Desacetyl epicaryoptin

The title compound, C₂₀H₃₀O₆, is a semisynthetic derivative of a diterpene, 3-epicaryoptin, isolated from Clerodendron calamitosum. The two fused cyclo­hexane rings adopt chair conformations and the two fused five-membered rings adopt an envelope and a planar conformation. The O atoms of the hydr­oxy groups participate in hydrogen bonding and R₂¹(6) and R₂²(4) ring motifs are formed in the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.051
• wR factor = 0.148
• Data-to-parameter ratio = 12.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT417_ALERT_2_B Short Inter D-H..H-D       H6A    ..  H18     ..       1.43 Ang.

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.55 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.37 Ratio
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.07
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5
PLAT410_ALERT_2_C Short Intra H...H Contact  H6     ..  H17A    ..       1.98 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           30.00
           From the CIF: _reflns_number_total               2972
           Count of symmetry unique reflns         2978
           Completeness (_total/calc)             99.80%
           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
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C5     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C6     = .          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 C10    = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C11    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C13    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C16    = .          S

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

  13 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 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

The fused cyclo hexane rings A and B adopt chair conformations, as evident from the ring puckering parameters (Cremer & Pople, 1975) [Q_T =0.604 (3) Å, φ₂ =-131.7(2.5)°, q₂ =0.091 (3)Å for ring A; Q_T =0.544 (3) Å, φ₂ =106.2(3.7)°, q₂ =0.054 (3)Å for ring B]. Ring C adopts an envelope conformation [φ₂=7.5 (5)°, q₂ =0.385 (3) Å] with apex at C11 which lies 0.581 (3)Å from the plane of the remaining four atoms. Ring D exists in a planar conformation with a maximum deviation -0.025 (3)Å for atom C16 from the plane formed by other atoms. Rings A/B and C/D are trans and cis fused as seen from the endocyclic dihedral angles of the ring junction atoms. The orientation of hydroxyl group at C3, C7 and C18 are in +ac (C1—C2—C3—O3 = 173.8 (4) °), +sc(C4—C5—C6—O6 = 70.8 (3)°) and +sc(C6—C5—C18—O18 = 78.1 (4) °) respectively (Klyne & Prelog, 1960). The intact epoxide ring at C4 is in ap conformation with respect to ring A (C2—C3—C4—O4 is 159.5 (3)). The orientation of furofuran at C9 is in -sc conformation with respect to ring B (C8—C9—C11—C12 is -77.1 (4)))°.

The molecules (Fig.2) in the crystal lattice are linked by intermolecular O—H···O hydrogen bonds (Table 2). The hydroxyl oxygen O3 acts as donor for the epoxide oxygen O4 and the hydroxyl group O6 forming a bifurcated hydrogen bond which generates a ring motif R₂¹(6) along 'c' axis. The tandem hydrogen bond configuration formed by the hydroxyl oxygen atoms, O6 and O18, act as hydrogen bond donors and acceptors, generating a ring motif R₂²(4) parallel to 'b' axis (Bernstein et al., 1995).

Related literature

For related literature, see: Bernstein et al. (1995); Cremer & Pople (1975); De la Torre et al. (1994); Klyne & Prelog (1960); Rodriguez et al. (1994); Rogers et al. (1979).

S2. Experimental

3-Epicaryoptin (50 mg) in MeOH (15 ml) and water (20 ml) was treated with KOH (70 mg) and refluxed on a water bath for 20 min. The crystalline product was filtered and was subjected to column chromatography resulting in compound (I). Rhombohedral shaped crystals were obtained from a mixture of three solvents viz., carbon tetrachloride, chloroform and methanol in the ratio 2:1:1 at room temperature (293 K).

S3. Refinement

In the absence of suitable anomalous scatters, Friedel equivalents could not be used to determine the absolute structure. Therefore, 1990 Friedel equivalents were merged before the final refinement. The enantiomer employed in the refined model was chosen to agree with the accepted configuration of diterpenes (Rogers et al., 1979; Rodriguez et al., 1994; De la Torre et al., 1994). The C—H and CH₂ atoms were constrained to an ideal geometry (C—H = 0.98, CH₂ = 0.97, O—H = 0.82 A°) with U_iso(H) = 1.2U_eq(parent atom), but where allowed to rotate freely about the C—C and C—O bonds, respectively. The remaining CH₃ and O—H hydrogen atoms were placed in geometrically idelaized positions (C—H = 0.97–0.98 Å) and constrained to ride on their parent atom with U_iso(H) = 1.5 U_eq(C).

Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 and PARST97 (Nardelli, 1995).

Figures

	Fig. 1. Molecular structure of the compound with 30% probability displacement ellipsoids and atomic numbering scheme.
	Fig. 2. A view of the crystal packing of (I), showing ring motifs R2^1(6) and R2^2(4). The molecules labeled with (*, $, #) correspond to symmetry positions (x, y, z), (x - 1/2, -y + 3/2, -z + 2) (x, y - 1/2, z) respectively.

Desacetyl epicaryoptin

Crystal data

C20H30O6	F(000) = 792
Mr = 366.44	Dx = 1.379 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 6.643 (5) Å	θ = 1.2–30.0°
b = 7.997 (3) Å	µ = 0.10 mm^−1
c = 33.230 (8) Å	T = 293 K
V = 1765.3 (15) Å^3	Rhombohedral, colourless
Z = 4	0.27 × 0.25 × 0.21 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	1723 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
Graphite monochromator	θmax = 30.0°, θmin = 1.2°
ω scans	h = 0→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = 0→11
Tmin = 0.973, Tmax = 0.979	l = −1→46
3065 measured reflections	3 standard reflections every 120 reflections
2972 independent reflections	intensity decay: 2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.077P)^2] where P = (Fo^2 + 2Fc^2)/3
2972 reflections	(Δ/σ)max < 0.001
240 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−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
C1	0.2940 (6)	0.5989 (4)	0.86301 (9)	0.0307 (8)
H1A	0.3183	0.6136	0.8344	0.037*
H1B	0.1807	0.5234	0.8660	0.037*
C2	0.2405 (7)	0.7668 (5)	0.88147 (10)	0.0418 (10)
H2A	0.3436	0.8475	0.8744	0.050*
H2B	0.1143	0.8052	0.8701	0.050*
C3	0.2208 (7)	0.7607 (4)	0.92697 (10)	0.0394 (9)
H3	0.1036	0.6932	0.9345	0.047*
C4	0.4105 (6)	0.6819 (4)	0.94354 (8)	0.0300 (8)
C5	0.4480 (5)	0.5003 (4)	0.92903 (8)	0.0242 (7)
C6	0.6390 (6)	0.4256 (4)	0.94735 (9)	0.0317 (8)
H6	0.7477	0.5077	0.9447	0.038*
C7	0.7023 (6)	0.2675 (4)	0.92603 (10)	0.0358 (8)
H7A	0.5965	0.1848	0.9289	0.043*
H7B	0.8221	0.2237	0.9389	0.043*
C8	0.7456 (6)	0.2928 (4)	0.88144 (10)	0.0339 (8)
H8	0.8531	0.3764	0.8795	0.041*
C9	0.5601 (5)	0.3649 (4)	0.85866 (8)	0.0247 (7)
C10	0.4800 (5)	0.5200 (4)	0.88236 (8)	0.0225 (7)
H10	0.5859	0.6045	0.8796	0.027*
C11	0.6397 (5)	0.4177 (4)	0.81656 (9)	0.0277 (7)
H11	0.7246	0.3262	0.8067	0.033*
C12	0.7590 (6)	0.5775 (4)	0.81173 (9)	0.0347 (8)
H12A	0.8959	0.5641	0.8214	0.042*
H12B	0.6958	0.6695	0.8259	0.042*
C13	0.7541 (5)	0.6050 (4)	0.76640 (9)	0.0322 (8)
H13	0.7524	0.7240	0.7593	0.039*
C14	0.9089 (7)	0.5105 (6)	0.74327 (11)	0.0449 (10)
H14	1.0469	0.5297	0.7442	0.054*
C15	0.8209 (7)	0.3971 (6)	0.72157 (11)	0.0465 (11)
H15	0.8930	0.3242	0.7052	0.056*
C16	0.5590 (6)	0.5156 (5)	0.75390 (9)	0.0325 (8)
H16	0.4629	0.5952	0.7424	0.039*
C17	0.5750 (7)	0.7929 (5)	0.95490 (11)	0.0439 (10)
H17A	0.7114	0.7510	0.9523	0.053*
H17B	0.5592	0.9115	0.9496	0.053*
