(9R,15R)-Methyl 3,15-diacetyl-4-(2-cyano­ethyl)-4,9,10-trimethyl­perhydro­cyclo­penta­[a]phenanthrene-13-carboxyl­ate

The title compound, C₂₉H₄₃NO₄, a seco-lupane triterpene, was synthesized from naturally occurring betulin. In the mol­ecule, all bond lengths and angles are normal. The crystal structure is stabilized by weak inter­molecular C—H...O hydrogen bonds and ordinary van der Waals inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.036
• wR factor = 0.075
• Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level C
STRVA01_ALERT_4_C           Flack test results are meaningless.
           From the CIF: _refine_ls_abs_structure_Flack    0.000
           From the CIF: _refine_ls_abs_structure_Flack_su   10.000
PLAT032_ALERT_4_C Std. Uncertainty in Flack Parameter too High ...      10.00
PLAT412_ALERT_2_C Short Intra XH3 .. XHn     H9A    ..  H26B    ..       1.85 Ang.
PLAT850_ALERT_2_C Check Flack Parameter Exact Value 0.00 and su ..      10.00

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           30.11
           From the CIF: _reflns_number_total               3928
           Count of symmetry unique reflns         3963
           Completeness (_total/calc)             99.12%
           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 C5     = .          R
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 C13    = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C14    = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C17    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C18    = .          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
   4 ALERT level C = Check and explain
  10 ALERT level G = General alerts; check

   9 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
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

In the last decade, the real burst of activity in the pharmacological properties of lupane triterpenoids was observed after revealing promising antiviral and antineoplastic agents among these compounds (Tolstikova et al., 2006; Krasutsky, 2006). The influence of A-ring modification in lupane series on the increasing of anti-cancer activity has been shown (Urban et al., 2005). In this connection design and synthesis of new seco-lupane triterpenoids is of great interest. Herein we report the crystal structure of the title compound, (I), which was synthesized via ozonolysis of 3-cyano-3,4-seco-4(23),20 (29)-lupdiene-28-oic acid methyl ester described by Valterova et al. (1983).

In (I) (Fig.1), all bond lengths and angles show normal values (Allen et al., 1987; CSD, Version 5.27, Allen, 2002). The cyclohexane rings adopt a chair conformation. The five-membered cycle is characterized by envelope conformation with the C17 atom being displaced from C18—C19—C21—C22 plane so that the C17—C18—C19—C21 and C19—C21—C22—C17 torsion angles are equal to 26.4 (2) and -27.3 (2)° correspondingly. The value of the C22—C21—C19—C20 torsion angle which describes the orientation of the acetyl group is equal to -120.4 (2)°. The acetyl group attached to the C5 atom adopts the equatorial position as well as the cyanoethyl substituent attached to the C10 atom.

The crystal packing is stabilized by the weak intermolecular C–H···O hydrogen bonds (Table 1) and ordinary Van der Waals interactions.

Related literature

For related literature, see: Allen (2002); Allen et al. (1987); Krasutsky (2006); Tolstikova et al. (2006); Urban et al. (2005); Valterova et al. (1983).

S2. Experimental

A solution of 3-cyano-3,4-seco-4(23),20 (29)-lupdiene-28-oic acid methyl ester (2 mmol, 0.94 g) (obtained as described by Valterova et al. (1983)) in CH₂Cl₂ (50 ml) was treated with ozone at 213 K. Then AcOH (10 ml) and Zn dust (1 g) were added at 273 K. After stirring for 1 h organic layer was filtered, washed by the saturated aqueous Na₂CO₃ (3×20 ml), H₂O (3×20 ml), dried over Na₂SO₄. The solvent was evaporated in vacuo. Crude material was subjected to column chromatography on silica gel and eluted with CHCl₃ to yield 0.65 g (70%) of the pure product which was crystallized from CHCl₃—MeOH for a few days to obtain colorless single crystals of (I) suitable for the X-ray analysis.

S3. Refinement

The H(C) atoms were positioned geometrically with C–H distances of 0.98Å for the mehtyl groups and 0.99Å for all the other hydrogen atoms. All the H atoms were refined within the riding model with U_iso(H)=1.5U_eq(parent atom) for the methyl groups and U_iso(H)=1.2U_eq(parent atom) for the other atoms. Due to the absence of any significant anomalous scatterers in the molecule, the 3429 Friedel pairs were merged before the final refinement.

