Accurate stereochemistry for two related 22,26-epimino­cholestene derivatives

Regioselective opening of ring E of solasodine under various conditions afforded (25R)-22,26-epimino­cholesta-5,22(N)-di­ene-3β,16β-diyl diacetate (previously known as 3,16-diacetyl pseudosolasodine B), C₃₁H₄₇NO₄, or (22S,25R)-16β-hydr­oxy-22,26-epimino­cholesta-5-en-3β-yl acetate (a derivative of the naturally occurring alkaloid oblonginine), C₂₉H₄₇NO₃. In both cases, the reactions are carried out with retention of chirality at the C16, C20 and C25 stereogenic centers, which are found to be S, S and R, respectively. Although pseudosolasodine was synthesized 50 years ago, these accurate assignments clarify some controversial points about the actual stereochemistry for these alkaloids. This is of particular importance in the case of oblonginine, since this compound is currently under consideration for the treatment of aphasia arising from apoplexy; the present study defines a diastereoisomerically pure compound for pharmacological studies.

Comment

Many plants of the Solanaceae family accumulate steroidal alkaloids based on the C₂₇ cholestane skeleton, e.g. solasodine, (1), and tomatidine, which are N-analogues of sapogenins (Friedman & McDonald, 1997). For a long time, (1) has been an essential starting material for the partial synthesis of pregnane derivatives (Sato et al., 1957). 22,26-Epimino­cholestenes are also accessible from (1), through a selective E-ring cleavage under reductive conditions (Bird et al., 1979) or by acidic acetolysis. For instance, Sato et al. (1957) performed a selective E-ring opening of (1) by treatment with Ac₂O/AcOH and ZnCl₂ at 298 K over a long time period, affording the 22,26-epimino­cholestadiene framework (I), also known as 3,16-diacetyl pseudosolasodine B.

During our work on sapogenin acetolysis, we probed a variety of Lewis acids with the hope of optimizing both the ability to regioselectively open ring E and the reaction rates. We have found that Et₂O·BF₃ gives excellent results. In this way, (I) may be prepared starting from (1) in quantitative yield in remarkably short reaction times (see scheme). All spectroscopic and physical data for the product fit well with those of an authentic sample of pseudosolasodine B diacetate. However, an X-ray study was necessary in order to assess the absolute configuration at atom C20. This aspect should not be seen as a trivial matter, since Yang et al. (2004) claimed that epimerization at C20 occurs if an acid harder than ZnCl₂ is used. We, however, have never detected such an epimerization in the case of sapogenins treated under similar conditions (Sandoval-Ramírez et al., 1999, 2003). It is also known that the reaction course may be complicated by nucleophilic attacks at atom C16 (Iglesias-Arteaga et al., 2004) and epimerization at atom C25 (LaCour et al., 1999).

A similar controversy about stereochemistry appeared in the case of oblonginine, a naturally occurring 22,26-epimino­cholestene. The mol­ecule was first assigned a stereochemistry of 22R,25S (Kadota et al., 1995). However, a re-examination using X-ray crystallography and high-resolution NMR spectroscopy revealed that oblonginine is (22S,25R)-22,26-epimino­cholest-5-en-3β-ol (Lowe et al., 1998). The X-ray structure of oblonginine monohydrate reported in that paper was unfortunately not deposited with the Cambridge Structural Database (Version 5.29; Allen, 2002) (see refcode CADNIE). We can now confirm this assignment on the basis of the X-ray structure of a C16-functionalized oblonginine monoacetate, (II), synthesized from (1) following a published procedure (Kusano et al., 1970; see scheme).

The A–D steroidal nucleus of (I) exhibits the expected geometry, identical to that of solasodine (Vega-Baez et al., 2006). The cleavage of the C22—O bond in ring E of solasodine occurs without inversion, and the stereogenic centers remain as 16S and 20S. The six-membered ring F includes a double bond (C22=N27; Table 1) and exhibits a half-chair conformation [the puckering parameters are θ = 127.1 (7)° and φ = 31.7 (9)°; the puckering amplitude is 0.466 (6) Å; the atom sequence defining ring F is N27/C22–C26 (Cremer & Pople, 1975)]. As mentioned by Sato et al. (1957), (I) should equilibrate only under constraint to its tautomeric form including a C20=N22 double bond. In the solid state, the C20—C22 bond length clearly shows that this bond is a σ single bond without participation of tautomeric forms. The absolute configuration for atom C25 is unchanged compared with the starting material, viz. 25R, with methyl atom C28 occupying an equatorial position in ring F (Fig. 1).

