Synthesis and crystal structures of C24-epimeric 20(R)-ocotillol-type saponins

Ocotillol-type saponins have a wide spectrum of biological activities. Previous studies indicated that the configuration at the C24 position may be responsible for their stereoselectivity in pharmacological action and pharmacokinetics. Natural ocotillol-type saponins share a 20(S)-form but it has been found that the 20(R)-stereoisomers have different pharmacological effects. The semisynthesis of 20(R)-ocotillol-type saponins has not been reported and it is therefore worthwhile clarifying their crystal structures. Two C24 epimeric 20(R)-ocotillol-type saponins, namely (20R,24S)-20,24-ep­oxy­dammarane-3β,12β,25-triol, C₃₀H₅₂O₄, (III), and (20R,24R)-20,24-ep­oxy­dammarane-3β,12β,25-triol monohydrate, C₃₀H₅₂O₄·H₂O, (IV), were synthesized, and their structures were elucidated by spectral studies and finally confirmed by single-crystal X-ray diffraction. The (Me)C—O—C—C(OH) torsion angle of (III) is 146.41 (14)°, whereas the corresponding torsion angle of (IV) is −146.4 (7)°, indicating a different conformation at the C24 position. The crystal stacking in (III) generates an R₄⁴(8) motif, through which the mol­ecules are linked into a one-dimensional double chain. The chains are linked via nonclassical C—H...O hydrogen bonds into a two-dimensional network, and further stacked into a three-dimensional structure. In contrast to (III), epimer (IV) crystallizes as a hydrate, in which the water mol­ecules act as hydrogen-bond donors linking one-dimensional chains into a two-dimensional network through inter­molecular O—H...O hydrogen bonds. The hydrogen-bonded chains extend helically along the crystallographic a axis and generate a C₄⁴(8) motif.

S1. Introduction

Ocotillol-type saponins share a tetra­hydro­furan ring and is poor in natural plants [not clear]. It has been found that they have a wide spectrum of biological activities, such as anti-amnesic (Wang, Liu et al., 2013), anti-oxidation (Wang, Yang et al., 2013), anti-inflammatory (Jeong et al., 2015; Wang, Wang et al., 2014), neuroprotective (Wang et al., 2011) and cardio-protective (Yu et al., 2007) properties. Potent anti­myocardial ischemic and myocardial injury activities of ocotillol-type saponins have been explored by several researchers in recent years (Jin et al., 2013; Fu et al., 2014).

In our previous study, two 20(S)-ocotillol-type epimers (see Scheme 1), 20S,24S-ep­oxy­dammarane-3β,12β,25-triol, (V), and 20S,24R-ep­oxy dammarane-3β,12β,25-triol, (VI), were prepared from 20(S)-protopanaxadiol [20(S)-PPD; Meng et al., 2013]. Their protective effects on cultured myocardiocytes in anoxia/re-oxygen injury showed that (VI) exhibits potent protective effect on cardiac muscle cells apoptosis, whereas (V) has no activity (Bi et al., 2011). Further pharmacokinetic studies found that (V) and (VI) have stereoselectivity in pharmacokinetics (Wang, Wu et al., 2014). These indicated that the stereo-configuration at the C-24 position may be responsible for their stereoselectivity in pharmacological action and pharmacokinetics.

Natural ocotillol-type saponins share a 20(S)-form. It has been found that 20(R)-stereoisomers have different pharmacological effects (Kwok et al., 2012; Oh et al., 2014). In 2012, the 20(R)-ocotillol-type saponin [20(R)-PF₁₁, 18 mg in 1kg] was isolated from red American ginseng and its complete signal assignments were carried out by means of two-dimensional NMR spectral analysis (Liu et al., 2012). However, the semisynthesis of 20(R)-ocotillol-type saponins have not been reported. In addition, different crystal forms of drugs may influence the bioavailability even the bioactivity. Therefore, it is worthwhile clarifying their crystal structures. In this paper, the syntheses and crystal structures of two C-24 epimeric 20(R)-ocotillol-type saponins, namely (20R,24S)-20,24-ep­oxy­dammarane-3β,12β,25-triol, (III), and (20R,24R)-20,24-ep­oxy­dammarane-3β,12β,25-triol monohydrate, (IV) (see Scheme 2), and their crystal structure characteristics are described. The synthetic route is illustrated in Scheme 2.

S2. Experimental

S2.1. Synthesis and crystallization

S2.1.1. Synthesis of 20 (R)-protopanaxadiol, (II)

The synthesis of 20(R)-ginsenside Rg3 (I) was reported previously (Sun et al., 2013). 20(R)-Protopanaxadiol, (II), was synthesized according to the reported method of Ma et al. (2005). 20(R)-Ginsenside Rg3, (I) (20 g, 25.5 mmol), and sodium hydroxide (80.0 g) were added to propane­triol (250 ml) in a round-bottomed flask (1000 ml). The mixture was heated at 473–513 K for 6 h [monitored by thin-layer chromatography (TLC)]. After cooling to room temperature, the mixture was diluted with water and the precipitate was extracted with ethyl acetate. The organic phase was washed successively with water and brine, and dried over sodium sulfate. The organic phase was concentrated in a vacuum. The brown solid was purified by flash chromatography and crystallized from ethyl acetate as a white solid [yield 6.4 g; m.p. 517–518 K (literature value: 518–520 K; Ma & Yang, 2015)]. ¹H NMR (CDCl₃, 400 MHz): δ 1.68 (s, 3H), 1.63 (s, 3H), 1.19 (s, 3H), 0.99 (s, 3H), 0.97 (s, 3H), 0.89 (s, 3H), 0.88 (s, 3H), 0.78 (s, 3H), 3.19 (dd, J = 11.6, 4,92 Hz, 1H), 3.67 (td, J = 10.2, 5.04 Hz, 1H), 5.13 (t, J = 7.36 Hz, 1H). ¹³C NMR (CDCl₃, 100 MHz): δ 16.3, 16.7, 16.9, 17.7, 18.1, 19.2, 23.0, 23.2, 26.2, 27.1, 28.6, 29.1, 31.8, 32.6, 35.6, 37.8, 39.7, 40.0, 40.4, 43.6, 49.6, 50.9, 51.0, 52.2, 56.7, 71.3, 73.3, 78.4, 126.4, 131.1. HRMS (FTMS) calculated for C₃₀H₅₃O₃ [M + H]⁺ 461.39892, found 461.39832.

S2.1.2. Synthesis of (III) and (IV)

A solution of 20(R)-protopanaxadiol, (II) (4.03 g, 8.75 mmol), in di­chloro­methane (20 ml) was cooled to 270 K. A di­chloro­methane solution (80 ml) with meta-chloro­per­oxy­benzoic acid (m-CPBA; 3.01 g, 17.50 mmol) was added slowly. After stirring 1 h, iso­propanol (0.8 ml, 10.37 mmol) was added and stirred for another 1 h (monitored by TLC). The organic phase was washed successively with saturated sodium bicarbonate solution, water and brine, and dried over sodium sulfate. The organic phase was evaporated in a vacuum, yielding a white solid. Products (III) and (IV) were prepared by flash chromatography. Suitable crystals of (III) (colourless block-shaped crystals; yield: 1.78 g, 42.4%) and (IV) (colourless prismatic crystals; yield: 1.70 g, 40.8%) were obtained by open-air evaporation of an acetone solution of (III) or (IV).

S2.1.3. Analytical data for (III) and (IV)

(III): m.p. 525-526 K; [α]_D²⁰ +8.14° (EA, c 1.04); ¹H NMR (CDCl₃, 400 MHz): δ 0.73 (d, J = 10.9 Hz, 1H), 0.78 (s, 3H), 0.88 (s, 3H), 0.89 (s, 3H), 0.97 (s, 3H), 0.99 (s, 3H), 0.99–1.07 (m, 2H), 1.13 (s, 3H), 1.19 (s, 3H), 1.24 (s, 3H), 1.24–1.30 (m, 2H), 1.42 (dd, J = 13.4, 2.48, 1H), 1.50–1.52–1.63 [?] (m, 6H), 1.71–1.74 (m, 4H), 1.87–2.10 (m, 6H), 3.19 (dd, J = 11.6, 5.04 Hz, 1H), 3.56 (td, J = 10.3, 5.16 Hz, 1H), 3.89 (t, J = 7.36 Hz, 1H) (49 H atoms are presented; 3 H atoms, as they are active H atoms, did not appear in the ¹H NMR spectrum); ¹³C NMR (CDCl₃, 100 MHz): δ 15.3, 15.5, 16.1, 17.0, 18.3, 19.3, 25.2, 25.4, 26.9, 27.3, 27.4, 28.0, 30.6, 31.3, 34.8, 37.1, 38.1 38.9, 38.9, 39.8, 49.0, 50.0, 50.4, 51.6, 55.8, 70.4, 70.9, 78.8, 85.3, 86.2. HRMS (FTMS) m/z calculated for C₃₀H₅₃O₄ [M + H]⁺: 477.3938, found: 477.3937.

(IV): m.p. 555-556 K; [α]_D²⁰ +25.16° (EA, c 1.03); ¹H NMR (CDCl₃, 400 MHz): δ 0.73 (d, J = 10.8 Hz, 1H), 0.78 (s, 3H), 0.88 (s, 3H), 0.89 (s, 3H), 0.97 (s, 3H), 0.99 (s, 3H), 0.99–1.07 (m, 2H), 1.12 (s, 3H), 1.19 (s, 3H), 1.22–1.30 (m, 3H), 1.23 (s, 3H), 1.42 (dd, J = 13.2, 2.7 Hz, 1H), 1.45–1.65 (m, 6H), 1.70–1.74 (m, 2H), 1.82–1.91 (m, 5H), 1.99–2.04 (m, 2H), 3.19 (dd, J = 11.2, 5.0 Hz, 1H), 3.55 (td, J = 10.4, 5.0 Hz, 1H), 3.89 (dd, J = 9.8, 5.04 Hz, 1H), 5.54 (s, 1H) [unlike (III), 50 H atoms are presented, because one of the three active H atoms appeared in the ¹H NMR spectrum]; ¹³C NMR (CDCl₃, 100 MHz): δ 15.3, 15.5, 16.2, 16.9, 18.2, 21.3, 24.6, 25.8, 26.8, 27.4, 27.9, 28.0, 30.5, 31.3, 34.8, 37.1, 38.9, 38.9, 39.0, 39.8, 49.0, 50.0, 50.6, 51.5, 55.8, 70.2, 70.5, 78.8, 86.3, 86.4. HRMS (FTMS) m/z calculated for C₃₀H₅₃O₄ [M + H]⁺: 477.3938, found: 477.3937.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in idealized positions and treated as riding, with O—H = 0.82 Å and U_iso(H) = 1.5U_eq(O) for (III), and O—H = 0.82 or 0.85 Å and U_iso(H) = 1.2U_eq(O) for (IV). H atoms on C atoms were placed in geometrically idealized positions and constrained to ride on their parent C atoms, with C—H = 0.98 and 0.97 Å (-CH₂) for methine and methyl­ene H atoms, respectively, both with U_iso(H) = 1.2U_eq(C), and C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms.

S3. Results and discussion

S3.1. Synthesis and absolute configuration confirmation

20(S)-Panaxadiol saponins were transformed to 20(R)-ginsenside Rg3, (I), by D,L-tartaric acid hydrolysis, and 20(R)-protopanaxadiol, (II), was degraded from (I) with NaOH in propane­triol, purified using silica-gel column chromatography and crystallized from ethyl acetate. (III) and (IV) were obtained by treating (II) with m-CPBA. Their structures were confirmed by HRMS, ¹H NMR, ¹³C NMR, DEPT (distortionless enhancement by polazization transfer), HMBC (heteronuclear multiple bond correlation), HSQC (heteronuclear single quantum coherence) and single-crystal X-ray diffraction. X-ray crystallography showed that the 20,24-ep­oxy fraction had been formed. The results confirm that the configuration of the C-20 position in (III) and (IV) are both R, and that the configuration of the C-24 are R and S, respectively. The difference between the 24(S)- and 24(R)-isomers in the ¹³C NMR spectra may be observed from the carbon signals of C-21 (S-form: δ 19.3; R-form: δ 21.3), C-22 (S-form: δ 38.1; R-form: δ 39.0) and C-24 (S-form: δ 85.3; R-form: δ 86.4). The ¹H NMR spectrum of (IV) showed a singlet at δ 5.54, whereas this singlet did not appear in the ¹H NMR spectrum of (III). The HMBC spectrum showed that the singlet correlates with C-11 and C-13; in addition, the HSQC spectrum revealed that the singlet has no relationship with any C atom. Therefore, the singlet was due to the –OH group at the C-12 position.

S3.2. Crystal packing arrangements

As shown in Fig. 1, the asymmetric unit of (III) contains one independent molecule. An intra­molecular O2—H2···O3 hydrogen bond is formed (Table 2). The C20—O3—C24—C25 torsion angle is -146.41 (14)° and indicates that the C-24 position has an S form. The molecules are connected by inter­molecular O—H···O hydrogen bonds (Table 2), giving a one-dimensional double chain along the crystallographic c axis (Fig. 2). Four unique molecules are connected by four groups of O—H···O hydrogen bonds to generate an R₄⁴(8) motif. These one-dimensional double chains are further linked to each other through weak inter­chain C—H···O bonding-bond inter­actions into a two-dimensional framework extended in the crystallographic bc plane (Fig. 3). The corresponding C15ⁱⁱⁱ···O2 and H15ⁱⁱⁱ···O2 distances are 3.31 (21) Å and 2.44 (14) Å, respectively, and the C15ⁱⁱⁱ—H15ⁱⁱⁱ···O2 angle is 149.26 (9)°.