Crystallographic data for (I) have been deposited with the Cambridge Crystallographic Data Centre (CCDC No. 630832).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. View of (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are presented as spheres of arbitrary radius.

(9R,15R)-Methyl 3,15-diacetyl-4-(2-cyanoethyl)-4,9,10- trimethylperhydrocyclopenta[a]phenanthrene-13-carboxylate

Crystal data

C29H43NO4	F(000) = 512
Mr = 469.64	Dx = 1.231 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 4959 reflections
a = 9.6438 (6) Å	θ = 2.3–29.4°
b = 8.9672 (5) Å	µ = 0.08 mm^−1
c = 15.0549 (9) Å	T = 100 K
β = 103.203 (1)°	Prism, colorless
V = 1267.50 (13) Å^3	0.35 × 0.25 × 0.20 mm
Z = 2

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer	3240 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.044
Graphite monochromator	θmax = 30.1°, θmin = 2.2°
φ and ω scans	h = −13→13
22169 measured reflections	k = −12→12
3928 independent reflections	l = −21→21

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)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.075	w = 1/[σ^2(Fo^2) + (0.034P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
3928 reflections	Δρmax = 0.28 e Å^−3
313 parameters	Δρmin = −0.16 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0 (10)

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	0.81804 (13)	0.42597 (15)	0.44072 (9)	0.0291 (3)
O2	−0.01272 (14)	0.91331 (16)	−0.01542 (8)	0.0284 (3)
O3	−0.08700 (14)	0.88309 (15)	0.32481 (9)	0.0290 (3)
O4	−0.04260 (14)	1.11365 (15)	0.38054 (9)	0.0254 (3)
N1	0.58447 (18)	0.2989 (2)	0.00197 (10)	0.0312 (4)
C1	0.56180 (17)	0.41733 (19)	0.21485 (10)	0.0168 (3)
H1A	0.6443	0.3509	0.2375	0.020*
H1B	0.4765	0.3531	0.1967	0.020*
C2	0.5850 (2)	0.4973 (2)	0.12878 (12)	0.0234 (4)
H2A	0.5073	0.5700	0.1072	0.028*
H2B	0.6763	0.5526	0.1435	0.028*
C3	0.58753 (19)	0.3876 (2)	0.05651 (12)	0.0228 (4)
C4	0.81035 (18)	0.5007 (2)	0.37217 (12)	0.0210 (4)
C5	0.68342 (17)	0.60158 (19)	0.33681 (11)	0.0168 (3)
H5A	0.7066	0.6631	0.2867	0.020*
C6	0.66693 (17)	0.70940 (19)	0.41249 (11)	0.0169 (3)
H6A	0.6377	0.6534	0.4619	0.020*
H6B	0.7596	0.7578	0.4385	0.020*
C7	0.55630 (17)	0.82771 (18)	0.37542 (11)	0.0162 (3)
H7A	0.5910	0.8890	0.3303	0.019*
H7B	0.5464	0.8942	0.4261	0.019*
C8	0.40807 (17)	0.76478 (18)	0.32973 (10)	0.0136 (3)
C9	0.42655 (17)	0.63972 (18)	0.25990 (11)	0.0143 (3)
