)	−0.013 (3)
O8'	0.149 (6)	0.086 (2)	0.055 (4)	0.010 (3)	−0.040 (4)	−0.013 (3)
O10	0.0485 (17)	0.0719 (18)	0.0404 (15)	−0.0043 (15)	0.0044 (13)	0.0009 (14)
C1	0.029 (2)	0.042 (2)	0.043 (2)	0.0020 (19)	−0.0021 (17)	0.0021 (19)
C2	0.040 (3)	0.053 (2)	0.039 (2)	0.000 (2)	−0.001 (2)	0.003 (2)
C4	0.031 (2)	0.048 (2)	0.047 (2)	−0.0017 (18)	−0.0044 (18)	−0.003 (2)
C5	0.051 (3)	0.046 (2)	0.065 (3)	0.005 (2)	−0.006 (2)	−0.018 (2)
C6	0.044 (3)	0.040 (2)	0.071 (3)	0.0091 (19)	−0.003 (2)	−0.008 (2)
C7	0.033 (2)	0.041 (2)	0.055 (2)	0.0015 (18)	−0.0008 (19)	0.0033 (19)
C8	0.031 (2)	0.033 (2)	0.044 (2)	−0.0046 (17)	−0.0001 (17)	0.0013 (17)
C9	0.035 (2)	0.049 (2)	0.047 (2)	0.003 (2)	−0.0100 (19)	0.002 (2)
C11	0.041 (2)	0.047 (2)	0.052 (2)	−0.0002 (19)	0.0001 (19)	0.006 (2)
C12	0.027 (2)	0.036 (2)	0.041 (2)	0.0007 (16)	0.0007 (17)	−0.0020 (19)
C13	0.029 (2)	0.041 (2)	0.040 (2)	−0.0036 (18)	−0.0019 (16)	0.0002 (19)
C14	0.039 (2)	0.051 (2)	0.050 (2)	−0.002 (2)	−0.0031 (19)	0.003 (2)
C15	0.050 (3)	0.047 (2)	0.070 (3)	−0.006 (2)	−0.005 (2)	0.011 (2)
C16	0.048 (3)	0.048 (2)	0.061 (3)	0.002 (2)	−0.006 (2)	0.010 (2)
C17	0.047 (3)	0.049 (2)	0.062 (3)	0.003 (2)	−0.009 (2)	−0.004 (2)
C18	0.038 (3)	0.054 (3)	0.052 (2)	0.005 (2)	−0.008 (2)	0.001 (2)
C19	0.039 (3)	0.055 (2)	0.048 (2)	0.002 (2)	−0.0060 (19)	0.009 (2)
C20	0.061 (3)	0.058 (3)	0.109 (3)	0.004 (3)	−0.004 (3)	−0.008 (3)
C21	0.040 (3)	0.053 (2)	0.074 (3)	0.005 (2)	−0.002 (2)	0.004 (2)
C22	0.056 (3)	0.048 (2)	0.085 (3)	−0.001 (2)	−0.001 (2)	0.015 (2)
C23	0.067 (4)	0.117 (5)	0.044 (3)	−0.011 (4)	0.000 (3)	0.006 (3)
C24	0.073 (4)	0.159 (5)	0.055 (3)	−0.024 (4)	−0.023 (3)	0.007 (3)
C25	0.072 (4)	0.065 (3)	0.072 (3)	0.008 (3)	−0.026 (3)	−0.015 (3)
C26	0.096 (4)	0.067 (3)	0.109 (4)	−0.011 (3)	−0.020 (3)	−0.022 (3)

Geometric parameters (Å, º)

O1—C18	1.207 (4)	C9—H9	0.9800
O2—C14	1.426 (4)	C11—C12	1.537 (4)
O2—H2	0.8200	C11—H11A	0.9700
O3—C2	1.334 (4)	C11—H11B	0.9700
O3—C4	1.458 (4)	C12—C13	1.557 (4)