In contrast to (III), (IV) crystallizes as a hydrate. As shown in Fig. 4, the asymmetric part of the unit cell contains two symmetry-independent molecules of (IV) and two water molecules. The two independent molecules in the unit cell have the same conformation, and there are only subtle differences in the geometric parameters between them. The C20A—O3A—C24A—C25A and C20B—O3B—C24B—C25B torsion angles are -146.4 (7) and -145.8 (7)°, respectively, which is obviously different from the corresponding torsion angle in (III), and indicates the C-24 position has the R form. The two molecules are arranged in a head-to-tail pattern and form stacks, and the water molecules are located in the channels between these stacks. The distance between the water O1 and O2 atoms is 4.71 (12) Å. Intra­molecular O2A—H2A···O3A and O2B—H2B···O3B hydrogen bonds are formed in (IV). The two independent molecules in the unit cell connect adjacent molecules through inter­molecular O1B—H1B···O4Bⁱⁱ and O1A—H1A···O4Aⁱ (Table 3) hydrogen bonds into two one-dimensional chains along the crystallographic c axis (Fig. 5). Compared to the crystal structure of (III), the water molecules play a key role in the construction of the crystal structure of hydrate (IV). Water molecules, as both hydrogen-bond donors and acceptors, associate with the –OH groups at atoms C12 and C24 of (IV) through inter­molecular hydrogen bonds. Molecules of (IV) and water are arranged alternately along the crystallographic a axis. The water molecules then act as hydrogen-bond donors and link the one-dimensional chains into a two-dimensional network through inter­molecular O1—H1···O2Bⁱⁱ and O2—H2···O2A hydrogen bonds. The hydrogen-bonded chain extends helically along the crystallographic a axis (Fig. 6) and generates a C₄⁴(8) motif.

In conclusion, two C24 epimeric 20(R)-ocotillol epimers were synthesized, and their structures were confirmed by spectral studies and single-crystal X-ray analysis. The epimerization of atom C24 resulted in remarkable differences in both the molecular conformation and the crystal packing arrangements.

Structure description

Ocotillol-type saponins share a tetra­hydro­furan ring and is poor in natural plants [not clear]. It has been found that they have a wide spectrum of biological activities, such as anti-amnesic (Wang, Liu et al., 2013), anti-oxidation (Wang, Yang et al., 2013), anti-inflammatory (Jeong et al., 2015; Wang, Wang et al., 2014), neuroprotective (Wang et al., 2011) and cardio-protective (Yu et al., 2007) properties. Potent anti­myocardial ischemic and myocardial injury activities of ocotillol-type saponins have been explored by several researchers in recent years (Jin et al., 2013; Fu et al., 2014).

In our previous study, two 20(S)-ocotillol-type epimers (see Scheme 1), 20S,24S-ep­oxy­dammarane-3β,12β,25-triol, (V), and 20S,24R-ep­oxy dammarane-3β,12β,25-triol, (VI), were prepared from 20(S)-protopanaxadiol [20(S)-PPD; Meng et al., 2013]. Their protective effects on cultured myocardiocytes in anoxia/re-oxygen injury showed that (VI) exhibits potent protective effect on cardiac muscle cells apoptosis, whereas (V) has no activity (Bi et al., 2011). Further pharmacokinetic studies found that (V) and (VI) have stereoselectivity in pharmacokinetics (Wang, Wu et al., 2014). These indicated that the stereo-configuration at the C-24 position may be responsible for their stereoselectivity in pharmacological action and pharmacokinetics.

Natural ocotillol-type saponins share a 20(S)-form. It has been found that 20(R)-stereoisomers have different pharmacological effects (Kwok et al., 2012; Oh et al., 2014). In 2012, the 20(R)-ocotillol-type saponin [20(R)-PF₁₁, 18 mg in 1kg] was isolated from red American ginseng and its complete signal assignments were carried out by means of two-dimensional NMR spectral analysis (Liu et al., 2012). However, the semisynthesis of 20(R)-ocotillol-type saponins have not been reported. In addition, different crystal forms of drugs may influence the bioavailability even the bioactivity. Therefore, it is worthwhile clarifying their crystal structures. In this paper, the syntheses and crystal structures of two C-24 epimeric 20(R)-ocotillol-type saponins, namely (20R,24S)-20,24-ep­oxy­dammarane-3β,12β,25-triol, (III), and (20R,24R)-20,24-ep­oxy­dammarane-3β,12β,25-triol monohydrate, (IV) (see Scheme 2), and their crystal structure characteristics are described. The synthetic route is illustrated in Scheme 2.

(III): m.p. 525-526 K; [α]_D²⁰ +8.14° (EA, c 1.04); ¹H NMR (CDCl₃, 400 MHz): δ 0.73 (d, J = 10.9 Hz, 1H), 0.78 (s, 3H), 0.88 (s, 3H), 0.89 (s, 3H), 0.97 (s, 3H), 0.99 (s, 3H), 0.99–1.07 (m, 2H), 1.13 (s, 3H), 1.19 (s, 3H), 1.24 (s, 3H), 1.24–1.30 (m, 2H), 1.42 (dd, J = 13.4, 2.48, 1H), 1.50–1.52–1.63 [?] (m, 6H), 1.71–1.74 (m, 4H), 1.87–2.10 (m, 6H), 3.19 (dd, J = 11.6, 5.04 Hz, 1H), 3.56 (td, J = 10.3, 5.16 Hz, 1H), 3.89 (t, J = 7.36 Hz, 1H) (49 H atoms are presented; 3 H atoms, as they are active H atoms, did not appear in the ¹H NMR spectrum); ¹³C NMR (CDCl₃, 100 MHz): δ 15.3, 15.5, 16.1, 17.0, 18.3, 19.3, 25.2, 25.4, 26.9, 27.3, 27.4, 28.0, 30.6, 31.3, 34.8, 37.1, 38.1 38.9, 38.9, 39.8, 49.0, 50.0, 50.4, 51.6, 55.8, 70.4, 70.9, 78.8, 85.3, 86.2. HRMS (FTMS) m/z calculated for C₃₀H₅₃O₄ [M + H]⁺: 477.3938, found: 477.3937.

(IV): m.p. 555-556 K; [α]_D²⁰ +25.16° (EA, c 1.03); ¹H NMR (CDCl₃, 400 MHz): δ 0.73 (d, J = 10.8 Hz, 1H), 0.78 (s, 3H), 0.88 (s, 3H), 0.89 (s, 3H), 0.97 (s, 3H), 0.99 (s, 3H), 0.99–1.07 (m, 2H), 1.12 (s, 3H), 1.19 (s, 3H), 1.22–1.30 (m, 3H), 1.23 (s, 3H), 1.42 (dd, J = 13.2, 2.7 Hz, 1H), 1.45–1.65 (m, 6H), 1.70–1.74 (m, 2H), 1.82–1.91 (m, 5H), 1.99–2.04 (m, 2H), 3.19 (dd, J = 11.2, 5.0 Hz, 1H), 3.55 (td, J = 10.4, 5.0 Hz, 1H), 3.89 (dd, J = 9.8, 5.04 Hz, 1H), 5.54 (s, 1H) [unlike (III), 50 H atoms are presented, because one of the three active H atoms appeared in the ¹H NMR spectrum]; ¹³C NMR (CDCl₃, 100 MHz): δ 15.3, 15.5, 16.2, 16.9, 18.2, 21.3, 24.6, 25.8, 26.8, 27.4, 27.9, 28.0, 30.5, 31.3, 34.8, 37.1, 38.9, 38.9, 39.0, 39.8, 49.0, 50.0, 50.6, 51.5, 55.8, 70.2, 70.5, 78.8, 86.3, 86.4. HRMS (FTMS) m/z calculated for C₃₀H₅₃O₄ [M + H]⁺: 477.3938, found: 477.3937.

As shown in Fig. 1, the asymmetric unit of (III) contains one independent molecule. An intra­molecular O2—H2···O3 hydrogen bond is formed (Table 2). The C20—O3—C24—C25 torsion angle is -146.41 (14)° and indicates that the C-24 position has an S form. The molecules are connected by inter­molecular O—H···O hydrogen bonds (Table 2), giving a one-dimensional double chain along the crystallographic c axis (Fig. 2). Four unique molecules are connected by four groups of O—H···O hydrogen bonds to generate an R₄⁴(8) motif. These one-dimensional double chains are further linked to each other through weak inter­chain C—H···O bonding-bond inter­actions into a two-dimensional framework extended in the crystallographic bc plane (Fig. 3). The corresponding C15ⁱⁱⁱ···O2 and H15ⁱⁱⁱ···O2 distances are 3.31 (21) Å and 2.44 (14) Å, respectively, and the C15ⁱⁱⁱ—H15ⁱⁱⁱ···O2 angle is 149.26 (9)°.

In contrast to (III), (IV) crystallizes as a hydrate. As shown in Fig. 4, the asymmetric part of the unit cell contains two symmetry-independent molecules of (IV) and two water molecules. The two independent molecules in the unit cell have the same conformation, and there are only subtle differences in the geometric parameters between them. The C20A—O3A—C24A—C25A and C20B—O3B—C24B—C25B torsion angles are -146.4 (7) and -145.8 (7)°, respectively, which is obviously different from the corresponding torsion angle in (III), and indicates the C-24 position has the R form. The two molecules are arranged in a head-to-tail pattern and form stacks, and the water molecules are located in the channels between these stacks. The distance between the water O1 and O2 atoms is 4.71 (12) Å. Intra­molecular O2A—H2A···O3A and O2B—H2B···O3B hydrogen bonds are formed in (IV). The two independent molecules in the unit cell connect adjacent molecules through inter­molecular O1B—H1B···O4Bⁱⁱ and O1A—H1A···O4Aⁱ (Table 3) hydrogen bonds into two one-dimensional chains along the crystallographic c axis (Fig. 5). Compared to the crystal structure of (III), the water molecules play a key role in the construction of the crystal structure of hydrate (IV). Water molecules, as both hydrogen-bond donors and acceptors, associate with the –OH groups at atoms C12 and C24 of (IV) through inter­molecular hydrogen bonds. Molecules of (IV) and water are arranged alternately along the crystallographic a axis. The water molecules then act as hydrogen-bond donors and link the one-dimensional chains into a two-dimensional network through inter­molecular O1—H1···O2Bⁱⁱ and O2—H2···O2A hydrogen bonds. The hydrogen-bonded chain extends helically along the crystallographic a axis (Fig. 6) and generates a C₄⁴(8) motif.

In conclusion, two C24 epimeric 20(R)-ocotillol epimers were synthesized, and their structures were confirmed by spectral studies and single-crystal X-ray analysis. The epimerization of atom C24 resulted in remarkable differences in both the molecular conformation and the crystal packing arrangements.

Synthesis and crystallization

The synthesis of 20(R)-ginsenside Rg3 (I) was reported previously (Sun et al., 2013). 20(R)-Protopanaxadiol, (II), was synthesized according to the reported method of Ma et al. (2005). 20(R)-Ginsenside Rg3, (I) (20 g, 25.5 mmol), and sodium hydroxide (80.0 g) were added to propane­triol (250 ml) in a round-bottomed flask (1000 ml). The mixture was heated at 473–513 K for 6 h [monitored by thin-layer chromatography (TLC)]. After cooling to room temperature, the mixture was diluted with water and the precipitate was extracted with ethyl acetate. The organic phase was washed successively with water and brine, and dried over sodium sulfate. The organic phase was concentrated in a vacuum. The brown solid was purified by flash chromatography and crystallized from ethyl acetate as a white solid [yield 6.4 g; m.p. 517–518 K (literature value: 518–520 K; Ma & Yang, 2015)]. ¹H NMR (CDCl₃, 400 MHz): δ 1.68 (s, 3H), 1.63 (s, 3H), 1.19 (s, 3H), 0.99 (s, 3H), 0.97 (s, 3H), 0.89 (s, 3H), 0.88 (s, 3H), 0.78 (s, 3H), 3.19 (dd, J = 11.6, 4,92 Hz, 1H), 3.67 (td, J = 10.2, 5.04 Hz, 1H), 5.13 (t, J = 7.36 Hz, 1H). ¹³C NMR (CDCl₃, 100 MHz): δ 16.3, 16.7, 16.9, 17.7, 18.1, 19.2, 23.0, 23.2, 26.2, 27.1, 28.6, 29.1, 31.8, 32.6, 35.6, 37.8, 39.7, 40.0, 40.4, 43.6, 49.6, 50.9, 51.0, 52.2, 56.7, 71.3, 73.3, 78.4, 126.4, 131.1. HRMS (FTMS) calculated for C₃₀H₅₃O₃ [M + H]⁺ 461.39892, found 461.39832.

A solution of 20(R)-protopanaxadiol, (II) (4.03 g, 8.75 mmol), in di­chloro­methane (20 ml) was cooled to 270 K. A di­chloro­methane solution (80 ml) with meta-chloro­per­oxy­benzoic acid (m-CPBA; 3.01 g, 17.50 mmol) was added slowly. After stirring 1 h, iso­propanol (0.8 ml, 10.37 mmol) was added and stirred for another 1 h (monitored by TLC). The organic phase was washed successively with saturated sodium bicarbonate solution, water and brine, and dried over sodium sulfate. The organic phase was evaporated in a vacuum, yielding a white solid. Products (III) and (IV) were prepared by flash chromatography. Suitable crystals of (III) (colourless block-shaped crystals; yield: 1.78 g, 42.4%) and (IV) (colourless prismatic crystals; yield: 1.70 g, 40.8%) were obtained by open-air evaporation of an acetone solution of (III) or (IV).

20(S)-Panaxadiol saponins were transformed to 20(R)-ginsenside Rg3, (I), by D,L-tartaric acid hydrolysis, and 20(R)-protopanaxadiol, (II), was degraded from (I) with NaOH in propane­triol, purified using silica-gel column chromatography and crystallized from ethyl acetate. (III) and (IV) were obtained by treating (II) with m-CPBA. Their structures were confirmed by HRMS, ¹H NMR, ¹³C NMR, DEPT (distortionless enhancement by polazization transfer), HMBC (heteronuclear multiple bond correlation), HSQC (heteronuclear single quantum coherence) and single-crystal X-ray diffraction. X-ray crystallography showed that the 20,24-ep­oxy fraction had been formed. The results confirm that the configuration of the C-20 position in (III) and (IV) are both R, and that the configuration of the C-24 are R and S, respectively. The difference between the 24(S)- and 24(R)-isomers in the ¹³C NMR spectra may be observed from the carbon signals of C-21 (S-form: δ 19.3; R-form: δ 21.3), C-22 (S-form: δ 38.1; R-form: δ 39.0) and C-24 (S-form: δ 85.3; R-form: δ 86.4). The ¹H NMR spectrum of (IV) showed a singlet at δ 5.54, whereas this singlet did not appear in the ¹H NMR spectrum of (III). The HMBC spectrum showed that the singlet correlates with C-11 and C-13; in addition, the HSQC spectrum revealed that the singlet has no relationship with any C atom. Therefore, the singlet was due to the –OH group at the C-12 position.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in idealized positions and treated as riding, with O—H = 0.82 Å and U_iso(H) = 1.5U_eq(O) for (III), and O—H = 0.82 or 0.85 Å and U_iso(H) = 1.2U_eq(O) for (IV). H atoms on C atoms were placed in geometrically idealized positions and constrained to ride on their parent C atoms, with C—H = 0.98 and 0.97 Å (-CH₂) for methine and methyl­ene H atoms, respectively, both with U_iso(H) = 1.2U_eq(C), and C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms.