H9A	0.4628	0.6940	0.2117	0.017*
C10	0.54217 (17)	0.51798 (18)	0.29564 (11)	0.0145 (3)
C11	0.28304 (17)	0.57591 (19)	0.20955 (11)	0.0179 (3)
H11A	0.2988	0.5012	0.1644	0.021*
H11B	0.2376	0.5246	0.2538	0.021*
C12	0.18349 (18)	0.69727 (19)	0.16060 (11)	0.0178 (3)
H12A	0.0894	0.6531	0.1331	0.021*
H12B	0.2228	0.7396	0.1108	0.021*
C13	0.16510 (17)	0.82152 (18)	0.22637 (11)	0.0148 (3)
H13A	0.1242	0.7750	0.2751	0.018*
C14	0.31060 (16)	0.89212 (18)	0.27426 (10)	0.0139 (3)
C15	0.28187 (18)	1.02064 (18)	0.33786 (11)	0.0169 (3)
H15A	0.2451	0.9768	0.3883	0.020*
H15B	0.3732	1.0706	0.3651	0.020*
C16	0.17522 (18)	1.13830 (19)	0.28897 (12)	0.0194 (4)
H16A	0.1607	1.2151	0.3332	0.023*
H16B	0.2136	1.1880	0.2410	0.023*
C17	0.03325 (17)	1.06386 (19)	0.24615 (12)	0.0176 (3)
C18	0.06059 (17)	0.94109 (19)	0.18050 (11)	0.0168 (3)
H18A	0.1074	0.9921	0.1360	0.020*
C19	−0.08772 (17)	0.8938 (2)	0.12546 (11)	0.0201 (3)
H19A	−0.1244	0.8084	0.1562	0.024*
C20	−0.09095 (18)	0.85498 (19)	0.02707 (12)	0.0210 (4)
C21	−0.1825 (2)	1.0356 (2)	0.12690 (14)	0.0275 (4)
H21A	−0.2235	1.0706	0.0640	0.033*
H21B	−0.2613	1.0130	0.1569	0.033*
C22	−0.08328 (19)	1.1552 (2)	0.18104 (13)	0.0239 (4)
H22A	−0.1353	1.2198	0.2157	0.029*
H22B	−0.0415	1.2181	0.1398	0.029*
C23	0.92889 (19)	0.5040 (2)	0.32213 (13)	0.0259 (4)
H23A	0.9981	0.4255	0.3460	0.039*
H23B	0.9762	0.6014	0.3309	0.039*
H23C	0.8895	0.4873	0.2569	0.039*
C24	0.50213 (17)	0.4071 (2)	0.36394 (11)	0.0181 (3)
H24A	0.5646	0.3197	0.3698	0.027*
H24B	0.4029	0.3757	0.3419	0.027*
H24C	0.5135	0.4554	0.4236	0.027*
C25	0.34075 (17)	0.7021 (2)	0.40602 (11)	0.0168 (3)
H25A	0.4138	0.6500	0.4514	0.025*
H25B	0.2644	0.6322	0.3795	0.025*
H25C	0.3015	0.7843	0.4355	0.025*
C26	0.38475 (18)	0.96652 (19)	0.20385 (11)	0.0178 (3)
H26A	0.3136	1.0193	0.1577	0.027*
H26B	0.4307	0.8896	0.1742	0.027*
H26C	0.4567	1.0375	0.2353	0.027*
C27	−0.03637 (17)	1.0043 (2)	0.32057 (12)	0.0200 (4)
C28	−0.1174 (2)	1.0780 (2)	0.45091 (13)	0.0275 (4)
H28A	−0.1034	1.1585	0.4961	0.041*
H28B	−0.0802	0.9845	0.4808	0.041*
H28C	−0.2193	1.0669	0.4235	0.041*
C29	−0.2014 (2)	0.7430 (2)	−0.01687 (13)	0.0277 (4)
H29A	−0.2181	0.7514	−0.0834	0.042*
H29B	−0.2904	0.7623	0.0021	0.042*
H29C	−0.1676	0.6422	0.0020	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0249 (7)	0.0290 (7)	0.0327 (7)	0.0033 (6)	0.0051 (6)	0.0120 (6)