The geometric features for the A–D nucleus in (II) are similar to those found in (I). Cleavage of the C22—O bond of solasodine occurs with retention of configuration for atoms C16, C20 and C25, as for (I). The 22R configuration of the spiro C atom of solasodine changes to 22S in (II), owing to the formation of a C—H bond at atom C22. The main difference between (I) and (II) is thus the conformation of ring F (Fig. 2 and Table 2), which now exhibits a chair form [the puckering parameters are θ = 177.6 (4)° and φ = 93 (8)°; atom sequence as for (I)]. The relative positions of the NH group in ring F and the hydr­oxy substituent at atom C16 in ring D allow the formation of a rather strong intra­molecular O—H⋯N hydrogen bond [D⋯A = 2.777 (4) Å, H⋯A = 1.93 (4) Å and D—H⋯A = 157 (5)°]. This stabilizing inter­action explains why the OH group at atom C3 in solasodine is acetyl­ated, while the OH group formed during E-ring opening is retained as a hydr­oxy group, at least when the conditions of Kusano et al. (1970) are applied. Such a protection of the C16—OH functionality is not possible for diacetate (I).

Figure 1 The structure of (I), with displacement ellipsoids at the 30% probability level for non-H atoms.

Figure 2 The structure of (II), with displacement ellipsoids at the 30% probability level for non-H atoms. Atoms O31B and C32B, disordered with O31A and C32A, have been omitted for clarity. The intra­molecular hydrogen bond is shown as a dashed line.

Experimental

For the synthesis of (I), a mixture of solasodine (300 mg, 0.72 mmol), Ac₂O (3.0 ml, 32 mmol), AcOH (1.0 ml, 17 mmol) and Et₂O·BF₃ (0.7 ml, 5.5 mmol) was stirred for 20 s at 298 K. The reaction mixture was poured into iced water and shaken vigorously. Concentrated NH₄OH was added until a basic pH was obtained, and the product was extracted with CH₂Cl₂ (3 × 10 ml), washed with brine and water, dried over anhydrous Mg₂SO₄, and finally concentrated to dryness under reduced pressure. The crude product was chromatographed over silica gel using hexane/EtOAc (7:3), affording (I) in quantitative yield. Suitable single crystals were obtained by slow evaporation of an AcOEt solution. Spectroscopic data are in full agreement with the crystal structure (see archived CIF). Compound (II) was prepared following a literature procedure (Kusano et al., 1970). Suitable single crystals of (II) were obtained by slow evaporation of an AcOEt solution. Spectroscopic data are in full agreement with the crystal structure (see archived CIF).

Compound (I)

Crystal data

• C₃₁H₄₇NO₄

• M_r = 497.70

• Orthorhombic, P 2₁ 2₁ 2₁

• a = 6.1137 (16) Å

• b = 11.6779 (14) Å

• c = 41.330 (5) Å

• V = 2950.8 (9) ų

• Z = 4

• Mo Kα radiation

• μ = 0.07 mm⁻¹

• T = 296 (1) K

• 0.60 × 0.26 × 0.16 mm

Data collection

• Bruker P4 diffractometer

• 3812 measured reflections

• 3026 independent reflections

• 1931 reflections with I > 2σ(I)

• R_int = 0.028

• 3 standard reflections every 97 reflections intensity decay: none

Refinement

• R[F² > 2σ(F²)] = 0.052

• wR(F²) = 0.154

• S = 1.03

• 3026 reflections

• 332 parameters

• H-atom parameters constrained

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.20 e Å⁻³

Table 1
Selected geometric parameters (Å, °) for (I)