Computing details

For both compounds, data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. A perspective view of (III), showing the atom-labelling scheme. Dashed lines indicate hydrogen bonds. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial packing diagram for (III), showing the formation of one-dimensional double-chain and an R4^4(8) motif. Dashed lines indicate hydrogen bonds. [Symmetry codes: (i) -x+2, y, -z+1; (ii) x, y, z+1.]
	Fig. 3. A partial packing diagram for (III), showing the formation of the two-dimensional framework via C—H···O hydrogen bonds (dashed lines). [Symmetry code: (iii) x, y-1, z.]
	Fig. 4. A perspective view of (IV), showing the atom-labelling scheme. Dashed lines indicate hydrogen bonds. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 5. A partial packing diagram for (IV), showing the formation of the one-dimensional double chain and a C4^4(8) motif. Dashed lines indicate hydrogen bonds. [Symmetry codes: (i) x, y, z+1; (ii) x, y, z-1.]
	Fig. 6. A partial packing diagram for (IV), showing the formation of a hydrogen-bond chain linked by water molecules. Dashed lines indicate hydrogen bonds. [Symmetry codes: (iii) x-1, y, z; (iv) x+1, y, z.]

(III) (20R,24S)-20-24-Epoxydammarane-3β,12β,25-triol

Crystal data

C30H52O4	F(000) = 1056
Mr = 476.72	Dx = 1.152 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
a = 23.908 (5) Å	Cell parameters from 2016 reflections
b = 7.4853 (15) Å	θ = 3.1–20.2°
c = 15.363 (3) Å	µ = 0.07 mm^−1
β = 91.89 (3)°	T = 153 K
V = 2747.8 (10) Å^3	Block, colourless
Z = 4	0.18 × 0.15 × 0.1 mm

Data collection

Bruker D8 Venture diffractometer	5377 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −29→30
Tmin = 0.987, Tmax = 0.993	k = −8→9
12854 measured reflections	l = −19→19
5868 independent reflections

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)] = 0.045	w = 1/[σ^2(Fo^2) + (0.0717P)^2 + 0.062P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.110	(Δ/σ)max < 0.001
S = 1.10	Δρmax = 0.24 e Å^−3
5868 reflections	Δρmin = −0.26 e Å^−3
318 parameters	Absolute structure: Flack x determined using 2072 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.2 (3)

Special details

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

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

	x	y	z	Uiso*/Ueq
O1	0.99413 (5)	0.9474 (3)	0.87361 (9)	0.0498 (4)
H1	0.9676	0.9100	0.9008	0.075*
O2	0.87969 (9)	0.7117 (2)	0.32727 (10)	0.0617 (5)
H2	0.8733	0.7322	0.2755	0.093*
O3	0.84950 (5)	0.8283 (2)	0.16378 (8)	0.0431 (3)
O4	0.91990 (5)	0.8384 (2)	0.01194 (9)	0.0491 (4)
H4	0.9389	0.8706	0.0545	0.074*
C1	0.94599 (7)	0.8202 (3)	0.64429 (11)	0.0377 (4)
H1A	0.9357	0.7045	0.6203	0.045*
H1B	0.9782	0.8630	0.6137	0.045*
C2	0.96228 (8)	0.7980 (3)	0.74096 (13)	0.0432 (4)
H2A	0.9314	0.7437	0.7706	0.052*
H2B	0.9941	0.7181	0.7466	0.052*
C3	0.97692 (7)	0.9736 (3)	0.78418 (12)	0.0399 (4)
H3	1.0098	1.0193	0.7548	0.048*
C4	0.93143 (7)	1.1185 (3)	0.77360 (11)	0.0383 (4)
C5	0.91274 (7)	1.1286 (2)	0.67534 (11)	0.0314 (3)
H5	0.9461	1.1704	0.6461	0.038*
C6	0.86863 (8)	1.2729 (3)	0.65535 (12)	0.0406 (4)
H6A	0.8325	1.2322	0.6742	0.049*
H6B	0.8783	1.3807	0.6875	0.049*
C7	0.86487 (8)	1.3147 (3)	0.55794 (11)	0.0384 (4)
H7A	0.9002	1.3648	0.5406	0.046*
H7B	0.8361	1.4043	0.5473	0.046*
C8	0.85131 (6)	1.1502 (2)	0.50126 (11)	0.0298 (3)
C9	0.89263 (6)	0.9963 (2)	0.52833 (10)	0.0283 (3)
H9	0.9297	1.0426	0.5149	0.034*
C10	0.89702 (6)	0.9508 (2)	0.62831 (11)	0.0296 (3)
C11	0.88471 (8)	0.8324 (3)	0.46879 (11)	0.0362 (4)
H11A	0.9125	0.7432	0.4853	0.043*
H11B	0.8481	0.7812	0.4779	0.043*
C12	0.88973 (8)	0.8754 (2)	0.37226 (12)	0.0364 (4)
H12	0.9279	0.9156	0.3618	0.044*
C13	0.84898 (7)	1.0233 (2)	0.34698 (11)	0.0306 (3)
H13	0.8116	0.9805	0.3609	0.037*
C14	0.85997 (7)	1.1932 (2)	0.40215 (11)	0.0298 (3)
C15	0.81762 (8)	1.3230 (3)	0.35862 (12)	0.0412 (4)
H15A	0.7804	1.3034	0.3800	0.049*
H15B	0.8284	1.4460	0.3700	0.049*
C16	0.81928 (10)	1.2812 (3)	0.26141 (13)	0.0505 (5)
H16A	0.8418	1.3692	0.2322	0.061*
H16B	0.7818	1.2836	0.2354	0.061*
C17	0.84524 (7)	1.0922 (3)	0.25209 (11)	0.0351 (4)
H17	0.8835	1.1073	0.2325	0.042*
C18	0.78941 (7)	1.0985 (3)	0.51493 (12)	0.0415 (4)
H18A	0.7818	1.1039	0.5758	0.062*
H18B	0.7828	0.9794	0.4939	0.062*
H18C	0.7653	1.1803	0.4835	0.062*
C19	0.84386 (8)	0.8585 (3)	0.66087 (13)	0.0419 (4)
H19A	0.8292	0.7791	0.6167	0.063*
H19B	0.8163	0.9473	0.6734	0.063*
H19C	0.8531	0.7918	0.7128	0.063*
C20	0.81341 (7)	0.9776 (3)	0.18420 (11)	0.0390 (4)
C21	0.75768 (9)	0.9071 (4)	0.21541 (16)	0.0608 (7)
H21A	0.7368	0.8557	0.1672	0.091*
H21B	0.7367	1.0035	0.2394	0.091*
H21C	0.7645	0.8176	0.2593	0.091*
C22	0.80683 (9)	1.0677 (4)	0.09520 (13)	0.0512 (5)
H22A	0.7733	1.1405	0.0917	0.061*
H22B	0.8390	1.1420	0.0836	0.061*
C23	0.80265 (8)	0.9125 (4)	0.03194 (14)	0.0551 (6)
H23A	0.8205	0.9414	−0.0221	0.066*
H23B	0.7639	0.8815	0.0191	0.066*
C24	0.83339 (8)	0.7586 (3)	0.07947 (12)	0.0444 (5)
H24	0.8074	0.6588	0.0865	0.053*
C25	0.88570 (8)	0.6914 (3)	0.03534 (12)	0.0449 (5)
C26	0.91900 (11)	0.5621 (4)	0.09325 (16)	0.0597 (6)
H26A	0.9512	0.5215	0.0633	0.090*
H26B	0.8959	0.4617	0.1070	0.090*
H26C	0.9309	0.6216	0.1461	0.090*
C27	0.86779 (11)	0.6000 (4)	−0.05008 (16)	0.0650 (7)
H27A	0.8458	0.6813	−0.0853	0.097*
H27B	0.8459	0.4960	−0.0378	0.097*
H27C	0.9004	0.5653	−0.0807	0.097*
C28	0.95870 (10)	1.2960 (3)	0.80067 (15)	0.0545 (5)
H28A	0.9306	1.3873	0.8025	0.082*
H28B	0.9861	1.3285	0.7592	0.082*
H28C	0.9765	1.2835	0.8573	0.082*
C29	0.88244 (8)	1.0848 (4)	0.83385 (13)	0.0500 (5)
H29A	0.8947	1.1033	0.8933	0.075*
H29B	0.8695	0.9641	0.8266	0.075*
H29C	0.8525	1.1660	0.8193	0.075*
C30	0.91886 (7)	1.2706 (3)	0.38668 (12)	0.0384 (4)
H30A	0.9260	1.2677	0.3256	0.058*
H30B	0.9465	1.2004	0.4178	0.058*
H30C	0.9206	1.3918	0.4070	0.058*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0408 (7)	0.0750 (11)	0.0332 (7)	0.0071 (8)	−0.0052 (5)	0.0001 (7)
O2	0.1170 (14)	0.0284 (8)	0.0387 (8)	0.0088 (8)	−0.0128 (8)	−0.0051 (6)
O3	0.0493 (7)	0.0485 (8)	0.0311 (6)	0.0049 (7)	−0.0029 (5)	−0.0037 (6)
O4	0.0438 (7)	0.0687 (10)	0.0344 (7)	−0.0133 (7)	−0.0029 (5)	0.0043 (7)
C1	0.0405 (8)	0.0353 (10)	0.0368 (9)	0.0087 (8)	−0.0048 (6)	−0.0019 (7)
C2	0.0446 (9)	0.0435 (11)	0.0409 (10)	0.0101 (9)	−0.0080 (7)	0.0015 (8)
C3	0.0334 (8)	0.0547 (12)	0.0316 (9)	0.0035 (9)	0.0001 (6)	−0.0014 (8)
C4	0.0386 (9)	0.0456 (11)	0.0308 (8)	0.0025 (8)	0.0036 (6)	−0.0040 (7)
C5	0.0314 (7)	0.0326 (9)	0.0306 (8)	−0.0010 (7)	0.0051 (6)	−0.0029 (6)
C6	0.0481 (10)	0.0364 (10)	0.0377 (9)	0.0097 (8)	0.0062 (7)	−0.0037 (8)
C7	0.0474 (9)	0.0291 (9)	0.0388 (9)	0.0082 (8)	0.0043 (7)	−0.0001 (7)
C8	0.0285 (7)	0.0282 (8)	0.0330 (8)	0.0028 (7)	0.0050 (6)	0.0030 (6)
C9	0.0283 (7)	0.0263 (8)	0.0306 (8)	0.0015 (7)	0.0029 (5)	0.0006 (6)
C10	0.0290 (7)	0.0286 (8)	0.0313 (8)	0.0010 (7)	0.0018 (5)	0.0019 (6)
C11	0.0476 (9)	0.0246 (8)	0.0360 (9)	0.0024 (8)	−0.0039 (7)	0.0016 (7)
C12	0.0456 (9)	0.0282 (9)	0.0352 (9)	0.0037 (8)	0.0003 (7)	−0.0019 (7)
C13	0.0305 (8)	0.0287 (8)	0.0326 (8)	−0.0005 (7)	0.0028 (6)	0.0035 (6)
C14	0.0296 (7)	0.0264 (8)	0.0336 (8)	0.0021 (7)	0.0042 (6)	0.0036 (6)
C15	0.0460 (9)	0.0371 (10)	0.0407 (9)	0.0129 (9)	0.0047 (7)	0.0092 (8)
C16	0.0667 (13)	0.0440 (12)	0.0407 (10)	0.0147 (11)	0.0017 (8)	0.0095 (9)
C17	0.0350 (8)	0.0376 (10)	0.0330 (8)	0.0009 (8)	0.0024 (6)	0.0037 (7)
C18	0.0292 (8)	0.0544 (12)	0.0413 (10)	0.0037 (8)	0.0061 (6)	0.0110 (8)
C19	0.0377 (8)	0.0478 (12)	0.0403 (9)	−0.0102 (8)	0.0013 (7)	0.0106 (8)
C20	0.0340 (8)	0.0488 (11)	0.0342 (9)	−0.0004 (8)	0.0015 (6)	0.0001 (8)
C21	0.0409 (10)	0.093 (2)	0.0484 (12)	−0.0172 (12)	0.0042 (8)	−0.0062 (12)
C22	0.0490 (10)	0.0662 (15)	0.0378 (10)	0.0083 (11)	−0.0053 (8)	0.0056 (9)
C23	0.0421 (10)	0.0854 (18)	0.0372 (10)	0.0037 (11)	−0.0065 (8)	−0.0031 (10)
C24	0.0418 (9)	0.0581 (13)	0.0332 (9)	−0.0101 (9)	−0.0003 (7)	−0.0057 (8)
C25	0.0463 (10)	0.0527 (12)	0.0356 (9)	−0.0062 (9)	0.0019 (7)	−0.0063 (8)
C26	0.0674 (14)	0.0583 (15)	0.0534 (13)	0.0075 (12)	0.0026 (10)	−0.0002 (11)
C27	0.0707 (14)	0.0778 (19)	0.0466 (12)	−0.0098 (13)	0.0039 (10)	−0.0226 (11)
C28	0.0671 (13)	0.0525 (14)	0.0439 (11)	−0.0052 (11)	−0.0007 (9)	−0.0147 (10)
C29	0.0442 (10)	0.0703 (15)	0.0359 (10)	0.0153 (10)	0.0099 (7)	0.0060 (9)
C30	0.0389 (8)	0.0359 (10)	0.0410 (9)	−0.0074 (8)	0.0084 (6)	0.0031 (8)

Geometric parameters (Å, º)