O2	0.0330 (7)	0.0298 (7)	0.0219 (6)	−0.0016 (7)	0.0050 (6)	0.0015 (6)
O3	0.0333 (7)	0.0242 (7)	0.0345 (7)	−0.0056 (6)	0.0180 (6)	−0.0054 (6)
O4	0.0321 (7)	0.0211 (7)	0.0276 (7)	−0.0016 (6)	0.0163 (6)	−0.0035 (5)
N1	0.0383 (10)	0.0336 (10)	0.0241 (8)	0.0031 (8)	0.0121 (8)	−0.0035 (7)
C1	0.0196 (8)	0.0145 (8)	0.0172 (8)	0.0024 (7)	0.0062 (6)	0.0001 (7)
C2	0.0327 (10)	0.0205 (9)	0.0186 (8)	0.0027 (8)	0.0090 (7)	0.0002 (7)
C3	0.0252 (9)	0.0276 (10)	0.0175 (8)	0.0071 (8)	0.0090 (7)	0.0035 (8)
C4	0.0190 (8)	0.0182 (8)	0.0257 (9)	−0.0024 (7)	0.0051 (7)	−0.0020 (7)
C5	0.0160 (8)	0.0187 (8)	0.0164 (8)	0.0007 (7)	0.0050 (6)	0.0020 (7)
C6	0.0144 (8)	0.0188 (8)	0.0167 (8)	−0.0024 (7)	0.0017 (6)	−0.0007 (7)
C7	0.0176 (8)	0.0163 (8)	0.0148 (7)	−0.0026 (7)	0.0038 (6)	−0.0023 (7)
C8	0.0148 (8)	0.0144 (8)	0.0126 (7)	−0.0009 (6)	0.0046 (6)	−0.0011 (6)
C9	0.0168 (8)	0.0132 (8)	0.0132 (7)	0.0005 (6)	0.0042 (6)	−0.0004 (6)
C10	0.0158 (7)	0.0137 (8)	0.0146 (7)	0.0016 (6)	0.0045 (6)	0.0009 (6)
C11	0.0177 (8)	0.0159 (8)	0.0183 (8)	0.0028 (7)	0.0005 (7)	−0.0034 (7)
C12	0.0171 (8)	0.0175 (8)	0.0172 (8)	0.0019 (7)	0.0009 (7)	−0.0038 (7)
C13	0.0153 (8)	0.0138 (8)	0.0162 (7)	0.0007 (6)	0.0053 (6)	−0.0018 (6)
C14	0.0153 (7)	0.0132 (7)	0.0135 (7)	−0.0010 (6)	0.0039 (6)	−0.0024 (6)
C15	0.0197 (8)	0.0151 (8)	0.0168 (8)	−0.0006 (7)	0.0062 (7)	−0.0031 (7)
C16	0.0208 (9)	0.0155 (8)	0.0233 (9)	0.0001 (7)	0.0081 (7)	−0.0025 (7)
C17	0.0179 (8)	0.0144 (8)	0.0209 (8)	0.0005 (7)	0.0053 (7)	−0.0028 (7)
C18	0.0157 (8)	0.0171 (8)	0.0181 (8)	0.0020 (7)	0.0048 (6)	−0.0018 (7)
C19	0.0168 (8)	0.0203 (9)	0.0222 (8)	0.0045 (7)	0.0026 (7)	−0.0011 (7)
C20	0.0190 (8)	0.0194 (9)	0.0217 (8)	0.0072 (7)	−0.0015 (7)	0.0010 (7)
C21	0.0211 (9)	0.0275 (10)	0.0318 (10)	0.0083 (8)	0.0016 (8)	−0.0062 (8)
C22	0.0227 (9)	0.0201 (9)	0.0291 (10)	0.0063 (7)	0.0062 (8)	0.0010 (8)
C23	0.0207 (9)	0.0257 (9)	0.0323 (10)	0.0032 (8)	0.0079 (8)	−0.0006 (8)
C24	0.0180 (8)	0.0188 (8)	0.0177 (8)	−0.0007 (7)	0.0046 (6)	0.0032 (7)
C25	0.0191 (8)	0.0176 (8)	0.0156 (8)	−0.0012 (7)	0.0077 (7)	0.0002 (7)
C26	0.0186 (8)	0.0180 (8)	0.0186 (8)	0.0003 (7)	0.0076 (7)	0.0017 (7)
C27	0.0172 (8)	0.0205 (9)	0.0228 (9)	0.0032 (7)	0.0057 (7)	−0.0020 (7)
C28	0.0304 (10)	0.0292 (10)	0.0271 (10)	−0.0017 (9)	0.0157 (8)	−0.0041 (8)
C29	0.0277 (10)	0.0271 (10)	0.0260 (9)	0.0001 (8)	0.0015 (8)	−0.0047 (8)