C5—C6	1.329 (5)
C16—O33	1.455 (5)
C20—C21	1.523 (6)
C20—C22	1.527 (5)
C22—N27	1.282 (5)
C26—N27	1.484 (6)

C5—C6—C7	125.7 (4)
C22—N27—C26	118.9 (4)

Compound (II)

Crystal data

• C₂₉H₄₇NO₃

• M_r = 457.68

• Monoclinic, C 2

• a = 10.026 (2) Å

• b = 7.4403 (14) Å

• c = 35.508 (6) Å

• β = 95.512 (18)°

• V = 2636.4 (9) ų

• Z = 4

• Mo Kα radiation

• μ = 0.07 mm⁻¹

• T = 296 (1) K

• 0.60 × 0.40 × 0.18 mm

Data collection

• Bruker P4 diffractometer

• 4449 measured reflections

• 2526 independent reflections

• 2236 reflections with I > 2σ(I)

• R_int = 0.043

• 3 standard reflections every 97 reflections intensity decay: 2%

Refinement

• R[F² > 2σ(F²)] = 0.049

• wR(F²) = 0.135

• S = 1.04

• 2526 reflections

• 322 parameters

• 5 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.16 e Å⁻³

• Δρ_min = −0.28 e Å⁻³

Table 2
Selected geometric parameters (Å, °) for (II)

C5—C6	1.313 (5)
C16—O33	1.435 (4)
C20—C21	1.536 (5)
C20—C22	1.557 (4)
C22—N27	1.483 (5)
C26—N27	1.466 (4)

C5—C6—C7	124.9 (3)
C22—N27—C26	112.7 (3)

Carbonyl atom O31 and methyl group C32 in (II) are disordered over two sites, for which occupancies were refined and converged to 0.47 (4) and 0.53 (4) for O31A/C32A and O31B/C32B, respectively. In order to obtain a sensible geometry for this acetate group, bond lengths involving disordered sites were restrained [C30—O31 = 1.20 (1) Å (two restraints) and C30—C32 = 1.53 (1) Å (two restraints)]. All C-bonded H atoms in (II) were placed in idealized positions and constrained to ride on their parent atoms, with C—H bond lengths fixed at 0.93 (H6A), 0.96 (methyl CH₃), 0.97 (methyl­ene CH₂) and 0.98 Å (methine CH). U_iso(H) values were calculated at 1.3U_eq(C) for methyl groups and 1.2U_eq(C) otherwise. Rigid methyl groups were allowed to rotate about their C—C bonds in order to obtain accurate torsion angles. H atoms bonded to heteroatoms N27 and O33 were found in a difference map and refined with free coordinates [U_iso(H) = 1.3U_eq(N,O)]. For (I), the acetate group at atom C3 is almost certainly disordered as in (II), as reflected in the displacement parameters for atoms O31 and C32. However, we were unable to model disordered sites satisfactorily. H atoms were placed in idealized positions, with C—H bond lengths fixed as for (II) and with U_iso(H) values of 1.5U_eq(C) for methyl groups and 1.2U_eq(C) otherwise. In both structures, Friedel pairs [663 for (I) and 394 for (II)] were merged and the stereochemistry assumed from the synthesis.

For both compounds, data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL-Plus (Release 5.10; Sheldrick, 2008); program(s) used to refine structure: SHELXTL-Plus; mol­ecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXTL-Plus and PLATON (Spek, 2003).

Supporting information

S1. Comment

Many plants of the Solanaceae family accumulate steroidal alkaloids based on the C₂₇ cholestane skeleton, e.g. solasodine (1) and tomatidine, which are N-analogues of sapogenins (Friedman & McDonald, 1997). For a long time, (1) has been an essential starting material for the partial synthesis of pregnane derivatives (Sato et al., 1957). 22,26-Epiminocholestenes are also accessible from (1), through a selective E-ring cleavage, under reductive conditions (Bird et al., 1979) or by acidic acetolysis. For instance, Sato et al. (1957) performed a selective E-ring opening of (1) by treatment with Ac₂O/AcOH and ZnCl₂, at 298 K, over a long time period, affording the 22,26-epiminocholestadiene framework (I), also known as 3,16-diacetyl pseudosolasodine B.