C18	0.2661 (6)	0.3910 (4)	0.94037 (9)	0.0344 (8)
H18A	0.1555	0.4148	0.9222	0.041*
H18B	0.3017	0.2741	0.9374	0.041*
C19	0.3977 (6)	0.2313 (4)	0.85247 (10)	0.0340 (8)
H19A	0.3441	0.1983	0.8781	0.051*
H19B	0.4556	0.1358	0.8393	0.051*
H19C	0.2915	0.2760	0.8361	0.051*
C20	0.8302 (8)	0.1290 (5)	0.86471 (13)	0.0572 (12)
H20A	0.8594	0.1422	0.8366	0.086*
H20B	0.7329	0.0414	0.8682	0.086*
H20C	0.9515	0.1005	0.8789	0.086*
O3	0.1930 (6)	0.9273 (3)	0.93974 (8)	0.0604 (10)
H3A	0.1624	0.9283	0.9636	0.091*
O4	0.4475 (5)	0.7183 (3)	0.98515 (7)	0.0432 (7)
O6	0.6073 (5)	0.3942 (3)	0.98937 (6)	0.0491 (8)
H6A	0.6489	0.3006	0.9950	0.074*
O11	0.4785 (4)	0.4392 (3)	0.78776 (6)	0.0337 (6)
O16	0.6173 (4)	0.3914 (3)	0.72424 (7)	0.0431 (7)
O18	0.2036 (5)	0.4212 (3)	0.98069 (7)	0.0519 (8)
H18	0.1107	0.3580	0.9864	0.078*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
c1	0.0370 (19)	0.0368 (17)	0.0183 (14)	0.0102 (18)	0.0001 (14)	−0.0005 (14)
c2	0.062 (3)	0.040 (2)	0.0230 (15)	0.025 (2)	−0.0049 (17)	0.0028 (14)
c3	0.053 (2)	0.0356 (18)	0.0295 (17)	0.013 (2)	0.0040 (18)	−0.0012 (15)
c4	0.049 (2)	0.0262 (15)	0.0148 (13)	0.0020 (17)	0.0010 (15)	0.0007 (12)
c5	0.0351 (18)	0.0207 (13)	0.0169 (12)	0.0012 (16)	−0.0008 (13)	0.0011 (11)
c6	0.043 (2)	0.0298 (17)	0.0227 (15)	0.0002 (18)	−0.0055 (15)	0.0030 (13)
c7	0.047 (2)	0.0330 (17)	0.0274 (16)	0.0126 (19)	−0.0032 (17)	0.0050 (14)
c8	0.038 (2)	0.0328 (17)	0.0305 (16)	0.0051 (18)	0.0044 (16)	0.0039 (14)
c9	0.0312 (17)	0.0234 (14)	0.0196 (13)	−0.0018 (15)	0.0024 (14)	0.0012 (12)
c10	0.0292 (17)	0.0232 (15)	0.0150 (11)	0.0001 (14)	−0.0001 (12)	0.0011 (11)
c11	0.0305 (19)	0.0312 (17)	0.0214 (14)	0.0001 (17)	0.0043 (13)	−0.0014 (13)
c12	0.039 (2)	0.0412 (19)	0.0242 (15)	−0.009 (2)	0.0024 (15)	−0.0012 (14)
c13	0.040 (2)	0.0289 (16)	0.0275 (15)	−0.0004 (18)	0.0092 (15)	0.0046 (14)
c14	0.043 (2)	0.057 (3)	0.0343 (17)	0.000 (2)	0.0099 (18)	0.0025 (19)
c15	0.054 (3)	0.055 (3)	0.0300 (18)	0.009 (2)	0.0130 (18)	−0.0013 (19)
c16	0.040 (2)	0.0360 (19)	0.0214 (14)	−0.0018 (19)	0.0030 (16)	0.0033 (14)
c17	0.061 (3)	0.0295 (18)	0.041 (2)	−0.010 (2)	0.000 (2)	−0.0037 (15)
c18	0.048 (2)	0.0335 (17)	0.0217 (14)	−0.004 (2)	0.0034 (16)	−0.0009 (14)
c19	0.045 (2)	0.0267 (16)	0.0302 (16)	−0.0094 (17)	0.0087 (16)	−0.0051 (13)
c20	0.072 (3)	0.055 (3)	0.045 (2)	0.030 (3)	0.006 (2)	0.001 (2)
o3	0.110 (3)	0.0377 (14)	0.0333 (13)	0.0339 (18)	0.0031 (17)	−0.0041 (12)
o4	0.073 (2)	0.0354 (14)	0.0212 (11)	−0.0002 (16)	−0.0067 (13)	−0.0045 (10)
o6	0.088 (2)	0.0416 (15)	0.0182 (11)	0.0190 (18)	−0.0095 (13)	0.0028 (11)
o11	0.0348 (14)	0.0452 (14)	0.0210 (10)	−0.0094 (13)	−0.0006 (10)	0.0038 (10)
o16	0.0570 (18)	0.0453 (16)	0.0269 (12)	−0.0074 (15)	0.0028 (12)	−0.0075 (12)
o18	0.080 (2)	0.0420 (16)	0.0335 (13)	−0.0132 (17)	0.0272 (14)	0.0000 (12)