Geometric parameters (Å, º)

O1—C4	1.219 (2)	C14—C26	1.558 (2)
O2—C20	1.213 (2)	C14—C15	1.563 (2)
O3—C27	1.199 (2)	C15—C16	1.538 (2)
O4—C27	1.344 (2)	C15—H15A	0.9900
O4—C28	1.447 (2)	C15—H15B	0.9900
N1—C3	1.139 (2)	C16—C17	1.527 (2)
C1—C2	1.542 (2)	C16—H16A	0.9900
C1—C10	1.560 (2)	C16—H16B	0.9900
C1—H1A	0.9900	C17—C27	1.528 (2)
C1—H1B	0.9900	C17—C18	1.542 (2)
C2—C3	1.471 (3)	C17—C22	1.546 (2)
C2—H2A	0.9900	C18—C19	1.540 (2)
C2—H2B	0.9900	C18—H18A	1.0000
C4—C23	1.506 (2)	C19—C20	1.515 (2)
C4—C5	1.517 (2)	C19—C21	1.569 (2)
C5—C6	1.530 (2)	C19—H19A	1.0000
C5—C10	1.554 (2)	C20—C29	1.503 (2)
C5—H5A	1.0000	C21—C22	1.540 (3)
C6—C7	1.518 (2)	C21—H21A	0.9900
C6—H6A	0.9900	C21—H21B	0.9900
C6—H6B	0.9900	C22—H22A	0.9900
C7—C8	1.545 (2)	C22—H22B	0.9900
C7—H7A	0.9900	C23—H23A	0.9800
C7—H7B	0.9900	C23—H23B	0.9800
C8—C25	1.548 (2)	C23—H23C	0.9800
C8—C9	1.575 (2)	C24—H24A	0.9800
C8—C14	1.589 (2)	C24—H24B	0.9800
C9—C11	1.529 (2)	C24—H24C	0.9800
C9—C10	1.565 (2)	C25—H25A	0.9800
C9—H9A	1.0000	C25—H25B	0.9800
C10—C24	1.542 (2)	C25—H25C	0.9800
C11—C12	1.525 (2)	C26—H26A	0.9800
C11—H11A	0.9900	C26—H26B	0.9800
C11—H11B	0.9900	C26—H26C	0.9800
C12—C13	1.528 (2)	C28—H28A	0.9800
C12—H12A	0.9900	C28—H28B	0.9800
C12—H12B	0.9900	C28—H28C	0.9800
C13—C18	1.525 (2)	C29—H29A	0.9800
C13—C14	1.558 (2)	C29—H29B	0.9800
C13—H13A	1.0000	C29—H29C	0.9800
C27—O4—C28	115.91 (14)	C14—C15—H15B	108.8
C2—C1—C10	116.92 (14)	H15A—C15—H15B	107.7
C2—C1—H1A	108.1	C17—C16—C15	109.82 (14)
C10—C1—H1A	108.1	C17—C16—H16A	109.7
C2—C1—H1B	108.1	C15—C16—H16A	109.7
C10—C1—H1B	108.1	C17—C16—H16B	109.7
H1A—C1—H1B	107.3	C15—C16—H16B	109.7
C3—C2—C1	109.90 (15)	H16A—C16—H16B	108.2
C3—C2—H2A	109.7	C16—C17—C27	110.18 (14)
C1—C2—H2A	109.7	C16—C17—C18	108.34 (13)
C3—C2—H2B	109.7	C27—C17—C18	112.85 (14)
C1—C2—H2B	109.7	C16—C17—C22	119.19 (14)
H2A—C2—H2B	108.2	C27—C17—C22	105.82 (13)
N1—C3—C2	176.7 (2)	C18—C17—C22	100.24 (13)
O1—C4—C23	121.87 (16)	C13—C18—C19	119.12 (14)
O1—C4—C5	120.88 (15)	C13—C18—C17	113.83 (13)
C23—C4—C5	117.17 (16)	C19—C18—C17	105.54 (13)
C4—C5—C6	109.15 (13)	C13—C18—H18A	105.8
C4—C5—C10	114.57 (14)	C19—C18—H18A	105.8
C6—C5—C10	111.78 (13)	C17—C18—H18A	105.8
C4—C5—H5A	107.0	C20—C19—C18	113.49 (13)
C6—C5—H5A	107.0	C20—C19—C21	108.51 (14)
C10—C5—H5A	107.0	C18—C19—C21	103.96 (14)
C7—C6—C5	110.60 (13)	C20—C19—H19A	110.2
C7—C6—H6A	109.5	C18—C19—H19A	110.2
C5—C6—H6A	109.5	C21—C19—H19A	110.2