O1—H1	0.8200	C14—C30	1.548 (2)
O1—C3	1.435 (2)	C15—H15A	0.9700
O2—H2	0.8200	C15—H15B	0.9700
O2—C12	1.424 (2)	C15—C16	1.528 (3)
O3—C20	1.453 (2)	C16—H16A	0.9700
O3—C24	1.437 (2)	C16—H16B	0.9700
O4—H4	0.8200	C16—C17	1.554 (3)
O4—C25	1.424 (3)	C17—H17	0.9800
C1—H1A	0.9700	C17—C20	1.533 (3)
C1—H1B	0.9700	C18—H18A	0.9600
C1—C2	1.532 (2)	C18—H18B	0.9600
C1—C10	1.539 (2)	C18—H18C	0.9600
C2—H2A	0.9700	C19—H19A	0.9600
C2—H2B	0.9700	C19—H19B	0.9600
C2—C3	1.509 (3)	C19—H19C	0.9600
C3—H3	0.9800	C20—C21	1.525 (3)
C3—C4	1.540 (3)	C20—C22	1.528 (3)
C4—C5	1.562 (2)	C21—H21A	0.9600
C4—C28	1.532 (3)	C21—H21B	0.9600
C4—C29	1.537 (3)	C21—H21C	0.9600
C5—H5	0.9800	C22—H22A	0.9700
C5—C6	1.533 (2)	C22—H22B	0.9700
C5—C10	1.555 (2)	C22—C23	1.515 (3)
C6—H6A	0.9700	C23—H23A	0.9700
C6—H6B	0.9700	C23—H23B	0.9700
C6—C7	1.529 (2)	C23—C24	1.538 (3)
C7—H7A	0.9700	C24—H24	0.9800
C7—H7B	0.9700	C24—C25	1.527 (3)
C7—C8	1.537 (2)	C25—C26	1.522 (3)
C8—C9	1.565 (2)	C25—C27	1.529 (3)
C8—C14	1.577 (2)	C26—H26A	0.9600
C8—C18	1.550 (2)	C26—H26B	0.9600
C9—H9	0.9800	C26—H26C	0.9600
C9—C10	1.574 (2)	C27—H27A	0.9600
C9—C11	1.538 (2)	C27—H27B	0.9600
C10—C19	1.544 (2)	C27—H27C	0.9600
C11—H11A	0.9700	C28—H28A	0.9600
C11—H11B	0.9700	C28—H28B	0.9600
C11—C12	1.526 (2)	C28—H28C	0.9600
C12—H12	0.9800	C29—H29A	0.9600
C12—C13	1.517 (2)	C29—H29B	0.9600
C13—H13	0.9800	C29—H29C	0.9600
C13—C14	1.546 (2)	C30—H30A	0.9600
C13—C17	1.546 (2)	C30—H30B	0.9600
C14—C15	1.540 (2)	C30—H30C	0.9600
C3—O1—H1	109.5	C16—C15—H15A	110.8
C12—O2—H2	109.5	C16—C15—H15B	110.8
C24—O3—C20	109.28 (14)	C15—C16—H16A	110.2
C25—O4—H4	109.5	C15—C16—H16B	110.2
H1A—C1—H1B	107.8	C15—C16—C17	107.44 (16)
C2—C1—H1A	109.0	H16A—C16—H16B	108.5
C2—C1—H1B	109.0	C17—C16—H16A	110.2
C2—C1—C10	113.04 (15)	C17—C16—H16B	110.2
C10—C1—H1A	109.0	C13—C17—C16	103.17 (14)
C10—C1—H1B	109.0	C13—C17—H17	107.6
C1—C2—H2A	109.1	C16—C17—H17	107.6
C1—C2—H2B	109.1	C20—C17—C13	117.82 (16)
H2A—C2—H2B	107.9	C20—C17—C16	112.43 (15)
C3—C2—C1	112.33 (17)	C20—C17—H17	107.6
C3—C2—H2A	109.1	C8—C18—H18A	109.5
C3—C2—H2B	109.1	C8—C18—H18B	109.5
O1—C3—C2	110.93 (17)	C8—C18—H18C	109.5
O1—C3—H3	106.2	H18A—C18—H18B	109.5
O1—C3—C4	112.11 (15)	H18A—C18—H18C	109.5
C2—C3—H3	106.2	H18B—C18—H18C	109.5
C2—C3—C4	114.46 (15)	C10—C19—H19A	109.5
C4—C3—H3	106.2	C10—C19—H19B	109.5
C3—C4—C5	108.34 (14)	C10—C19—H19C	109.5
C28—C4—C3	106.82 (16)	H19A—C19—H19B	109.5
C28—C4—C5	109.01 (16)	H19A—C19—H19C	109.5
C28—C4—C29	107.74 (17)	H19B—C19—H19C	109.5
C29—C4—C3	111.75 (17)	O3—C20—C17	107.01 (13)
C29—C4—C5	112.99 (15)	O3—C20—C21	109.45 (19)
C4—C5—H5	104.4	O3—C20—C22	100.98 (15)
C6—C5—C4	113.62 (14)	C21—C20—C17	113.51 (16)
C6—C5—H5	104.4	C21—C20—C22	111.65 (17)
C6—C5—C10	110.84 (13)	C22—C20—C17	113.32 (18)
C10—C5—C4	117.68 (15)	C20—C21—H21A	109.5
C10—C5—H5	104.4	C20—C21—H21B	109.5
C5—C6—H6A	109.4	C20—C21—H21C	109.5
C5—C6—H6B	109.4	H21A—C21—H21B	109.5
H6A—C6—H6B	108.0	H21A—C21—H21C	109.5
C7—C6—C5	110.98 (14)	H21B—C21—H21C	109.5
C7—C6—H6A	109.4	C20—C22—H22A	111.0
C7—C6—H6B	109.4	C20—C22—H22B	111.0
C6—C7—H7A	108.9	H22A—C22—H22B	109.0
C6—C7—H7B	108.9	C23—C22—C20	103.8 (2)
C6—C7—C8	113.28 (15)	C23—C22—H22A	111.0
H7A—C7—H7B	107.7	C23—C22—H22B	111.0
C8—C7—H7A	108.9	C22—C23—H23A	110.9
C8—C7—H7B	108.9	C22—C23—H23B	110.9
C7—C8—C9	108.65 (13)	C22—C23—C24	104.42 (16)
C7—C8—C14	110.57 (14)	H23A—C23—H23B	108.9
C7—C8—C18	107.91 (14)	C24—C23—H23A	110.9
C9—C8—C14	107.77 (12)	C24—C23—H23B	110.9
C18—C8—C9	112.18 (14)	O3—C24—C23	105.43 (18)
C18—C8—C14	109.77 (14)	O3—C24—H24	109.2
C8—C9—H9	104.5	O3—C24—C25	108.69 (14)
C8—C9—C10	116.11 (13)	C23—C24—H24	109.2
C10—C9—H9	104.5	C25—C24—C23	114.92 (17)
C11—C9—C8	111.39 (13)	C25—C24—H24	109.2
C11—C9—H9	104.5	O4—C25—C24	110.07 (19)
C11—C9—C10	114.24 (14)	O4—C25—C26	110.21 (17)
C1—C10—C5	107.38 (13)	O4—C25—C27	106.03 (18)
C1—C10—C9	108.62 (13)	C24—C25—C27	108.55 (17)
C1—C10—C19	107.12 (15)	C26—C25—C24	111.73 (18)
C5—C10—C9	105.99 (13)	C26—C25—C27	110.1 (2)
C19—C10—C5	114.92 (14)	C25—C26—H26A	109.5
C19—C10—C9	112.58 (13)	C25—C26—H26B	109.5
C9—C11—H11A	108.9	C25—C26—H26C	109.5
C9—C11—H11B	108.9	H26A—C26—H26B	109.5
H11A—C11—H11B	107.7	H26A—C26—H26C	109.5
C12—C11—C9	113.43 (15)	H26B—C26—H26C	109.5
C12—C11—H11A	108.9	C25—C27—H27A	109.5
C12—C11—H11B	108.9	C25—C27—H27B	109.5
O2—C12—C11	105.83 (15)	C25—C27—H27C	109.5
O2—C12—H12	109.1	H27A—C27—H27B	109.5
O2—C12—C13	114.05 (15)	H27A—C27—H27C	109.5
C11—C12—H12	109.1	H27B—C27—H27C	109.5
C13—C12—C11	109.40 (15)	C4—C28—H28A	109.5
C13—C12—H12	109.1	C4—C28—H28B	109.5
C12—C13—H13	106.8	C4—C28—H28C	109.5
C12—C13—C14	111.35 (13)	H28A—C28—H28B	109.5
C12—C13—C17	120.10 (15)	H28A—C28—H28C	109.5
C14—C13—H13	106.8	H28B—C28—H28C	109.5
C17—C13—H13	106.8	C4—C29—H29A	109.5
C17—C13—C14	104.23 (14)	C4—C29—H29B	109.5
C13—C14—C8	109.62 (14)	C4—C29—H29C	109.5
C13—C14—C30	111.26 (14)	H29A—C29—H29B	109.5
C15—C14—C8	116.28 (14)	H29A—C29—H29C	109.5
C15—C14—C13	100.57 (13)	H29B—C29—H29C	109.5
C15—C14—C30	106.59 (15)	C14—C30—H30A	109.5
C30—C14—C8	111.96 (14)	C14—C30—H30B	109.5
C14—C15—H15A	110.8	C14—C30—H30C	109.5
C14—C15—H15B	110.8	H30A—C30—H30B	109.5
H15A—C15—H15B	108.8	H30A—C30—H30C	109.5
C16—C15—C14	104.92 (16)	H30B—C30—H30C	109.5
O1—C3—C4—C5	−176.38 (15)	C11—C9—C10—C5	172.57 (13)
O1—C3—C4—C28	66.3 (2)	C11—C9—C10—C19	−61.00 (19)
O1—C3—C4—C29	−51.3 (2)	C11—C12—C13—C14	58.21 (18)
O2—C12—C13—C14	176.51 (14)	C11—C12—C13—C17	−179.67 (15)
O2—C12—C13—C17	−61.4 (2)	C12—C13—C14—C8	−61.78 (17)
O3—C20—C22—C23	38.47 (18)	C12—C13—C14—C15	175.21 (14)
O3—C24—C25—O4	−70.2 (2)	C12—C13—C14—C30	62.61 (18)
O3—C24—C25—C26	52.6 (2)	C12—C13—C17—C16	−158.19 (16)
O3—C24—C25—C27	174.2 (2)	C12—C13—C17—C20	77.3 (2)
C1—C2—C3—O1	−177.67 (14)	C13—C14—C15—C16	−38.63 (19)
C1—C2—C3—C4	54.3 (2)	C13—C17—C20—O3	−75.92 (18)
C2—C1—C10—C5	53.3 (2)	C13—C17—C20—C21	44.9 (2)
C2—C1—C10—C9	167.55 (15)	C13—C17—C20—C22	173.67 (16)
C2—C1—C10—C19	−70.60 (19)	C14—C8—C9—C10	171.63 (13)
C2—C3—C4—C5	−48.9 (2)	C14—C8—C9—C11	−55.28 (17)
C2—C3—C4—C28	−166.20 (16)	C14—C13—C17—C16	−32.66 (16)
C2—C3—C4—C29	76.2 (2)	C14—C13—C17—C20	−157.17 (14)
C3—C4—C5—C6	−178.13 (15)	C14—C15—C16—C17	19.2 (2)
C3—C4—C5—C10	49.97 (19)	C15—C16—C17—C13	8.28 (19)
C4—C5—C6—C7	163.06 (15)	C15—C16—C17—C20	136.24 (17)
C4—C5—C10—C1	−52.39 (18)	C16—C17—C20—O3	164.32 (15)
C4—C5—C10—C9	−168.35 (13)	C16—C17—C20—C21	−74.8 (2)
C4—C5—C10—C19	66.65 (19)	C16—C17—C20—C22	53.9 (2)
C5—C6—C7—C8	57.4 (2)	C17—C13—C14—C8	167.33 (13)
C6—C5—C10—C1	174.46 (14)	C17—C13—C14—C15	44.32 (16)
C6—C5—C10—C9	58.51 (16)	C17—C13—C14—C30	−68.29 (16)
C6—C5—C10—C19	−66.49 (19)	C17—C20—C22—C23	152.56 (16)
C6—C7—C8—C9	−50.52 (18)	C18—C8—C9—C10	−67.43 (18)
C6—C7—C8—C14	−168.60 (14)	C18—C8—C9—C11	65.67 (18)
C6—C7—C8—C18	71.34 (17)	C18—C8—C14—C13	−63.89 (17)
C7—C8—C9—C10	51.79 (18)	C18—C8—C14—C15	49.3 (2)
C7—C8—C9—C11	−175.12 (13)	C18—C8—C14—C30	172.14 (15)
C7—C8—C14—C13	177.17 (13)	C20—O3—C24—C23	22.66 (19)
C7—C8—C14—C15	−69.67 (19)	C20—O3—C24—C25	146.36 (17)
C7—C8—C14—C30	53.19 (18)	C20—C22—C23—C24	−25.6 (2)
C8—C9—C10—C1	−170.76 (14)	C21—C20—C22—C23	−77.8 (2)
C8—C9—C10—C5	−55.65 (16)	C22—C23—C24—O3	3.0 (2)
C8—C9—C10—C19	70.8 (2)	C22—C23—C24—C25	−116.68 (19)
C8—C9—C11—C12	55.06 (19)	C23—C24—C25—O4	47.7 (2)
C8—C14—C15—C16	−156.87 (16)	C23—C24—C25—C26	170.44 (18)
C9—C8—C14—C13	58.56 (16)	C23—C24—C25—C27	−68.0 (3)
C9—C8—C14—C15	171.72 (14)	C24—O3—C20—C17	−157.16 (15)
C9—C8—C14—C30	−65.42 (17)	C24—O3—C20—C21	79.44 (19)
C9—C11—C12—O2	−178.28 (15)	C24—O3—C20—C22	−38.41 (19)
C9—C11—C12—C13	−54.99 (19)	C28—C4—C5—C6	−62.2 (2)
C10—C1—C2—C3	−56.7 (2)	C28—C4—C5—C10	165.85 (15)
C10—C5—C6—C7	−61.8 (2)	C29—C4—C5—C6	57.5 (2)
C10—C9—C11—C12	−170.92 (14)	C29—C4—C5—C10	−74.4 (2)
C11—C9—C10—C1	57.46 (17)	C30—C14—C15—C16	77.51 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4^i	0.82	2.15	2.929 (2)	158
O2—H2···O3	0.82	1.93	2.733 (2)	167
O4—H4···O1^ii	0.82	2.00	2.783 (2)	160

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

(IV) (20R,24R)-20,24-Epoxydammarane-3β,12β,25-triol monohydrate

Crystal data

C30H52O4·H2O	F(000) = 1096
Mr = 494.73	Dx = 1.138 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
a = 6.8503 (6) Å	Cell parameters from 2016 reflections
b = 29.1839 (18) Å	θ = 2–26°
c = 14.8014 (9) Å	µ = 0.59 mm^−1
β = 102.70 (1)°	T = 293 K
V = 2886.7 (4) Å^3	Prism, colourless
Z = 4	0.45 × 0.38 × 0.35 mm