O4—C2	1.213 (4)	C13—C14	1.527 (4)
O5—C23	1.355 (5)	C13—H13	0.9800
O5—C19	1.430 (4)	C14—C15	1.530 (4)
O6—C23	1.192 (5)	C14—H14	0.9800
O7—C25	1.328 (4)	C15—C16	1.542 (4)
O7—C9	1.439 (4)	C15—H15A	0.9700
O8—C25	1.223 (6)	C15—H15B	0.9700
O8'—C25	1.23 (2)	C16—C17	1.502 (5)
O10—C9	1.394 (3)	C16—C19	1.519 (4)
O10—C11	1.437 (4)	C16—H16	0.9800
C1—C2	1.507 (4)	C17—C20	1.319 (4)
C1—C18	1.528 (5)	C17—C18	1.487 (5)
C1—C19	1.551 (4)	C19—H19	0.9800
C1—C13	1.591 (4)	C20—H20A	0.9300
C4—C5	1.516 (4)	C20—H20B	0.9300
C4—C12	1.518 (4)	C21—H21A	0.9600
C4—H4	0.9800	C21—H21B	0.9600
C5—C6	1.527 (5)	C21—H21C	0.9600
C5—H5A	0.9700	C22—H22A	0.9600
C5—H5B	0.9700	C22—H22B	0.9600
C6—C7	1.517 (4)	C22—H22C	0.9600
C6—H6A	0.9700	C23—C24	1.505 (6)
C6—H6B	0.9700	C24—H24A	0.9600
C7—C21	1.538 (4)	C24—H24B	0.9600
C7—C22	1.549 (4)	C24—H24C	0.9600
C7—C8	1.563 (4)	C25—C26	1.477 (5)
C8—C9	1.513 (4)	C26—H26A	0.9600
C8—C12	1.550 (4)	C26—H26B	0.9600
C8—H8	0.9800	C26—H26C	0.9600
C14—O2—H2	109.5	C1—C13—H13	105.7
C2—O3—C4	117.3 (3)	O2—C14—C13	112.5 (3)
C23—O5—C19	117.0 (3)	O2—C14—C15	109.6 (3)
C25—O7—C9	118.7 (3)	C13—C14—C15	110.5 (3)
C9—O10—C11	110.8 (2)	O2—C14—H14	108.0
C2—C1—C18	111.0 (3)	C13—C14—H14	108.0
C2—C1—C19	112.2 (3)	C15—C14—H14	108.0
C18—C1—C19	100.2 (3)	C14—C15—C16	113.7 (3)
C2—C1—C13	117.5 (3)	C14—C15—H15A	108.8
C18—C1—C13	104.7 (3)	C16—C15—H15A	108.8
C19—C1—C13	109.7 (3)	C14—C15—H15B	108.8
O4—C2—O3	118.1 (3)	C16—C15—H15B	108.8
O4—C2—C1	122.0 (4)	H15A—C15—H15B	107.7
O3—C2—C1	119.9 (3)	C17—C16—C19	101.8 (3)
O3—C4—C5	106.3 (3)	C17—C16—C15	113.1 (3)
O3—C4—C12	108.8 (3)	C19—C16—C15	108.5 (3)
C5—C4—C12	115.2 (3)	C17—C16—H16	111.0
O3—C4—H4	108.8	C19—C16—H16	111.0
C5—C4—H4	108.8	C15—C16—H16	111.0
C12—C4—H4	108.8	C20—C17—C18	121.6 (4)
C4—C5—C6	108.2 (3)	C20—C17—C16	130.7 (4)
C4—C5—H5A	110.0	C18—C17—C16	107.7 (3)
C6—C5—H5A	110.0	O1—C18—C17	127.0 (4)
C4—C5—H5B	110.0	O1—C18—C1	126.7 (3)
C6—C5—H5B	110.0	C17—C18—C1	106.2 (3)
H5A—C5—H5B	108.4	O5—C19—C16	106.6 (3)
C7—C6—C5	111.8 (3)	O5—C19—C1	108.8 (3)