During our work on sapogenin acetolysis, we probed a variety of Lewis acids with the hope of optimizing both the ability to regioselectively open ring E and the reaction rates. We have found that Et₂O·BF₃ gives excellent results. In this way, (I) may be prepared starting from (1) in quantitative yield, in remarkably short reaction times (see scheme). All spectroscopic and physical data for the product fit well with those of an authentic sample of pseudosolasodine B diacetate. However, an X-ray study was necessary in order to assess the absolute configuration at C20. This aspect should not be seen as a trivial matter, since Yang et al. (2004) claimed that epimerization at C20 occurs if an acid harder than ZnCl₂ is used. We, however, have never detected such an epimerization in the case of sapogenins treated under similar conditions (Sandoval-Ramírez et al., 1999, 2003). It is also known that the reaction course may be complicated by nucleophilic attacks at C16 (Iglesias-Arteaga et al., 2004) and epimerization at C25 (LaCour et al., 1999).

A similar controversy about stereochemistry appeared in the case of oblonginine, a naturally occurring 22,26-epiminocholestene. The molecule was first assigned a sterochemistry of 22R,25S (Kadota et al., 1995). However, a re-examination using X-ray crystallography and high-resolution NMR spectroscopy revealed that oblonginine is (22S,25R)-22,26-epiminocholest-5-en-3β-ol (Lowe et al., 1998). The X-ray structure of oblonginine monohydrate reported in that paper was unfortunately not deposited with the Cambridge Structural Database [Version 5.29 (Allen, 2002); see refcode CADNIE]. We can now confirm this assignment on the basis of the X-ray structure of a C16-functionalized oblonginine monoacetate, (II), synthesized from (1) following a published procedure (Kusano et al., 1970; see scheme).

The A–D steroidal nucleus of (I) exhibits the expected geometry, identical to that of solasodine (Vega-Baez et al., 2006). The cleavage of the C22—O bond in ring E of solasodine occurs without inversion, and the stereogenic centers remain as 16S and 20S. The six-membered ring F includes a double bond (C22═N27; Table 1) and exhibits a half-chair conformation [puckering parameters θ = 127.1 (7)° and ϕ = 31.7 (9)°; puckering amplitude 0.466 (6) Å; atom sequence defining ring F: N27/C22–C26; Cremer & Pople, 1975]. As mentioned by Sato et al. (1957), (I) should equilibrate only under constraint to its tautomeric form including a C20═N22 double bond. In the solid state, the C20—C22 bond length clearly shows that this bond is a σ single bond without participation of tautomeric forms. The absolute configuration for atom C25 is unchanged compared with the starting material, 25R, with methyl atom C28 occupying an equatorial position in ring F (Fig. 1).

The geometric features for the A–D nucleus in (II) are similar to those found in (I). Cleavage of the C22—O bond of solasodine occurs with retention of configuration for atoms C16, C20 and C25, as for (I). The 22R configuration of the spiro C atom of solasodine changes to 22S in (II), owing to the formation of a C—H bond at atom C22. The main difference between (I) and (II) is thus the conformation of ring F (Fig. 2 and Table 2), which now exhibits a chair form [puckering parameters θ = 177.6 (4)° and ϕ = 93 (8)°; atom sequence as for (I)]. The relative positions of the NH group in ring F and the hydroxy substituent at atom C16 in ring D allow the formation of a rather strong intramolecular O—H···N hydrogen bond [D···A = ?, H···A = 1.93 (4) Å and D—H···A = 157 (5)°]. This stabilizing interaction explains why the OH group at atom C3 in solasodine is acetylated, while the OH group formed during E-ring opening is retained as a hydroxy group, at least when the conditions of Kusano et al. (1970) are applied. Such a protection of the C16—OH functionality is not possible for diacetate (I).