Data collection

Bruker D8 Venture diffractometer	3528 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.057
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	θmax = 66.2°, θmin = 3.0°
Tmin = 0.777, Tmax = 0.820	h = −8→5
9666 measured reflections	k = −34→26
6932 independent reflections	l = −17→17

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.093	w = 1/[σ^2(Fo^2) + (0.1333P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.277	(Δ/σ)max < 0.001
S = 0.97	Δρmax = 0.25 e Å^−3
6932 reflections	Δρmin = −0.29 e Å^−3
647 parameters	Absolute structure: Flack x determined using 581 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.7 (5)

Special details

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

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

	x	y	z	Uiso*/Ueq
O1A	0.7768 (11)	0.2486 (3)	1.4487 (5)	0.072 (2)
H1A	0.7281	0.2704	1.4711	0.108*
O1	0.5102 (13)	0.3885 (4)	0.9094 (7)	0.109 (3)
H1C	0.5404	0.3623	0.8910	0.163*
H1D	0.3931	0.3923	0.8764	0.163*
O2A	0.6001 (11)	0.2979 (3)	0.8419 (4)	0.072 (2)
H2A	0.5393	0.2973	0.7876	0.108*
O3A	0.4448 (11)	0.2740 (3)	0.6671 (4)	0.0662 (19)
O4A	0.6458 (9)	0.3197 (3)	0.5495 (5)	0.074 (2)
H4A	0.7156	0.3188	0.6021	0.110*
C1A	0.7086 (16)	0.2769 (4)	1.1953 (8)	0.068 (3)
H1AA	0.7828	0.2982	1.1651	0.082*
H1AB	0.5694	0.2864	1.1807	0.082*
C2A	0.7887 (18)	0.2797 (4)	1.3003 (8)	0.072 (3)
H2AA	0.9318	0.2742	1.3144	0.087*
H2AB	0.7665	0.3104	1.3213	0.087*
C3A	0.6907 (16)	0.2461 (4)	1.3506 (7)	0.066 (3)
H3A	0.5487	0.2542	1.3408	0.079*
C4A	0.7045 (14)	0.1966 (4)	1.3197 (7)	0.059 (3)
C5A	0.6310 (14)	0.1946 (3)	1.2146 (7)	0.055 (2)
H5A	0.4911	0.2045	1.2043	0.066*
C6A	0.6177 (15)	0.1468 (4)	1.1734 (7)	0.062 (3)
H6AA	0.5634	0.1260	1.2127	0.074*
H6AB	0.7507	0.1363	1.1710	0.074*
C7A	0.4846 (15)	0.1463 (4)	1.0758 (7)	0.059 (2)
H7AA	0.4785	0.1153	1.0517	0.071*
H7AB	0.3500	0.1553	1.0791	0.071*
C8A	0.5583 (13)	0.1778 (4)	1.0101 (7)	0.055 (2)
C9A	0.5971 (13)	0.2267 (3)	1.0532 (7)	0.056 (2)
H9A	0.4642	0.2371	1.0588	0.067*
C10A	0.7248 (13)	0.2282 (3)	1.1558 (6)	0.051 (2)
C11A	0.6586 (15)	0.2615 (4)	0.9888 (7)	0.060 (3)
H11A	0.7900	0.2533	0.9795	0.071*
H11B	0.6696	0.2913	1.0185	0.071*
C12A	0.5144 (15)	0.2652 (4)	0.8943 (7)	0.061 (3)
H12A	0.3857	0.2770	0.9029	0.073*
C13A	0.4825 (14)	0.2182 (3)	0.8503 (6)	0.051 (2)
H13A	0.6143	0.2071	0.8446	0.061*
C14A	0.4069 (13)	0.1848 (3)	0.9144 (7)	0.053 (2)
C15A	0.3645 (18)	0.1421 (4)	0.8511 (7)	0.072 (3)
H15A	0.4872	0.1256	0.8505	0.086*
H15B	0.2719	0.1215	0.8717	0.086*
C16A	0.2722 (16)	0.1615 (4)	0.7550 (7)	0.069 (3)
H16A	0.1274	0.1599	0.7431	0.083*
H16B	0.3173	0.1442	0.7075	0.083*
C17A	0.3411 (15)	0.2121 (4)	0.7546 (6)	0.059 (2)
H17A	0.2237	0.2315	0.7533	0.070*
C18A	0.7549 (14)	0.1569 (4)	0.9897 (7)	0.066 (3)
H18A	0.8456	0.1495	1.0471	0.099*
H18B	0.8165	0.1788	0.9563	0.099*
H18C	0.7232	0.1296	0.9532	0.099*
C19A	0.9538 (13)	0.2192 (4)	1.1605 (8)	0.072 (3)
H19A	0.9836	0.2261	1.1015	0.108*
H19B	0.9843	0.1876	1.1755	0.108*
H19C	1.0330	0.2384	1.2072	0.108*
C20A	0.4215 (14)	0.2240 (4)	0.6699 (6)	0.054 (2)
C21A	0.6313 (15)	0.2029 (5)	0.6701 (7)	0.079 (3)
H21A	0.6688	0.2104	0.6130	0.119*
H21B	0.6254	0.1703	0.6762	0.119*
H21C	0.7287	0.2152	0.7210	0.119*
C22A	0.2706 (16)	0.2132 (4)	0.5776 (6)	0.069 (3)
H22A	0.3009	0.1840	0.5523	0.083*
H22B	0.1344	0.2125	0.5864	0.083*
C23A	0.2996 (16)	0.2516 (4)	0.5165 (8)	0.073 (3)
H23A	0.1826	0.2558	0.4667	0.087*
H23B	0.4154	0.2465	0.4901	0.087*
C24A	0.3309 (16)	0.2922 (4)	0.5802 (8)	0.068 (3)
H24A	0.2004	0.3025	0.5893	0.081*
C25A	0.4414 (15)	0.3330 (4)	0.5535 (7)	0.065 (3)
C26A	0.3436 (19)	0.3473 (5)	0.4556 (9)	0.088 (4)
H26A	0.3986	0.3761	0.4419	0.131*
H26B	0.2020	0.3505	0.4502	0.131*
H26C	0.3683	0.3245	0.4129	0.131*
C27A	0.4568 (17)	0.3724 (4)	0.6230 (9)	0.081 (3)
H27A	0.5362	0.3628	0.6818	0.121*
H27B	0.3253	0.3807	0.6300	0.121*
H27C	0.5188	0.3983	0.6009	0.121*
C28A	0.5651 (18)	0.1673 (5)	1.3659 (8)	0.082 (4)
H28A	0.6016	0.1713	1.4319	0.124*
H28B	0.5784	0.1356	1.3512	0.124*
H28C	0.4290	0.1768	1.3434	0.124*
C29A	0.9193 (15)	0.1781 (4)	1.3540 (8)	0.072 (3)
H29A	1.0133	0.2001	1.3405	0.109*
H29B	0.9337	0.1498	1.3232	0.109*
H29C	0.9446	0.1731	1.4196	0.109*
C30A	0.1981 (13)	0.1998 (4)	0.9296 (8)	0.073 (3)
H30A	0.1479	0.1769	0.9650	0.109*
H30B	0.1071	0.2035	0.8707	0.109*
H30C	0.2109	0.2284	0.9626	0.109*
O1B	0.6482 (11)	0.4578 (3)	0.1989 (5)	0.080 (2)
H1B	0.5803	0.4357	0.1769	0.119*
O2B	1.0811 (11)	0.4066 (3)	0.8071 (5)	0.075 (2)
H2B	1.0832	0.4096	0.8623	0.112*
O3B	1.1090 (10)	0.4317 (3)	0.9819 (5)	0.0666 (19)
O4B	1.4250 (9)	0.3857 (3)	1.0984 (5)	0.069 (2)
H4B	1.4443	0.3857	1.0457	0.104*
C1B	0.8295 (16)	0.4288 (4)	0.4513 (7)	0.063 (3)
H1BA	0.9266	0.4064	0.4815	0.075*
H1BB	0.7016	0.4210	0.4652	0.075*
C2B	0.8107 (17)	0.4257 (4)	0.3467 (7)	0.066 (3)
H2BA	0.9399	0.4317	0.3325	0.079*
H2BB	0.7702	0.3949	0.3258	0.079*
C3B	0.6583 (17)	0.4599 (4)	0.2957 (8)	0.070 (3)
H3B	0.5267	0.4516	0.3065	0.084*
C4B	0.7038 (15)	0.5097 (4)	0.3286 (7)	0.061 (3)
C5B	0.7369 (15)	0.5113 (4)	0.4341 (7)	0.059 (2)
H5B	0.6082	0.5015	0.4462	0.071*
C6B	0.7692 (16)	0.5589 (4)	0.4777 (8)	0.068 (3)
H6BA	0.9032	0.5693	0.4764	0.082*
H6BB	0.6753	0.5801	0.4406	0.082*
C7B	0.7433 (15)	0.5603 (4)	0.5757 (8)	0.066 (3)
H7BA	0.6049	0.5534	0.5760	0.079*
H7BB	0.7710	0.5912	0.5996	0.079*
C8B	0.8822 (12)	0.5259 (3)	0.6418 (7)	0.054 (2)
C9B	0.8615 (14)	0.4775 (3)	0.5935 (6)	0.052 (2)
H9B	0.7221	0.4684	0.5890	0.062*
C10B	0.8932 (13)	0.4761 (3)	0.4915 (7)	0.056 (2)
C11B	0.9885 (15)	0.4417 (4)	0.6580 (7)	0.060 (3)
H11C	0.9648	0.4117	0.6295	0.072*
H11D	1.1291	0.4489	0.6641	0.072*
C12B	0.9430 (16)	0.4399 (4)	0.7539 (7)	0.064 (3)
H12B	0.8054	0.4291	0.7486	0.077*
C13B	0.9655 (13)	0.4865 (4)	0.7985 (7)	0.055 (2)
H13B	1.1033	0.4966	0.8017	0.067*
C14B	0.8228 (13)	0.5216 (3)	0.7359 (7)	0.053 (2)
C15B	0.8540 (17)	0.5637 (4)	0.8014 (8)	0.078 (3)
H15C	0.9784	0.5791	0.7995	0.094*
H15D	0.7446	0.5853	0.7835	0.094*
C16B	0.8602 (17)	0.5455 (4)	0.8950 (8)	0.074 (3)
H16C	0.7300	0.5486	0.9102	0.088*
H16D	0.9573	0.5623	0.9406	0.088*
C17B	0.9206 (15)	0.4937 (4)	0.8955 (7)	0.061 (3)
H17B	0.8026	0.4754	0.8988	0.073*
C18B	1.1007 (12)	0.5453 (4)	0.6553 (7)	0.066 (3)
H18D	1.1842	0.5230	0.6346	0.098*
H18E	1.1528	0.5518	0.7197	0.098*
H18F	1.0985	0.5729	0.6199	0.098*