C7—C6—H6A	109.2	C16—C19—C1	101.1 (3)
C5—C6—H6A	109.2	O5—C19—H19	113.1
C7—C6—H6B	109.2	C16—C19—H19	113.1
C5—C6—H6B	109.2	C1—C19—H19	113.1
H6A—C6—H6B	107.9	C17—C20—H20A	120.0
C6—C7—C21	109.0 (3)	C17—C20—H20B	120.0
C6—C7—C22	109.9 (3)	H20A—C20—H20B	120.0
C21—C7—C22	106.7 (3)	C7—C21—H21A	109.5
C6—C7—C8	108.8 (3)	C7—C21—H21B	109.5
C21—C7—C8	106.8 (3)	H21A—C21—H21B	109.5
C22—C7—C8	115.4 (3)	C7—C21—H21C	109.5
C9—C8—C12	101.7 (3)	H21A—C21—H21C	109.5
C9—C8—C7	111.8 (3)	H21B—C21—H21C	109.5
C12—C8—C7	115.4 (3)	C7—C22—H22A	109.5
C9—C8—H8	109.2	C7—C22—H22B	109.5
C12—C8—H8	109.2	H22A—C22—H22B	109.5
C7—C8—H8	109.2	C7—C22—H22C	109.5
O10—C9—O7	108.3 (3)	H22A—C22—H22C	109.5
O10—C9—C8	107.2 (3)	H22B—C22—H22C	109.5
O7—C9—C8	108.7 (3)	O6—C23—O5	123.1 (5)
O10—C9—H9	110.8	O6—C23—C24	126.8 (5)
O7—C9—H9	110.8	O5—C23—C24	110.1 (5)
C8—C9—H9	110.8	C23—C24—H24A	109.5
O10—C11—C12	106.0 (3)	C23—C24—H24B	109.5
O10—C11—H11A	110.5	H24A—C24—H24B	109.5
C12—C11—H11A	110.5	C23—C24—H24C	109.5
O10—C11—H11B	110.5	H24A—C24—H24C	109.5
C12—C11—H11B	110.5	H24B—C24—H24C	109.5
H11A—C11—H11B	108.7	O8—C25—O7	123.7 (4)
C4—C12—C11	114.3 (3)	O8'—C25—O7	110.6 (10)
C4—C12—C8	114.2 (3)	O8—C25—C26	124.7 (4)
C11—C12—C8	100.6 (3)	O8'—C25—C26	119.4 (11)
C4—C12—C13	106.9 (3)	O7—C25—C26	111.3 (4)
C11—C12—C13	107.1 (3)	C25—C26—H26A	109.5
C8—C12—C13	113.7 (3)	C25—C26—H26B	109.5
C14—C13—C12	117.5 (3)	H26A—C26—H26B	109.5
C14—C13—C1	112.3 (3)	C25—C26—H26C	109.5
C12—C13—C1	109.1 (3)	H26A—C26—H26C	109.5
C14—C13—H13	105.7	H26B—C26—H26C	109.5
C12—C13—H13	105.7
C4—O3—C2—O4	−179.9 (3)	C4—C12—C13—C1	−44.2 (3)
C4—O3—C2—C1	0.6 (4)	C11—C12—C13—C1	78.7 (3)
C18—C1—C2—O4	−33.5 (5)	C8—C12—C13—C1	−171.1 (3)
C19—C1—C2—O4	77.7 (4)	C2—C1—C13—C14	−132.9 (3)
C13—C1—C2—O4	−153.8 (3)	C18—C1—C13—C14	103.5 (3)
C18—C1—C2—O3	146.1 (3)	C19—C1—C13—C14	−3.2 (4)
C19—C1—C2—O3	−102.8 (3)	C2—C1—C13—C12	−0.8 (4)
C13—C1—C2—O3	25.7 (4)	C18—C1—C13—C12	−124.4 (3)
C2—O3—C4—C5	−174.9 (3)	C19—C1—C13—C12	128.9 (3)
C2—O3—C4—C12	−50.3 (4)	C12—C13—C14—O2	−54.3 (4)