Geometric parameters (Å, º)

C1—C2	1.519 (5)	C11—C12	1.512 (5)
C1—C10	1.529 (5)	C11—H11	0.9800
C1—H1A	0.9700	C12—C13	1.523 (4)
C1—H1B	0.9700	C12—H12A	0.9700
C2—C3	1.518 (5)	C12—H12B	0.9700
C2—H2A	0.9700	C13—C14	1.490 (5)
C2—H2B	0.9700	C13—C16	1.538 (5)
C3—O3	1.410 (4)	C13—H13	0.9800
C3—C4	1.513 (6)	C14—C15	1.298 (6)
C3—H3	0.9800	C14—H14	0.9300
C4—O4	1.434 (4)	C15—O16	1.356 (5)
C4—C17	1.458 (5)	C15—H15	0.9300
C4—C5	1.550 (5)	C16—O11	1.387 (4)
C5—C6	1.529 (5)	C16—O16	1.452 (4)
C5—C18	1.538 (5)	C16—H16	0.9800
C5—C10	1.573 (4)	C17—O4	1.444 (5)
C6—O6	1.434 (4)	C17—H17A	0.9700
C6—C7	1.509 (5)	C17—H17B	0.9700
C6—H6	0.9800	C18—O18	1.423 (4)
C7—C8	1.523 (4)	C18—H18A	0.9700
C7—H7A	0.9700	C18—H18B	0.9700
C7—H7B	0.9700	C19—H19A	0.9600
C8—C20	1.530 (5)	C19—H19B	0.9600
C8—C9	1.557 (5)	C19—H19C	0.9600
C8—H8	0.9800	C20—H20A	0.9600
C9—C19	1.532 (5)	C20—H20B	0.9600
C9—C11	1.554 (4)	C20—H20C	0.9600
C9—C10	1.562 (4)	O3—H3A	0.8200
C10—H10	0.9800	O6—H6A	0.8200
C11—O11	1.447 (4)	O18—H18	0.8200
C2—C1—C10	112.6 (3)	O11—C11—C12	102.5 (3)
C2—C1—H1A	109.1	O11—C11—C9	112.1 (3)
C10—C1—H1A	109.1	C12—C11—C9	120.2 (3)
C2—C1—H1B	109.1	O11—C11—H11	107.1
C10—C1—H1B	109.1	C12—C11—H11	107.1
H1A—C1—H1B	107.8	C9—C11—H11	107.1
C3—C2—C1	113.2 (3)	C11—C12—C13	102.5 (3)
C3—C2—H2A	108.9	C11—C12—H12A	111.3
C1—C2—H2A	108.9	C13—C12—H12A	111.3
C3—C2—H2B	108.9	C11—C12—H12B	111.3
C1—C2—H2B	108.9	C13—C12—H12B	111.3
H2A—C2—H2B	107.8	H12A—C12—H12B	109.2
O3—C3—C4	113.1 (3)	C14—C13—C12	115.0 (3)
O3—C3—C2	106.3 (3)	C14—C13—C16	101.9 (3)
C4—C3—C2	107.7 (3)	C12—C13—C16	102.6 (3)
O3—C3—H3	109.9	C14—C13—H13	112.2
C4—C3—H3	109.9	C12—C13—H13	112.2
C2—C3—H3	109.9	C16—C13—H13	112.2
O4—C4—C17	59.9 (2)	C15—C14—C13	109.3 (4)
O4—C4—C3	114.1 (3)	C15—C14—H14	125.4
C17—C4—C3	117.7 (3)	C13—C14—H14	125.4
O4—C4—C5	117.6 (3)	C14—C15—O16	115.9 (4)