Related literature

For related literature, see: Allen (2002); Bird et al. (1979); Cremer & Pople (1975); Friedman & McDonald (1997); Iglesias-Arteaga, Sandoval-Ramírez, Mata-Esma, Viñas-Bravo & Bernès (2004); Kadota et al. (1995); Kusano et al. (1970); LaCour, Tong & Fuchs (1999); Lowe et al. (1998); Sandoval-Ramírez, Castro-Méndez, Meza-Reyes, Reyes-Vázquez, Santillán & Farfán (1999); Sandoval-Ramírez, Meza-Reyes, del Río, Hernández-Linares, Suárez-Rojas, Rincón, Farfán & Santillan (2003); Sato et al. (1957); Vega-Baez, Sandoval-Ramírez, Montiel-Smith, Meza-Reyes & Bernès (2006); Yang et al. (2004).

S2. Experimental

For the synthesis of (I), a mixture of solasodine (300 mg, 0.72 mmol), Ac₂O (3.0 ml, 32 mmol), AcOH (1.0 ml, 17 mmol) and Et₂O·BF₃ (0.7 ml, 5.5 mmol) was stirred for 20 s at 298 K. The reaction mixture was poured into iced water and shaken vigorously. Concentrated NH₄OH was added until a basic pH was obtained, and the product was extracted with CH₂Cl₂ (3 × 10 ml), washed with brine and water, dried over anhydrous Mg₂SO₄, and finally concentrated to dryness under reduced pressure. The crude product was chromatographed over silica gel using hexane/EtOAc (7:3), affording (I) in quantitative yield. Suitable single crystals were obtained by slow evaporation of an AcOEt solution. Spectroscopic data are in full agreement with the crystal structure (see archived CIF).

Compound (II) was prepared following a literature procedure (Kusano et al., 1970). Suitable single crystals of (II) were obtained by slow evaporation of an AcOEt solution. Spectroscopic data are in full agreement with the crystal structure (see archived CIF).

S3. Refinement

Carbonyl atom O31 and methyl group C32 in (II) are disordered over two sites, for which occupancies were refined and converged to 0.47 (4) and 0.53 (4), for O31A/C32A and O31B/C32B, respectively. In order to obtain a sensible geometry for this OAc group, bond lengths involving disordered sites were restrained [C30—O31 = 1.20 (1) Å (two restraints) and C30—C32 = 1.53 (1) Å (two restraints)]. All C-bonded H atoms in (II) were placed in idealized positions and constrained to ride on their parent atoms, with C—H bond lengths fixed at 0.93 (H6A), 0.96 (methyl CH₃), 0.97 (methylene CH₂) and 0.98 Å (methine CH). U_iso(H) values were calculated at 1.3U_eq(C) for methyl groups and 1.2U_eq(carrier C) otherwise. Rigid methyl groups were allowed to rotate about their C—C bonds in order to obtain accurate torsion angles. H atoms bonded to heteroatoms N27 and O33 were found in a difference map and refined with free coordinates [U_iso(H) = 1.3U_eq(N,O)]. For (I), the OAc group at atom C3 is almost certainly disordered as in (II), as reflected in the displacement parameters for atoms O31 and C32. However, we were unable to model satisfactorily disordered sites. H atoms were placed in idealized positions, with C—H bond lengths fixed as for (II) and U_iso(H) values of 1.5U_eq(C) for methyl groups and 1.2U_eq(C) otherwise. In both structures, Friedel pairs [663 for (I) and 394 for (II)] were merged and the stereochemistry assumed from thesynthesis.

Computing details

For both compounds, data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXTL-Plus (Release 5.10; Sheldrick, 2008); program(s) used to refine structure: SHELXTL-Plus (Release 5.10; Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Release 5.10; Sheldrick, 2008); software used to prepare material for publication: SHELXTL-Plus (Release 5.10; Sheldrick, 2008) and PLATON (Spek, 2003).

Figures

	Fig. 1. The structure of (I), with displacement ellipsoids at the 30% probability level for non-H atoms.
	Fig. 2. The structure of (II), with displacement ellipsoids at the 30% probability level for non-H atoms. Atoms O31B and C32B, disordered with O31A and C32A, have been omitted for clarity. The intramolecular hydrogen bond is shown as a dashed line.