C19B	1.1100 (14)	0.4852 (4)	0.4849 (8)	0.070 (3)
H19D	1.1994	0.4731	0.5388	0.105*
H19E	1.1310	0.5176	0.4812	0.105*
H19F	1.1353	0.4706	0.4305	0.105*
C20B	1.0874 (15)	0.4816 (4)	0.9802 (7)	0.063 (3)
C21B	1.2931 (15)	0.5009 (5)	0.9745 (7)	0.075 (3)
H21D	1.3852	0.4968	1.0330	0.112*
H21E	1.2807	0.5330	0.9599	0.112*
H21F	1.3419	0.4850	0.9272	0.112*
C22B	1.0265 (17)	0.4931 (4)	1.0705 (8)	0.077 (3)
H22C	0.8820	0.4942	1.0616	0.092*
H22D	1.0813	0.5225	1.0944	0.092*
C23B	1.1140 (17)	0.4544 (4)	1.1361 (8)	0.072 (3)
H23C	1.0421	0.4505	1.1852	0.086*
H23D	1.2550	0.4591	1.1629	0.086*
C24B	1.0799 (16)	0.4143 (4)	1.0683 (8)	0.067 (3)
H24B	0.9408	0.4041	1.0600	0.080*
C25B	1.2205 (16)	0.3719 (4)	1.0960 (8)	0.068 (3)
C26B	1.1577 (17)	0.3337 (4)	1.0273 (9)	0.083 (4)
H26D	1.1710	0.3436	0.9671	0.124*
H26E	1.0208	0.3257	1.0252	0.124*
H26F	1.2413	0.3074	1.0459	0.124*
C27B	1.217 (2)	0.3577 (5)	1.1946 (8)	0.093 (4)
H27D	1.2882	0.3294	1.2091	0.140*
H27E	1.0808	0.3537	1.2001	0.140*
H27F	1.2794	0.3811	1.2369	0.140*
C28B	0.5067 (15)	0.5375 (4)	0.2854 (8)	0.078 (3)
H28D	0.5260	0.5692	0.3020	0.117*
H28E	0.3970	0.5255	0.3088	0.117*
H28F	0.4777	0.5346	0.2192	0.117*
C29B	0.8692 (16)	0.5303 (5)	0.2890 (8)	0.082 (4)
H29D	0.9883	0.5122	0.3074	0.122*
H29E	0.8953	0.5610	0.3117	0.122*
H29F	0.8292	0.5308	0.2226	0.122*
C30B	0.6024 (12)	0.5069 (4)	0.7260 (7)	0.070 (3)
H30D	0.5157	0.5309	0.6962	0.105*
H30E	0.5770	0.5011	0.7862	0.105*
H30F	0.5776	0.4795	0.6893	0.105*
O2	0.9238 (12)	0.3164 (3)	0.7365 (6)	0.100 (3)
H2C	0.8332	0.3117	0.7665	0.150*
H2D	0.9722	0.3424	0.7547	0.150*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.081 (5)	0.097 (6)	0.037 (4)	0.008 (4)	0.010 (3)	−0.006 (4)
O1	0.095 (6)	0.106 (7)	0.127 (9)	0.000 (5)	0.027 (6)	−0.025 (7)
O2A	0.100 (5)	0.076 (5)	0.036 (4)	−0.026 (4)	0.006 (3)	0.000 (4)
O3A	0.086 (5)	0.078 (5)	0.030 (3)	−0.011 (4)	0.002 (3)	0.004 (3)
O4A	0.056 (4)	0.101 (6)	0.063 (5)	−0.002 (4)	0.012 (3)	−0.011 (4)
C1A	0.078 (7)	0.061 (7)	0.057 (7)	−0.011 (5)	−0.004 (5)	−0.003 (5)
C2A	0.093 (8)	0.063 (7)	0.057 (7)	−0.012 (6)	0.009 (6)	−0.016 (6)
C3A	0.070 (6)	0.076 (7)	0.048 (6)	−0.001 (6)	0.007 (5)	−0.005 (6)
C4A	0.054 (5)	0.066 (7)	0.054 (6)	0.007 (5)	0.009 (4)	0.009 (5)
C5A	0.053 (5)	0.059 (6)	0.053 (6)	−0.004 (4)	0.012 (4)	0.001 (5)
C6A	0.072 (6)	0.075 (7)	0.039 (5)	−0.016 (5)	0.012 (4)	−0.006 (5)
C7A	0.069 (6)	0.057 (6)	0.051 (6)	−0.010 (5)	0.011 (5)	0.002 (5)
C8A	0.049 (5)	0.076 (7)	0.041 (5)	−0.001 (4)	0.013 (4)	−0.005 (5)
C9A	0.048 (5)	0.064 (6)	0.054 (6)	−0.002 (5)	0.007 (4)	0.007 (5)
C10A	0.049 (5)	0.062 (6)	0.041 (5)	0.006 (4)	0.011 (4)	−0.001 (4)
C11A	0.067 (6)	0.058 (6)	0.055 (6)	−0.012 (5)	0.016 (5)	0.002 (5)
C12A	0.064 (6)	0.062 (6)	0.051 (6)	−0.001 (5)	0.001 (4)	0.014 (5)
C13A	0.062 (5)	0.058 (6)	0.034 (5)	−0.004 (5)	0.013 (4)	−0.001 (4)
C14A	0.055 (5)	0.058 (6)	0.047 (5)	−0.007 (4)	0.011 (4)	−0.002 (5)
C15A	0.083 (7)	0.081 (8)	0.052 (6)	−0.015 (6)	0.014 (5)	−0.006 (6)
C16A	0.072 (7)	0.093 (8)	0.041 (5)	−0.013 (6)	0.009 (5)	−0.012 (6)
C17A	0.070 (6)	0.063 (6)	0.041 (5)	−0.007 (5)	0.007 (4)	−0.003 (5)
C18A	0.047 (5)	0.089 (8)	0.064 (7)	0.003 (5)	0.013 (5)	−0.008 (6)
C19A	0.042 (5)	0.106 (9)	0.068 (7)	−0.014 (6)	0.010 (5)	−0.002 (7)
C20A	0.063 (6)	0.065 (7)	0.033 (5)	−0.004 (5)	0.009 (4)	−0.001 (4)
C21A	0.064 (6)	0.118 (10)	0.054 (6)	0.006 (6)	0.007 (5)	−0.008 (7)
C22A	0.077 (7)	0.090 (8)	0.033 (5)	−0.005 (6)	−0.006 (4)	−0.007 (6)
C23A	0.072 (7)	0.093 (9)	0.051 (6)	−0.006 (6)	0.011 (5)	−0.003 (6)
C24A	0.065 (6)	0.073 (7)	0.060 (7)	0.000 (5)	0.006 (5)	0.006 (6)
C25A	0.060 (6)	0.076 (7)	0.053 (6)	0.007 (5)	0.000 (4)	0.007 (6)
C26A	0.105 (10)	0.081 (9)	0.075 (9)	0.003 (7)	0.015 (7)	0.014 (7)
C27A	0.083 (8)	0.080 (8)	0.078 (9)	−0.004 (6)	0.014 (6)	−0.016 (7)
C28A	0.091 (8)	0.104 (10)	0.058 (7)	−0.012 (7)	0.029 (6)	0.006 (7)
C29A	0.066 (6)	0.080 (8)	0.064 (7)	0.003 (6)	−0.003 (5)	−0.005 (6)
C30A	0.044 (5)	0.100 (9)	0.071 (7)	−0.015 (5)	0.003 (5)	−0.003 (7)
O1B	0.081 (5)	0.091 (6)	0.058 (5)	−0.010 (4)	−0.003 (4)	−0.007 (4)
O2B	0.091 (5)	0.071 (5)	0.057 (4)	0.018 (4)	0.005 (4)	0.000 (4)
O3B	0.076 (5)	0.075 (5)	0.048 (4)	0.008 (4)	0.011 (3)	−0.004 (4)
O4B	0.049 (3)	0.107 (6)	0.047 (4)	−0.001 (4)	0.001 (3)	−0.014 (4)
C1B	0.082 (7)	0.063 (7)	0.046 (6)	−0.004 (5)	0.020 (5)	−0.006 (5)
C2B	0.087 (7)	0.064 (7)	0.046 (6)	0.002 (6)	0.012 (5)	−0.009 (5)
C3B	0.083 (7)	0.074 (8)	0.052 (7)	−0.004 (6)	0.011 (5)	0.001 (6)
C4B	0.060 (5)	0.071 (7)	0.049 (6)	−0.004 (5)	0.008 (4)	0.004 (5)
C5B	0.065 (6)	0.061 (6)	0.048 (6)	0.005 (5)	0.005 (4)	−0.001 (5)
C6B	0.071 (6)	0.060 (7)	0.068 (7)	0.006 (5)	0.004 (5)	−0.004 (6)
C7B	0.060 (6)	0.067 (7)	0.068 (7)	0.014 (5)	0.010 (5)	−0.005 (6)
C8B	0.038 (4)	0.062 (6)	0.054 (6)	0.002 (4)	−0.004 (4)	0.004 (5)
C9B	0.060 (5)	0.057 (6)	0.039 (5)	−0.004 (4)	0.010 (4)	−0.004 (4)
C10B	0.043 (5)	0.059 (6)	0.062 (6)	0.000 (4)	0.003 (4)	0.005 (5)
C11B	0.072 (6)	0.056 (6)	0.046 (6)	0.012 (5)	0.002 (5)	0.007 (5)
C12B	0.072 (7)	0.061 (7)	0.057 (6)	0.006 (5)	0.008 (5)	0.002 (6)
C13B	0.045 (5)	0.065 (6)	0.051 (6)	0.006 (4)	−0.002 (4)	−0.008 (5)
C14B	0.045 (5)	0.061 (6)	0.050 (6)	0.006 (4)	0.006 (4)	−0.005 (5)
C15B	0.076 (7)	0.070 (7)	0.084 (9)	0.028 (6)	0.004 (6)	−0.004 (7)
C16B	0.071 (7)	0.089 (8)	0.061 (7)	0.009 (6)	0.016 (5)	−0.013 (6)
C17B	0.060 (6)	0.075 (7)	0.045 (6)	0.004 (5)	0.002 (4)	−0.009 (5)
C18B	0.033 (4)	0.083 (7)	0.075 (7)	−0.004 (5)	−0.001 (4)	−0.003 (6)
C19B	0.050 (5)	0.091 (8)	0.068 (7)	0.010 (5)	0.008 (5)	0.001 (6)
C20B	0.068 (6)	0.072 (7)	0.042 (6)	0.001 (5)	−0.005 (5)	−0.005 (5)
C21B	0.063 (6)	0.112 (10)	0.043 (6)	−0.007 (6)	−0.002 (4)	−0.008 (6)
C22B	0.074 (7)	0.080 (8)	0.069 (7)	0.003 (6)	0.000 (6)	−0.019 (7)
C23B	0.079 (7)	0.081 (8)	0.054 (6)	−0.004 (6)	0.012 (5)	−0.004 (6)
C24B	0.065 (6)	0.071 (7)	0.062 (7)	0.000 (5)	0.008 (5)	−0.007 (6)
C25B	0.070 (6)	0.074 (8)	0.060 (7)	0.008 (6)	0.013 (5)	0.001 (6)
C26B	0.081 (8)	0.066 (7)	0.087 (9)	0.011 (6)	−0.011 (6)	−0.013 (7)
C27B	0.114 (10)	0.114 (11)	0.052 (7)	0.012 (8)	0.017 (7)	0.015 (7)
C28B	0.063 (6)	0.096 (9)	0.065 (7)	0.009 (6)	−0.007 (5)	−0.003 (7)
C29B	0.074 (7)	0.092 (9)	0.079 (9)	−0.021 (6)	0.020 (6)	−0.011 (7)
C30B	0.039 (5)	0.108 (9)	0.064 (7)	0.012 (5)	0.011 (4)	−0.009 (7)
O2	0.087 (5)	0.107 (7)	0.100 (7)	−0.004 (5)	0.007 (5)	−0.013 (6)