C17—C4—C5	122.1 (3)	C14—C15—H15	122.1
C3—C4—C5	114.3 (3)	O16—C15—H15	122.1
C6—C5—C18	109.4 (3)	O11—C16—O16	110.6 (3)
C6—C5—C4	112.0 (3)	O11—C16—C13	108.1 (3)
C18—C5—C4	109.3 (3)	O16—C16—C13	106.0 (3)
C6—C5—C10	108.6 (3)	O11—C16—H16	110.6
C18—C5—C10	113.9 (3)	O16—C16—H16	110.6
C4—C5—C10	103.6 (2)	C13—C16—H16	110.6
O6—C6—C7	110.6 (3)	O4—C17—C4	59.3 (2)
O6—C6—C5	109.5 (3)	O4—C17—H17A	117.8
C7—C6—C5	111.8 (3)	C4—C17—H17A	117.8
O6—C6—H6	108.3	O4—C17—H17B	117.8
C7—C6—H6	108.3	C4—C17—H17B	117.8
C5—C6—H6	108.3	H17A—C17—H17B	115.0
C6—C7—C8	113.5 (3)	O18—C18—C5	111.3 (3)
C6—C7—H7A	108.9	O18—C18—H18A	109.4
C8—C7—H7A	108.9	C5—C18—H18A	109.4
C6—C7—H7B	108.9	O18—C18—H18B	109.4
C8—C7—H7B	108.9	C5—C18—H18B	109.4
H7A—C7—H7B	107.7	H18A—C18—H18B	108.0
C7—C8—C20	108.0 (3)	C9—C19—H19A	109.5
C7—C8—C9	111.9 (3)	C9—C19—H19B	109.5
C20—C8—C9	115.6 (3)	H19A—C19—H19B	109.5
C7—C8—H8	107.0	C9—C19—H19C	109.5
C20—C8—H8	107.0	H19A—C19—H19C	109.5
C9—C8—H8	107.0	H19B—C19—H19C	109.5
C19—C9—C11	108.0 (2)	C8—C20—H20A	109.5
C19—C9—C8	111.4 (3)	C8—C20—H20B	109.5
C11—C9—C8	105.6 (3)	H20A—C20—H20B	109.5
C19—C9—C10	112.4 (3)	C8—C20—H20C	109.5
C11—C9—C10	110.7 (2)	H20A—C20—H20C	109.5
C8—C9—C10	108.6 (2)	H20B—C20—H20C	109.5
C1—C10—C9	113.0 (2)	C3—O3—H3A	109.5
C1—C10—C5	110.3 (3)	C4—O4—C17	60.9 (2)
C9—C10—C5	117.6 (2)	C6—O6—H6A	109.5
C1—C10—H10	104.9	C16—O11—C11	107.7 (3)
C9—C10—H10	104.9	C15—O16—C16	106.7 (3)
C5—C10—H10	104.9	C18—O18—H18	109.5
C10—C1—C2—C3	−52.8 (5)	C11—C9—C10—C5	−164.0 (3)
C1—C2—C3—O3	173.8 (4)	C8—C9—C10—C5	−48.5 (4)
C1—C2—C3—C4	52.2 (5)	C6—C5—C10—C1	−178.5 (3)
O3—C3—C4—O4	42.3 (4)	C18—C5—C10—C1	59.4 (4)
C2—C3—C4—O4	159.5 (3)	C4—C5—C10—C1	−59.2 (3)
O3—C3—C4—C17	−25.0 (4)	C6—C5—C10—C9	50.0 (4)
C2—C3—C4—C17	92.2 (4)	C18—C5—C10—C9	−72.2 (4)
O3—C3—C4—C5	−178.4 (3)	C4—C5—C10—C9	169.2 (3)