C7—C6—H6B	109.5	O2—C20—C29	121.30 (16)
C5—C6—H6B	109.5	O2—C20—C19	122.69 (16)
H6A—C6—H6B	108.1	C29—C20—C19	115.98 (15)
C6—C7—C8	114.19 (13)	C22—C21—C19	106.17 (14)
C6—C7—H7A	108.7	C22—C21—H21A	110.5
C8—C7—H7A	108.7	C19—C21—H21A	110.5
C6—C7—H7B	108.7	C22—C21—H21B	110.5
C8—C7—H7B	108.7	C19—C21—H21B	110.5
H7A—C7—H7B	107.6	H21A—C21—H21B	108.7
C7—C8—C25	107.74 (13)	C21—C22—C17	103.90 (14)
C7—C8—C9	108.85 (12)	C21—C22—H22A	111.0
C25—C8—C9	111.53 (13)	C17—C22—H22A	111.0
C7—C8—C14	110.34 (12)	C21—C22—H22B	111.0
C25—C8—C14	110.66 (12)	C17—C22—H22B	111.0
C9—C8—C14	107.72 (12)	H22A—C22—H22B	109.0
C11—C9—C10	113.73 (13)	C4—C23—H23A	109.5
C11—C9—C8	111.70 (12)	C4—C23—H23B	109.5
C10—C9—C8	116.58 (13)	H23A—C23—H23B	109.5
C11—C9—H9A	104.4	C4—C23—H23C	109.5
C10—C9—H9A	104.4	H23A—C23—H23C	109.5
C8—C9—H9A	104.4	H23B—C23—H23C	109.5
C24—C10—C5	112.04 (13)	C10—C24—H24A	109.5
C24—C10—C1	103.90 (13)	C10—C24—H24B	109.5
C5—C10—C1	109.78 (12)	H24A—C24—H24B	109.5
C24—C10—C9	114.32 (12)	C10—C24—H24C	109.5
C5—C10—C9	106.93 (13)	H24A—C24—H24C	109.5
C1—C10—C9	109.83 (13)	H24B—C24—H24C	109.5
C12—C11—C9	111.78 (14)	C8—C25—H25A	109.5
C12—C11—H11A	109.3	C8—C25—H25B	109.5
C9—C11—H11A	109.3	H25A—C25—H25B	109.5
C12—C11—H11B	109.3	C8—C25—H25C	109.5
C9—C11—H11B	109.3	H25A—C25—H25C	109.5
H11A—C11—H11B	107.9	H25B—C25—H25C	109.5
C11—C12—C13	111.15 (13)	C14—C26—H26A	109.5
C11—C12—H12A	109.4	C14—C26—H26B	109.5
C13—C12—H12A	109.4	H26A—C26—H26B	109.5
C11—C12—H12B	109.4	C14—C26—H26C	109.5
C13—C12—H12B	109.4	H26A—C26—H26C	109.5
H12A—C12—H12B	108.0	H26B—C26—H26C	109.5
C18—C13—C12	112.46 (13)	O3—C27—O4	123.00 (15)
C18—C13—C14	110.86 (13)	O3—C27—C17	127.48 (16)
C12—C13—C14	111.76 (12)	O4—C27—C17	109.38 (15)
C18—C13—H13A	107.1	O4—C28—H28A	109.5
C12—C13—H13A	107.1	O4—C28—H28B	109.5
C14—C13—H13A	107.1	H28A—C28—H28B	109.5
C26—C14—C13	111.35 (12)	O4—C28—H28C	109.5
C26—C14—C15	105.92 (13)	H28A—C28—H28C	109.5
C13—C14—C15	108.43 (12)	H28B—C28—H28C	109.5
C26—C14—C8	110.92 (12)	C20—C29—H29A	109.5
C13—C14—C8	108.25 (12)	C20—C29—H29B	109.5
C15—C14—C8	111.97 (12)	H29A—C29—H29B	109.5
C16—C15—C14	113.91 (13)	C20—C29—H29C	109.5
C16—C15—H15A	108.8	H29A—C29—H29C	109.5
C14—C15—H15A	108.8	H29B—C29—H29C	109.5
C16—C15—H15B	108.8
C10—C1—C2—C3	−174.50 (15)	C7—C8—C14—C13	177.66 (12)
O1—C4—C5—C6	55.9 (2)	C25—C8—C14—C13	−63.19 (15)
C23—C4—C5—C6	−120.78 (17)	C9—C8—C14—C13	58.97 (14)
O1—C4—C5—C10	−70.3 (2)	C7—C8—C14—C15	−62.86 (15)