Geometric parameters (Å, º)

O1A—H1A	0.8200	O1B—H1B	0.8200
O1A—C3A	1.443 (11)	O1B—C3B	1.420 (12)
O1—H1C	0.8500	O2B—H2B	0.8200
O1—H1D	0.8498	O2B—C12B	1.460 (12)
O2A—H2A	0.8200	O3B—C20B	1.463 (13)
O2A—C12A	1.435 (12)	O3B—C24B	1.429 (13)
O3A—C20A	1.469 (12)	O4B—H4B	0.8200
O3A—C24A	1.450 (12)	O4B—C25B	1.451 (12)
O4A—H4A	0.8200	C1B—H1BA	0.9700
O4A—C25A	1.466 (11)	C1B—H1BB	0.9700
C1A—H1AA	0.9700	C1B—C2B	1.528 (13)
C1A—H1AB	0.9700	C1B—C10B	1.528 (14)
C1A—C2A	1.532 (14)	C2B—H2BA	0.9700
C1A—C10A	1.552 (14)	C2B—H2BB	0.9700
C2A—H2AA	0.9700	C2B—C3B	1.520 (15)
C2A—H2AB	0.9700	C3B—H3B	0.9800
C2A—C3A	1.481 (15)	C3B—C4B	1.542 (16)
C3A—H3A	0.9800	C4B—C5B	1.529 (13)
C3A—C4A	1.525 (15)	C4B—C28B	1.584 (14)
C4A—C5A	1.527 (13)	C4B—C29B	1.511 (14)
C4A—C28A	1.548 (14)	C5B—H5B	0.9800
C4A—C29A	1.544 (13)	C5B—C6B	1.529 (14)
C5A—H5A	0.9800	C5B—C10B	1.587 (13)
C5A—C6A	1.515 (14)	C6B—H6BA	0.9700
C5A—C10A	1.542 (13)	C6B—H6BB	0.9700
C6A—H6AA	0.9700	C6B—C7B	1.500 (15)
C6A—H6AB	0.9700	C7B—H7BA	0.9700
C6A—C7A	1.529 (13)	C7B—H7BB	0.9700
C7A—H7AA	0.9700	C7B—C8B	1.571 (13)
C7A—H7AB	0.9700	C8B—C9B	1.574 (13)
C7A—C8A	1.504 (13)	C8B—C14B	1.540 (13)
C8A—C9A	1.561 (14)	C8B—C18B	1.571 (11)
C8A—C14A	1.575 (12)	C9B—H9B	0.9800
C8A—C18A	1.567 (12)	C9B—C10B	1.572 (13)
C9A—H9A	0.9800	C9B—C11B	1.547 (13)
C9A—C10A	1.578 (12)	C10B—C19B	1.533 (13)
C9A—C11A	1.514 (13)	C11B—H11C	0.9700
C10A—C19A	1.577 (12)	C11B—H11D	0.9700
C11A—H11A	0.9700	C11B—C12B	1.520 (14)
C11A—H11B	0.9700	C12B—H12B	0.9800
C11A—C12A	1.529 (13)	C12B—C13B	1.505 (14)
C12A—H12A	0.9800	C13B—H13B	0.9800
C12A—C13A	1.515 (14)	C13B—C14B	1.571 (13)
C13A—H13A	0.9800	C13B—C17B	1.547 (14)
C13A—C14A	1.526 (13)	C14B—C15B	1.550 (15)
C13A—C17A	1.540 (12)	C14B—C30B	1.546 (12)
C14A—C15A	1.550 (14)	C15B—H15C	0.9700
C14A—C30A	1.559 (13)	C15B—H15D	0.9700
C15A—H15A	0.9700	C15B—C16B	1.476 (16)
C15A—H15B	0.9700	C16B—H16C	0.9700
C15A—C16A	1.533 (14)	C16B—H16D	0.9700
C16A—H16A	0.9700	C16B—C17B	1.566 (15)
C16A—H16B	0.9700	C17B—H17B	0.9800
C16A—C17A	1.551 (15)	C17B—C20B	1.540 (13)
C17A—H17A	0.9800	C18B—H18D	0.9600
C17A—C20A	1.516 (13)	C18B—H18E	0.9600
C18A—H18A	0.9600	C18B—H18F	0.9600
C18A—H18B	0.9600	C19B—H19D	0.9600
C18A—H18C	0.9600	C19B—H19E	0.9600
C19A—H19A	0.9600	C19B—H19F	0.9600
C19A—H19B	0.9600	C20B—C21B	1.537 (15)
C19A—H19C	0.9600	C20B—C22B	1.523 (15)
C20A—C21A	1.563 (14)	C21B—H21D	0.9600
C20A—C22A	1.554 (12)	C21B—H21E	0.9600
C21A—H21A	0.9600	C21B—H21F	0.9600
C21A—H21B	0.9600	C22B—H22C	0.9700
C21A—H21C	0.9600	C22B—H22D	0.9700
C22A—H22A	0.9700	C22B—C23B	1.524 (16)
C22A—H22B	0.9700	C23B—H23C	0.9700
C22A—C23A	1.481 (16)	C23B—H23D	0.9700
C23A—H23A	0.9700	C23B—C24B	1.527 (15)
C23A—H23B	0.9700	C24B—H24B	0.9800
C23A—C24A	1.499 (16)	C24B—C25B	1.566 (15)
C24A—H24A	0.9800	C25B—C26B	1.506 (15)
C24A—C25A	1.510 (15)	C25B—C27B	1.523 (15)
C25A—C26A	1.514 (15)	C26B—H26D	0.9600
C25A—C27A	1.531 (15)	C26B—H26E	0.9600
C26A—H26A	0.9600	C26B—H26F	0.9600
C26A—H26B	0.9600	C27B—H27D	0.9600
C26A—H26C	0.9600	C27B—H27E	0.9600
C27A—H27A	0.9600	C27B—H27F	0.9600
C27A—H27B	0.9600	C28B—H28D	0.9600
C27A—H27C	0.9600	C28B—H28E	0.9600
C28A—H28A	0.9600	C28B—H28F	0.9600
C28A—H28B	0.9600	C29B—H29D	0.9600
C28A—H28C	0.9600	C29B—H29E	0.9600
C29A—H29A	0.9600	C29B—H29F	0.9600
C29A—H29B	0.9600	C30B—H30D	0.9600
C29A—H29C	0.9600	C30B—H30E	0.9600
C30A—H30A	0.9600	C30B—H30F	0.9600
C30A—H30B	0.9600	O2—H2C	0.8498
C30A—H30C	0.9600	O2—H2D	0.8501
C3A—O1A—H1A	109.5	C3B—O1B—H1B	109.5
H1C—O1—H1D	101.5	C12B—O2B—H2B	109.5
C12A—O2A—H2A	109.5	C24B—O3B—C20B	109.7 (8)
C24A—O3A—C20A	110.3 (7)	C25B—O4B—H4B	109.5
C25A—O4A—H4A	109.5	H1BA—C1B—H1BB	107.7
H1AA—C1A—H1AB	107.8	C2B—C1B—H1BA	108.8
C2A—C1A—H1AA	109.0	C2B—C1B—H1BB	108.8
C2A—C1A—H1AB	109.0	C2B—C1B—C10B	113.7 (9)
C2A—C1A—C10A	113.1 (9)	C10B—C1B—H1BA	108.8
C10A—C1A—H1AA	109.0	C10B—C1B—H1BB	108.8
C10A—C1A—H1AB	109.0	C1B—C2B—H2BA	109.4
C1A—C2A—H2AA	109.2	C1B—C2B—H2BB	109.4
C1A—C2A—H2AB	109.2	H2BA—C2B—H2BB	108.0
H2AA—C2A—H2AB	107.9	C3B—C2B—C1B	111.1 (9)
C3A—C2A—C1A	112.0 (9)	C3B—C2B—H2BA	109.4
C3A—C2A—H2AA	109.2	C3B—C2B—H2BB	109.4
C3A—C2A—H2AB	109.2	O1B—C3B—C2B	110.4 (9)
O1A—C3A—C2A	110.0 (9)	O1B—C3B—H3B	108.2
O1A—C3A—H3A	108.0	O1B—C3B—C4B	108.7 (9)
O1A—C3A—C4A	108.2 (9)	C2B—C3B—H3B	108.2
C2A—C3A—H3A	108.0	C2B—C3B—C4B	113.1 (9)
C2A—C3A—C4A	114.4 (9)	C4B—C3B—H3B	108.2
C4A—C3A—H3A	108.0	C3B—C4B—C28B	105.0 (9)
C3A—C4A—C5A	108.3 (8)	C5B—C4B—C3B	108.9 (9)
C3A—C4A—C28A	107.8 (9)	C5B—C4B—C28B	108.6 (9)
C3A—C4A—C29A	110.4 (9)	C29B—C4B—C3B	111.7 (9)
C5A—C4A—C28A	109.4 (8)	C29B—C4B—C5B	115.4 (9)
C5A—C4A—C29A	113.5 (8)	C29B—C4B—C28B	106.6 (9)
C29A—C4A—C28A	107.4 (9)	C4B—C5B—H5B	104.0
C4A—C5A—H5A	103.8	C4B—C5B—C6B	115.6 (9)
C4A—C5A—C10A	117.8 (8)	C4B—C5B—C10B	117.3 (9)
C6A—C5A—C4A	115.0 (8)	C6B—C5B—H5B	104.0
C6A—C5A—H5A	103.8	C6B—C5B—C10B	110.1 (8)
C6A—C5A—C10A	110.7 (8)	C10B—C5B—H5B	104.0
C10A—C5A—H5A	103.8	C5B—C6B—H6BA	108.9
C5A—C6A—H6AA	109.4	C5B—C6B—H6BB	108.9
C5A—C6A—H6AB	109.4	H6BA—C6B—H6BB	107.7
C5A—C6A—C7A	111.1 (9)	C7B—C6B—C5B	113.3 (10)
H6AA—C6A—H6AB	108.0	C7B—C6B—H6BA	108.9
C7A—C6A—H6AA	109.4	C7B—C6B—H6BB	108.9
C7A—C6A—H6AB	109.4	C6B—C7B—H7BA	108.8
C6A—C7A—H7AA	109.0	C6B—C7B—H7BB	108.8
C6A—C7A—H7AB	109.0	C6B—C7B—C8B	113.6 (8)
H7AA—C7A—H7AB	107.8	H7BA—C7B—H7BB	107.7
C8A—C7A—C6A	112.9 (8)	C8B—C7B—H7BA	108.8
C8A—C7A—H7AA	109.0	C8B—C7B—H7BB	108.8
C8A—C7A—H7AB	109.0	C7B—C8B—C9B	108.0 (7)
C7A—C8A—C9A	110.2 (8)	C7B—C8B—C18B	106.2 (8)
C7A—C8A—C14A	114.4 (8)	C14B—C8B—C7B	111.8 (8)
C7A—C8A—C18A	108.2 (9)	C14B—C8B—C9B	108.9 (8)
C9A—C8A—C14A	105.5 (8)	C14B—C8B—C18B	110.4 (8)
C9A—C8A—C18A	111.0 (8)	C18B—C8B—C9B	111.7 (8)
C18A—C8A—C14A	107.5 (8)	C8B—C9B—H9B	105.4
C8A—C9A—H9A	103.8	C10B—C9B—C8B	116.2 (8)
C8A—C9A—C10A	115.2 (8)	C10B—C9B—H9B	105.4
C10A—C9A—H9A	103.8	C11B—C9B—C8B	110.1 (7)
C11A—C9A—C8A	113.7 (8)	C11B—C9B—H9B	105.4
C11A—C9A—H9A	103.8	C11B—C9B—C10B	113.4 (8)
C11A—C9A—C10A	114.6 (8)	C1B—C10B—C5B	105.9 (8)
C1A—C10A—C9A	108.5 (8)	C1B—C10B—C9B	108.1 (8)
C1A—C10A—C19A	106.8 (8)	C1B—C10B—C19B	109.2 (9)
C5A—C10A—C1A	107.3 (8)	C9B—C10B—C5B	106.1 (8)
C5A—C10A—C9A	108.3 (7)	C19B—C10B—C5B	113.8 (9)
C5A—C10A—C19A	113.8 (8)	C19B—C10B—C9B	113.4 (8)
C19A—C10A—C9A	111.9 (8)	C9B—C11B—H11C	108.9
C9A—C11A—H11A	108.7	C9B—C11B—H11D	108.9
C9A—C11A—H11B	108.7	H11C—C11B—H11D	107.7
C9A—C11A—C12A	114.2 (8)	C12B—C11B—C9B	113.4 (8)
H11A—C11A—H11B	107.6	C12B—C11B—H11C	108.9
C12A—C11A—H11A	108.7	C12B—C11B—H11D	108.9
C12A—C11A—H11B	108.7	O2B—C12B—C11B	106.6 (8)
O2A—C12A—C11A	106.5 (8)	O2B—C12B—H12B	109.2
O2A—C12A—H12A	108.9	O2B—C12B—C13B	111.9 (8)
O2A—C12A—C13A	114.1 (8)	C11B—C12B—H12B	109.2
C11A—C12A—H12A	108.9	C13B—C12B—C11B	110.8 (9)
C13A—C12A—C11A	109.3 (8)	C13B—C12B—H12B	109.2
C13A—C12A—H12A	108.9	C12B—C13B—H13B	107.4
C12A—C13A—H13A	106.7	C12B—C13B—C14B	109.9 (8)
C12A—C13A—C14A	110.3 (8)	C12B—C13B—C17B	120.5 (10)
C12A—C13A—C17A	120.1 (8)	C14B—C13B—H13B	107.4
C14A—C13A—H13A	106.7	C17B—C13B—H13B	107.4
C14A—C13A—C17A	105.6 (7)	C17B—C13B—C14B	103.5 (7)
C17A—C13A—H13A	106.7	C8B—C14B—C13B	109.4 (7)
C13A—C14A—C8A	113.3 (8)	C8B—C14B—C15B	118.3 (9)
C13A—C14A—C15A	100.5 (8)	C8B—C14B—C30B	112.6 (7)
C13A—C14A—C30A	111.0 (8)	C15B—C14B—C13B	99.5 (7)
C15A—C14A—C8A	116.0 (8)	C30B—C14B—C13B	110.0 (9)
C15A—C14A—C30A	104.9 (8)	C30B—C14B—C15B	106.1 (8)
C30A—C14A—C8A	110.5 (8)	C14B—C15B—H15C	110.6
C14A—C15A—H15A	110.9	C14B—C15B—H15D	110.6
C14A—C15A—H15B	110.9	H15C—C15B—H15D	108.7
H15A—C15A—H15B	108.9	C16B—C15B—C14B	105.9 (10)
C16A—C15A—C14A	104.2 (9)	C16B—C15B—H15C	110.6
C16A—C15A—H15A	110.9	C16B—C15B—H15D	110.6
C16A—C15A—H15B	110.9	C15B—C16B—H16C	110.2
C15A—C16A—H16A	110.3	C15B—C16B—H16D	110.2
C15A—C16A—H16B	110.3	C15B—C16B—C17B	107.7 (9)
C15A—C16A—C17A	107.1 (8)	H16C—C16B—H16D	108.5
H16A—C16A—H16B	108.6	C17B—C16B—H16C	110.2
C17A—C16A—H16A	110.3	C17B—C16B—H16D	110.2
C17A—C16A—H16B	110.3	C13B—C17B—C16B	103.5 (9)
C13A—C17A—C16A	103.6 (8)	C13B—C17B—H17B	107.9
C13A—C17A—H17A	107.4	C16B—C17B—H17B	107.9
C16A—C17A—H17A	107.4	C20B—C17B—C13B	117.5 (8)
C20A—C17A—C13A	117.7 (8)	C20B—C17B—C16B	111.8 (9)
C20A—C17A—C16A	112.9 (9)	C20B—C17B—H17B	107.9
C20A—C17A—H17A	107.4	C8B—C18B—H18D	109.5
C8A—C18A—H18A	109.5	C8B—C18B—H18E	109.5
C8A—C18A—H18B	109.5	C8B—C18B—H18F	109.5
C8A—C18A—H18C	109.5	H18D—C18B—H18E	109.5
H18A—C18A—H18B	109.5	H18D—C18B—H18F	109.5
H18A—C18A—H18C	109.5	H18E—C18B—H18F	109.5
H18B—C18A—H18C	109.5	C10B—C19B—H19D	109.5
C10A—C19A—H19A	109.5	C10B—C19B—H19E	109.5
C10A—C19A—H19B	109.5	C10B—C19B—H19F	109.5
C10A—C19A—H19C	109.5	H19D—C19B—H19E	109.5
H19A—C19A—H19B	109.5	H19D—C19B—H19F	109.5
H19A—C19A—H19C	109.5	H19E—C19B—H19F	109.5
H19B—C19A—H19C	109.5	O3B—C20B—C17B	107.2 (8)
O3A—C20A—C17A	108.2 (8)	O3B—C20B—C21B	106.0 (9)
O3A—C20A—C21A	106.6 (8)	O3B—C20B—C22B	104.5 (9)
O3A—C20A—C22A	103.5 (8)	C21B—C20B—C17B	113.4 (9)
C17A—C20A—C21A	114.2 (9)	C22B—C20B—C17B	111.5 (9)
C17A—C20A—C22A	112.8 (8)	C22B—C20B—C21B	113.5 (9)
C22A—C20A—C21A	110.8 (8)	C20B—C21B—H21D	109.5