C2—C3—C4—C5	−61.2 (4)	C19—C9—C11—O11	43.2 (3)
O4—C4—C5—C6	−41.0 (4)	C8—C9—C11—O11	162.4 (3)
C17—C4—C5—C6	29.1 (4)	C10—C9—C11—O11	−80.3 (3)
C3—C4—C5—C6	−178.8 (3)	C19—C9—C11—C12	163.7 (3)
O4—C4—C5—C18	80.4 (4)	C8—C9—C11—C12	−77.1 (4)
C17—C4—C5—C18	150.5 (3)	C10—C9—C11—C12	40.2 (4)
C3—C4—C5—C18	−57.4 (3)	O11—C11—C12—C13	−39.6 (3)
O4—C4—C5—C10	−157.9 (3)	C9—C11—C12—C13	−164.7 (3)
C17—C4—C5—C10	−87.8 (3)	C11—C12—C13—C14	−83.3 (4)
C3—C4—C5—C10	64.3 (4)	C11—C12—C13—C16	26.4 (3)
C18—C5—C6—O6	−50.6 (3)	C12—C13—C14—C15	111.9 (4)
C4—C5—C6—O6	70.8 (3)	C16—C13—C14—C15	1.8 (4)
C10—C5—C6—O6	−175.4 (3)	C13—C14—C15—O16	0.8 (5)
C18—C5—C6—C7	72.3 (3)	C14—C13—C16—O11	115.3 (3)
C4—C5—C6—C7	−166.3 (3)	C12—C13—C16—O11	−4.0 (4)
C10—C5—C6—C7	−52.5 (4)	C14—C13—C16—O16	−3.4 (3)
O6—C6—C7—C8	−178.0 (3)	C12—C13—C16—O16	−122.7 (3)
C5—C6—C7—C8	59.6 (4)	C3—C4—C17—O4	103.3 (3)
C6—C7—C8—C20	173.7 (4)	C5—C4—C17—O4	−105.5 (3)
C6—C7—C8—C9	−58.0 (4)	C6—C5—C18—O18	77.7 (4)
C7—C8—C9—C19	−74.5 (4)	C4—C5—C18—O18	−45.3 (4)
C20—C8—C9—C19	49.6 (4)	C10—C5—C18—O18	−160.6 (3)
C7—C8—C9—C11	168.6 (3)	C3—C4—O4—C17	−109.2 (3)
C20—C8—C9—C11	−67.3 (4)	C5—C4—O4—C17	112.9 (4)
C7—C8—C9—C10	49.8 (4)	O16—C16—O11—C11	94.1 (3)
C20—C8—C9—C10	173.9 (3)	C13—C16—O11—C11	−21.6 (4)
C2—C1—C10—C9	−169.3 (3)	C12—C11—O11—C16	38.7 (3)
C2—C1—C10—C5	56.8 (4)	C9—C11—O11—C16	169.0 (3)
C19—C9—C10—C1	−55.1 (3)	C14—C15—O16—C16	−3.1 (5)
C11—C9—C10—C1	65.7 (4)	O11—C16—O16—C15	−113.0 (3)
C8—C9—C10—C1	−178.8 (3)	C13—C16—O16—C15	4.0 (4)
C19—C9—C10—C5	75.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O4^i	0.82	2.51	3.201 (4)	142
O3—H3A···O6^i	0.82	2.14	2.813 (3)	139
O6—H6A···O18^ii	0.82	1.98	2.786 (4)	166
O18—H18···O6^iii	0.82	2.17	2.786 (4)	132

Symmetry codes: (i) x−1/2, −y+3/2, −z+2; (ii) x+1/2, −y+1/2, −z+2; (iii) x−1/2, −y+1/2, −z+2.