C23—C4—C5—C10	113.01 (17)	C25—C8—C14—C15	56.28 (17)
C4—C5—C6—C7	170.99 (13)	C9—C8—C14—C15	178.45 (12)
C10—C5—C6—C7	−61.22 (17)	C26—C14—C15—C16	65.12 (17)
C5—C6—C7—C8	57.12 (17)	C13—C14—C15—C16	−54.48 (17)
C6—C7—C8—C25	71.70 (16)	C8—C14—C15—C16	−173.85 (13)
C6—C7—C8—C9	−49.39 (17)	C14—C15—C16—C17	58.37 (18)
C6—C7—C8—C14	−167.39 (12)	C15—C16—C17—C27	66.66 (17)
C7—C8—C9—C11	−178.04 (13)	C15—C16—C17—C18	−57.24 (18)
C25—C8—C9—C11	63.23 (17)	C15—C16—C17—C22	−170.80 (13)
C14—C8—C9—C11	−58.39 (16)	C12—C13—C18—C19	51.31 (19)
C7—C8—C9—C10	48.85 (17)	C14—C13—C18—C19	177.25 (13)
C25—C8—C9—C10	−69.88 (17)	C12—C13—C18—C17	176.86 (14)
C14—C8—C9—C10	168.49 (12)	C14—C13—C18—C17	−57.21 (17)
C4—C5—C10—C24	56.14 (18)	C16—C17—C18—C13	59.01 (18)
C6—C5—C10—C24	−68.69 (17)	C27—C17—C18—C13	−63.27 (18)
C4—C5—C10—C1	−58.76 (17)	C22—C17—C18—C13	−175.40 (13)
C6—C5—C10—C1	176.41 (13)	C16—C17—C18—C19	−168.54 (14)
C4—C5—C10—C9	−177.86 (13)	C27—C17—C18—C19	69.18 (17)
C6—C5—C10—C9	57.31 (16)	C22—C17—C18—C19	−42.95 (16)
C2—C1—C10—C24	172.80 (14)	C13—C18—C19—C20	−86.52 (18)
C2—C1—C10—C5	−67.21 (18)	C17—C18—C19—C20	144.07 (15)
C2—C1—C10—C9	50.09 (18)	C13—C18—C19—C21	155.79 (15)
C11—C9—C10—C24	−60.36 (18)	C17—C18—C19—C21	26.38 (17)
C8—C9—C10—C24	71.84 (17)	C18—C19—C20—O2	−30.7 (2)
C11—C9—C10—C5	175.03 (13)	C21—C19—C20—O2	84.3 (2)
C8—C9—C10—C5	−52.78 (16)	C18—C19—C20—C29	151.45 (15)
C11—C9—C10—C1	55.96 (17)	C21—C19—C20—C29	−93.53 (18)
C8—C9—C10—C1	−171.85 (13)	C20—C19—C21—C22	−120.36 (16)
C10—C9—C11—C12	−169.10 (13)	C18—C19—C21—C22	0.73 (19)
C8—C9—C11—C12	56.39 (17)	C19—C21—C22—C17	−27.28 (19)
C9—C11—C12—C13	−54.56 (18)	C16—C17—C22—C21	160.51 (15)
C11—C12—C13—C18	−177.28 (13)	C27—C17—C22—C21	−74.81 (17)
C11—C12—C13—C14	57.27 (18)	C18—C17—C22—C21	42.66 (17)
C18—C13—C14—C26	−64.09 (16)	C28—O4—C27—O3	−1.2 (3)
C12—C13—C14—C26	62.23 (17)	C28—O4—C27—C17	174.75 (14)
C18—C13—C14—C15	52.06 (16)	C16—C17—C27—O3	−132.21 (19)
C12—C13—C14—C15	178.38 (13)	C18—C17—C27—O3	−11.0 (3)
C18—C13—C14—C8	173.74 (12)	C22—C17—C27—O3	97.7 (2)
C12—C13—C14—C8	−59.94 (15)	C16—C17—C27—O4	52.10 (18)
C7—C8—C14—C26	55.22 (16)	C18—C17—C27—O4	173.35 (14)
C25—C8—C14—C26	174.37 (13)	C22—C17—C27—O4	−78.00 (17)
C9—C8—C14—C26	−63.47 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C28—H28A···O1^i	0.98	2.60	3.178 (2)	118
C28—H28B···O1^ii	0.98	2.59	3.272 (3)	127

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