C20A—C21A—H21A	109.5	C20B—C21B—H21E	109.5
C20A—C21A—H21B	109.5	C20B—C21B—H21F	109.5
C20A—C21A—H21C	109.5	H21D—C21B—H21E	109.5
H21A—C21A—H21B	109.5	H21D—C21B—H21F	109.5
H21A—C21A—H21C	109.5	H21E—C21B—H21F	109.5
H21B—C21A—H21C	109.5	C20B—C22B—H22C	110.9
C20A—C22A—H22A	111.1	C20B—C22B—H22D	110.9
C20A—C22A—H22B	111.1	C20B—C22B—C23B	104.5 (9)
H22A—C22A—H22B	109.1	H22C—C22B—H22D	108.9
C23A—C22A—C20A	103.3 (9)	C23B—C22B—H22C	110.9
C23A—C22A—H22A	111.1	C23B—C22B—H22D	110.9
C23A—C22A—H22B	111.1	C22B—C23B—H23C	111.8
C22A—C23A—H23A	111.1	C22B—C23B—H23D	111.8
C22A—C23A—H23B	111.1	C22B—C23B—C24B	99.7 (9)
C22A—C23A—C24A	103.5 (9)	H23C—C23B—H23D	109.6
H23A—C23A—H23B	109.0	C24B—C23B—H23C	111.8
C24A—C23A—H23A	111.1	C24B—C23B—H23D	111.8
C24A—C23A—H23B	111.1	O3B—C24B—C23B	106.5 (9)
O3A—C24A—C23A	104.2 (9)	O3B—C24B—H24B	108.6
O3A—C24A—H24A	108.6	O3B—C24B—C25B	108.5 (9)
O3A—C24A—C25A	108.6 (8)	C23B—C24B—H24B	108.6
C23A—C24A—H24A	108.6	C23B—C24B—C25B	116.0 (9)
C23A—C24A—C25A	117.9 (10)	C25B—C24B—H24B	108.6
C25A—C24A—H24A	108.6	O4B—C25B—C24B	108.8 (9)
O4A—C25A—C24A	109.9 (9)	O4B—C25B—C26B	110.7 (9)
O4A—C25A—C26A	105.1 (9)	O4B—C25B—C27B	105.7 (9)
O4A—C25A—C27A	107.4 (8)	C26B—C25B—C24B	109.9 (9)
C24A—C25A—C26A	109.1 (9)	C26B—C25B—C27B	112.5 (11)
C24A—C25A—C27A	112.4 (10)	C27B—C25B—C24B	109.1 (10)
C26A—C25A—C27A	112.7 (10)	C25B—C26B—H26D	109.5
C25A—C26A—H26A	109.5	C25B—C26B—H26E	109.5
C25A—C26A—H26B	109.5	C25B—C26B—H26F	109.5
C25A—C26A—H26C	109.5	H26D—C26B—H26E	109.5
H26A—C26A—H26B	109.5	H26D—C26B—H26F	109.5
H26A—C26A—H26C	109.5	H26E—C26B—H26F	109.5
H26B—C26A—H26C	109.5	C25B—C27B—H27D	109.5
C25A—C27A—H27A	109.5	C25B—C27B—H27E	109.5
C25A—C27A—H27B	109.5	C25B—C27B—H27F	109.5
C25A—C27A—H27C	109.5	H27D—C27B—H27E	109.5
H27A—C27A—H27B	109.5	H27D—C27B—H27F	109.5
H27A—C27A—H27C	109.5	H27E—C27B—H27F	109.5
H27B—C27A—H27C	109.5	C4B—C28B—H28D	109.5
C4A—C28A—H28A	109.5	C4B—C28B—H28E	109.5
C4A—C28A—H28B	109.5	C4B—C28B—H28F	109.5
C4A—C28A—H28C	109.5	H28D—C28B—H28E	109.5
H28A—C28A—H28B	109.5	H28D—C28B—H28F	109.5
H28A—C28A—H28C	109.5	H28E—C28B—H28F	109.5
H28B—C28A—H28C	109.5	C4B—C29B—H29D	109.5
C4A—C29A—H29A	109.5	C4B—C29B—H29E	109.5
C4A—C29A—H29B	109.5	C4B—C29B—H29F	109.5
C4A—C29A—H29C	109.5	H29D—C29B—H29E	109.5
H29A—C29A—H29B	109.5	H29D—C29B—H29F	109.5
H29A—C29A—H29C	109.5	H29E—C29B—H29F	109.5
H29B—C29A—H29C	109.5	C14B—C30B—H30D	109.5
C14A—C30A—H30A	109.5	C14B—C30B—H30E	109.5
C14A—C30A—H30B	109.5	C14B—C30B—H30F	109.5
C14A—C30A—H30C	109.5	H30D—C30B—H30E	109.5
H30A—C30A—H30B	109.5	H30D—C30B—H30F	109.5
H30A—C30A—H30C	109.5	H30E—C30B—H30F	109.5
H30B—C30A—H30C	109.5	H2C—O2—H2D	104.9
O1A—C3A—C4A—C5A	−174.9 (7)	O1B—C3B—C4B—C5B	−174.0 (8)
O1A—C3A—C4A—C28A	66.8 (11)	O1B—C3B—C4B—C28B	69.8 (11)
O1A—C3A—C4A—C29A	−50.1 (11)	O1B—C3B—C4B—C29B	−45.3 (12)
O2A—C12A—C13A—C14A	175.5 (8)	O2B—C12B—C13B—C14B	176.8 (8)
O2A—C12A—C13A—C17A	−61.5 (12)	O2B—C12B—C13B—C17B	−63.1 (12)
O3A—C20A—C22A—C23A	25.7 (11)	O3B—C20B—C22B—C23B	26.9 (11)
O3A—C24A—C25A—O4A	55.8 (11)	O3B—C24B—C25B—O4B	56.0 (11)
O3A—C24A—C25A—C26A	170.5 (9)	O3B—C24B—C25B—C26B	−65.3 (12)
O3A—C24A—C25A—C27A	−63.8 (12)	O3B—C24B—C25B—C27B	170.8 (9)
C1A—C2A—C3A—O1A	177.5 (9)	C1B—C2B—C3B—O1B	177.8 (9)
C1A—C2A—C3A—C4A	55.6 (13)	C1B—C2B—C3B—C4B	55.7 (13)
C2A—C1A—C10A—C5A	50.9 (11)	C2B—C1B—C10B—C5B	54.6 (11)
C2A—C1A—C10A—C9A	167.7 (8)	C2B—C1B—C10B—C9B	168.0 (8)
C2A—C1A—C10A—C19A	−71.5 (11)	C2B—C1B—C10B—C19B	−68.3 (11)
C2A—C3A—C4A—C5A	−52.0 (12)	C2B—C3B—C4B—C5B	−51.1 (12)
C2A—C3A—C4A—C28A	−170.2 (9)	C2B—C3B—C4B—C28B	−167.2 (9)
C2A—C3A—C4A—C29A	72.8 (12)	C2B—C3B—C4B—C29B	77.7 (12)
C3A—C4A—C5A—C6A	−174.8 (8)	C3B—C4B—C5B—C6B	−175.8 (9)
C3A—C4A—C5A—C10A	51.9 (11)	C3B—C4B—C5B—C10B	51.6 (12)
C4A—C5A—C6A—C7A	162.2 (8)	C4B—C5B—C6B—C7B	163.8 (8)
C4A—C5A—C10A—C1A	−51.8 (11)	C4B—C5B—C10B—C1B	−52.9 (11)
C4A—C5A—C10A—C9A	−168.8 (8)	C4B—C5B—C10B—C9B	−167.6 (8)
C4A—C5A—C10A—C19A	66.1 (11)	C4B—C5B—C10B—C19B	67.0 (12)
C5A—C6A—C7A—C8A	59.1 (12)	C5B—C6B—C7B—C8B	56.3 (12)
C6A—C5A—C10A—C1A	173.1 (8)	C6B—C5B—C10B—C1B	172.1 (8)
C6A—C5A—C10A—C9A	56.1 (10)	C6B—C5B—C10B—C9B	57.4 (11)
C6A—C5A—C10A—C19A	−69.0 (10)	C6B—C5B—C10B—C19B	−68.0 (12)
C6A—C7A—C8A—C9A	−51.1 (11)	C6B—C7B—C8B—C9B	−49.2 (11)
C6A—C7A—C8A—C14A	−169.8 (8)	C6B—C7B—C8B—C14B	−168.9 (9)
C6A—C7A—C8A—C18A	70.4 (11)	C6B—C7B—C8B—C18B	70.7 (11)
C7A—C8A—C9A—C10A	48.8 (10)	C7B—C8B—C9B—C10B	52.0 (10)
C7A—C8A—C9A—C11A	−176.1 (8)	C7B—C8B—C9B—C11B	−177.4 (8)
C7A—C8A—C14A—C13A	178.1 (8)	C7B—C8B—C14B—C13B	179.5 (8)
C7A—C8A—C14A—C15A	−66.4 (11)	C7B—C8B—C14B—C15B	−67.6 (11)
C7A—C8A—C14A—C30A	52.8 (12)	C7B—C8B—C14B—C30B	56.9 (11)
C8A—C9A—C10A—C1A	−167.3 (8)	C8B—C9B—C10B—C1B	−169.7 (8)
C8A—C9A—C10A—C5A	−51.1 (10)	C8B—C9B—C10B—C5B	−56.5 (10)
C8A—C9A—C10A—C19A	75.2 (10)	C8B—C9B—C10B—C19B	69.1 (11)
C8A—C9A—C11A—C12A	54.0 (11)	C8B—C9B—C11B—C12B	53.6 (12)
C8A—C14A—C15A—C16A	−162.5 (8)	C8B—C14B—C15B—C16B	−158.9 (8)
C9A—C8A—C14A—C13A	56.8 (9)	C9B—C8B—C14B—C13B	60.3 (9)
C9A—C8A—C14A—C15A	172.2 (8)	C9B—C8B—C14B—C15B	173.2 (7)
C9A—C8A—C14A—C30A	−68.5 (10)	C9B—C8B—C14B—C30B	−62.4 (10)
C9A—C11A—C12A—O2A	−177.6 (8)	C9B—C11B—C12B—O2B	−177.1 (8)
C9A—C11A—C12A—C13A	−53.9 (12)	C9B—C11B—C12B—C13B	−55.1 (12)
C10A—C1A—C2A—C3A	−55.1 (13)	C10B—C1B—C2B—C3B	−59.2 (12)
C10A—C5A—C6A—C7A	−61.4 (10)	C10B—C5B—C6B—C7B	−60.4 (11)
C10A—C9A—C11A—C12A	−170.6 (8)	C10B—C9B—C11B—C12B	−174.3 (8)
C11A—C9A—C10A—C1A	58.0 (11)	C11B—C9B—C10B—C1B	61.3 (10)
C11A—C9A—C10A—C5A	174.2 (8)	C11B—C9B—C10B—C5B	174.5 (8)
C11A—C9A—C10A—C19A	−59.5 (11)	C11B—C9B—C10B—C19B	−59.9 (11)
C11A—C12A—C13A—C14A	56.4 (11)	C11B—C12B—C13B—C14B	58.0 (11)
C11A—C12A—C13A—C17A	179.4 (8)	C11B—C12B—C13B—C17B	178.1 (8)
C12A—C13A—C14A—C8A	−61.6 (10)	C12B—C13B—C14B—C8B	−62.1 (11)
C12A—C13A—C14A—C15A	174.1 (8)	C12B—C13B—C14B—C15B	173.2 (9)
C12A—C13A—C14A—C30A	63.5 (10)	C12B—C13B—C14B—C30B	62.1 (11)
C12A—C13A—C17A—C16A	−154.4 (9)	C12B—C13B—C17B—C16B	−153.5 (9)
C12A—C13A—C17A—C20A	80.3 (12)	C12B—C13B—C17B—C20B	82.7 (12)
C13A—C14A—C15A—C16A	−40.0 (10)	C13B—C14B—C15B—C16B	−40.6 (10)
C13A—C17A—C20A—O3A	−70.3 (11)	C13B—C17B—C20B—O3B	−69.6 (12)
C13A—C17A—C20A—C21A	48.1 (13)	C13B—C17B—C20B—C21B	47.0 (13)
C13A—C17A—C20A—C22A	175.8 (9)	C13B—C17B—C20B—C22B	176.6 (10)
C14A—C8A—C9A—C10A	172.8 (7)	C14B—C8B—C9B—C10B	173.5 (7)
C14A—C8A—C9A—C11A	−52.1 (9)	C14B—C8B—C9B—C11B	−55.9 (9)
C14A—C13A—C17A—C16A	−29.2 (10)	C14B—C13B—C17B—C16B	−30.3 (10)
C14A—C13A—C17A—C20A	−154.5 (9)	C14B—C13B—C17B—C20B	−154.1 (9)
C14A—C15A—C16A—C17A	22.9 (11)	C14B—C15B—C16B—C17B	22.8 (11)
C15A—C16A—C17A—C13A	3.4 (11)	C15B—C16B—C17B—C13B	5.0 (11)
C15A—C16A—C17A—C20A	131.8 (9)	C15B—C16B—C17B—C20B	132.4 (10)
C16A—C17A—C20A—O3A	169.1 (8)	C16B—C17B—C20B—O3B	170.9 (9)
C16A—C17A—C20A—C21A	−72.5 (11)	C16B—C17B—C20B—C21B	−72.4 (12)
C16A—C17A—C20A—C22A	55.2 (12)	C16B—C17B—C20B—C22B	57.1 (12)
C17A—C13A—C14A—C8A	167.3 (8)	C17B—C13B—C14B—C8B	167.9 (8)
C17A—C13A—C14A—C15A	43.0 (10)	C17B—C13B—C14B—C15B	43.2 (10)
C17A—C13A—C14A—C30A	−67.6 (10)	C17B—C13B—C14B—C30B	−67.9 (9)
C17A—C20A—C22A—C23A	142.4 (10)	C17B—C20B—C22B—C23B	142.4 (9)
C18A—C8A—C9A—C10A	−71.0 (10)	C18B—C8B—C9B—C10B	−64.4 (10)
C18A—C8A—C9A—C11A	64.1 (11)	C18B—C8B—C9B—C11B	66.2 (10)
C18A—C8A—C14A—C13A	−61.7 (11)	C18B—C8B—C14B—C13B	−62.6 (10)
C18A—C8A—C14A—C15A	53.7 (11)	C18B—C8B—C14B—C15B	50.3 (11)
C18A—C8A—C14A—C30A	172.9 (9)	C18B—C8B—C14B—C30B	174.8 (9)
C20A—O3A—C24A—C23A	−20.4 (11)	C20B—O3B—C24B—C23B	−20.3 (11)
C20A—O3A—C24A—C25A	−146.8 (9)	C20B—O3B—C24B—C25B	−145.7 (8)
C20A—C22A—C23A—C24A	−38.2 (11)	C20B—C22B—C23B—C24B	−37.5 (11)
C21A—C20A—C22A—C23A	−88.2 (11)	C21B—C20B—C22B—C23B	−88.1 (12)
C22A—C23A—C24A—O3A	36.6 (11)	C22B—C23B—C24B—O3B	35.6 (11)
C22A—C23A—C24A—C25A	156.9 (9)	C22B—C23B—C24B—C25B	156.4 (10)
C23A—C24A—C25A—O4A	−62.3 (12)	C23B—C24B—C25B—O4B	−63.7 (12)
C23A—C24A—C25A—C26A	52.5 (13)	C23B—C24B—C25B—C26B	175.0 (10)
C23A—C24A—C25A—C27A	178.2 (9)	C23B—C24B—C25B—C27B	51.1 (14)
C24A—O3A—C20A—C17A	−123.1 (8)	C24B—O3B—C20B—C17B	−122.7 (9)
C24A—O3A—C20A—C21A	113.7 (9)	C24B—O3B—C20B—C21B	115.9 (9)
C24A—O3A—C20A—C22A	−3.2 (11)	C24B—O3B—C20B—C22B	−4.2 (10)
C28A—C4A—C5A—C6A	−57.6 (11)	C28B—C4B—C5B—C6B	−61.9 (11)
C28A—C4A—C5A—C10A	169.1 (9)	C28B—C4B—C5B—C10B	165.4 (9)
C29A—C4A—C5A—C6A	62.3 (11)	C29B—C4B—C5B—C6B	57.6 (13)
C29A—C4A—C5A—C10A	−71.0 (12)	C29B—C4B—C5B—C10B	−75.0 (13)
C30A—C14A—C15A—C16A	75.3 (10)	C30B—C14B—C15B—C16B	73.6 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1A···O4A^i	0.82	2.01	2.816 (11)	169
O1—H1C···O2A	0.85	2.09	2.937 (12)	177
O1—H1D···O2B^ii	0.85	2.20	3.043 (11)	173
O2A—H2A···O3A	0.82	1.88	2.664 (9)	159
O4A—H4A···O2	0.82	2.18	2.997 (11)	175
O1B—H1B···O4B^iii	0.82	2.02	2.825 (10)	169
O2B—H2B···O3B	0.82	1.86	2.657 (10)	165
O4B—H4B···O1^iv	0.82	2.16	2.982 (12)	177
O2—H2C···O2A	0.85	2.18	3.026 (12)	179
O2—H2D···O2B	0.85	2.10	2.947 (12)	176

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