O3—C4—C5—C6	174.6 (3)	C1—C13—C14—O2	73.4 (3)
C12—C4—C5—C6	54.0 (4)	C12—C13—C14—C15	−177.2 (3)
C4—C5—C6—C7	−64.5 (4)	C1—C13—C14—C15	−49.5 (4)
C5—C6—C7—C21	176.4 (3)	O2—C14—C15—C16	−84.4 (4)
C5—C6—C7—C22	−67.0 (4)	C13—C14—C15—C16	40.1 (4)
C5—C6—C7—C8	60.3 (4)	C14—C15—C16—C17	−89.6 (4)
C6—C7—C8—C9	−161.7 (3)	C14—C15—C16—C19	22.6 (4)
C21—C7—C8—C9	80.8 (4)	C19—C16—C17—C20	150.7 (4)
C22—C7—C8—C9	−37.6 (4)	C15—C16—C17—C20	−93.1 (5)
C6—C7—C8—C12	−46.2 (4)	C19—C16—C17—C18	−26.5 (3)
C21—C7—C8—C12	−163.7 (3)	C15—C16—C17—C18	89.7 (4)
C22—C7—C8—C12	78.0 (4)	C20—C17—C18—O1	3.6 (6)
C11—O10—C9—O7	−103.6 (3)	C16—C17—C18—O1	−178.9 (4)
C11—O10—C9—C8	13.5 (4)	C20—C17—C18—C1	179.9 (4)
C25—O7—C9—O10	−105.0 (4)	C16—C17—C18—C1	−2.6 (4)
C25—O7—C9—C8	138.8 (3)	C2—C1—C18—O1	−35.2 (5)
C12—C8—C9—O10	−31.5 (3)	C19—C1—C18—O1	−153.9 (4)
C7—C8—C9—O10	92.2 (3)	C13—C1—C18—O1	92.5 (4)
C12—C8—C9—O7	85.3 (3)	C2—C1—C18—C17	148.5 (3)
C7—C8—C9—O7	−151.0 (3)	C19—C1—C18—C17	29.8 (3)
C9—O10—C11—C12	10.7 (4)	C13—C1—C18—C17	−83.8 (3)
O3—C4—C12—C11	−45.8 (4)	C23—O5—C19—C16	−155.6 (3)
C5—C4—C12—C11	73.3 (4)	C23—O5—C19—C1	96.1 (4)
O3—C4—C12—C8	−160.9 (3)	C17—C16—C19—O5	−69.0 (3)
C5—C4—C12—C8	−41.8 (4)	C15—C16—C19—O5	171.5 (3)
O3—C4—C12—C13	72.4 (3)	C17—C16—C19—C1	44.7 (3)
C5—C4—C12—C13	−168.4 (3)	C15—C16—C19—C1	−74.8 (3)
O10—C11—C12—C4	−152.1 (3)	C2—C1—C19—O5	−51.6 (4)
O10—C11—C12—C8	−29.3 (3)	C18—C1—C19—O5	66.2 (3)
O10—C11—C12—C13	89.8 (3)	C13—C1—C19—O5	175.9 (3)
C9—C8—C12—C4	158.8 (3)	C2—C1—C19—C16	−163.6 (3)
C7—C8—C12—C4	37.6 (4)	C18—C1—C19—C16	−45.9 (3)
C9—C8—C12—C11	35.9 (3)	C13—C1—C19—C16	63.8 (3)
C7—C8—C12—C11	−85.3 (3)	C19—O5—C23—O6	4.7 (6)
C9—C8—C12—C13	−78.2 (3)	C19—O5—C23—C24	−174.7 (3)
C7—C8—C12—C13	160.6 (3)	C9—O7—C25—O8	6.5 (8)
C4—C12—C13—C14	85.1 (3)	C9—O7—C25—O8'	−44.3 (15)
C11—C12—C13—C14	−152.0 (3)	C9—O7—C25—C26	−179.5 (3)
C8—C12—C13—C14	−41.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4^i	0.82	2.37	2.873 (3)	120

Symmetry code: (i) x−1, y, z.