(I) (25R)-22,26-epiminocholesta-5,22(N)-diene-3β,16β-diyl diacetate

Crystal data

C31H47NO4	Dx = 1.120 Mg m^−3
Mr = 497.70	Melting point: 462 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 71 reflections
a = 6.1137 (16) Å	θ = 4.8–11.4°
b = 11.6779 (14) Å	µ = 0.07 mm^−1
c = 41.330 (5) Å	T = 296 K
V = 2950.8 (9) Å^3	Needle, colourless
Z = 4	0.60 × 0.26 × 0.16 mm
F(000) = 1088

Data collection

Bruker P4 diffractometer	Rint = 0.028
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.0°
Graphite monochromator	h = −7→1
ω scans	k = −1→13
3812 measured reflections	l = −49→1
3026 independent reflections	3 standard reflections every 97 reflections
1931 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.052	H-atom parameters constrained
wR(F^2) = 0.154	w = 1/[σ^2(Fo^2) + (0.0744P)^2 + 0.5847P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
3026 reflections	Δρmax = 0.21 e Å^−3
332 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Extinction correction: SHELXTL-Plus, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.0077 (13)
Primary atom site location: structure-invariant direct methods

Special details

Experimental. m.p. 462–464 K; [α]_D = +45.3° (c. 0.70, CHCl₃) [Lit. +46.6°, CHCl₃ (Sato et al., 1957)]. ¹H-NMR, δ: 5.36 (1H, d, J=5.2 Hz, H-6), 4.58 (1H, m, H-3), 4.18 (1H, m, H-16), 2.98 (2H, ddd, J=11.3 and 3.3 Hz, H-26), 2.54 (1H, d, J=11.3 Hz, H-22), 2.20 (3H, s, CH₃CO—N), 2.03 (3H, s, CH₃COO-3), 1.08 (3H, d, J=7.2 Hz, H-21), 1.03 (3H, s, H-19), 0.91 (3H, s, H-18), 0.82 (3H, d, J=6.8 Hz, H-27). ¹³C-NMR, δ: 36.9 (C-1), 27.7 (C-2), 73.7 (C-3), 38.1 (C-4), 139.5 (C-5), 122.0 (C-6), 32.1 (C-7), 31.0 (C-8), 49.9 (C-9), 36.7 (C-10), 20.9 (C-11), 40.9 (C-12), 40.1 (C-13), 55.7 (C-14), 32.0 (C-15), 78.7 (C-16), 61.9 (C-17), 16.4 (C-18), 19.4 (C-19), 38.1 (C-20), 16.3 (C-21), 101.0 (C-22), 24.2 (C-23), 23.9 (C-24), 27.9 (C-25), 49.2 (C-26), 18.6 (C-27), 170.7 (CH₃CON), 170.2 (CH₃COO-3), 25.3 (CH₃CON), 21.5 (CH₃COO-3).

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

	x	y	z	Uiso*/Ueq
C1	0.1943 (8)	0.3111 (3)	0.29891 (8)	0.0497 (10)
H1A	0.0916	0.2518	0.2926	0.060*
H1B	0.3390	0.2863	0.2923	0.060*
C2	0.1909 (8)	0.3224 (3)	0.33613 (8)	0.0547 (11)
H2A	0.0446	0.3417	0.3434	0.066*
H2B	0.2329	0.2503	0.3460	0.066*
C3	0.3482 (8)	0.4147 (3)	0.34586 (8)	0.0524 (11)
H3D	0.4967	0.3948	0.3389	0.063*
C4	0.2803 (8)	0.5279 (3)	0.33117 (8)	0.0526 (11)
H4A	0.3840	0.5867	0.3374	0.063*
H4B	0.1377	0.5495	0.3395	0.063*
C5	0.2703 (6)	0.5206 (3)	0.29454 (9)	0.0439 (9)
C6	0.3745 (7)	0.5962 (3)	0.27612 (9)	0.0494 (10)
H6A	0.4557	0.6523	0.2866	0.059*
C7	0.3728 (7)	0.5991 (3)	0.23998 (8)	0.0493 (10)
H7A	0.5163	0.5774	0.2321	0.059*
H7B	0.3443	0.6768	0.2329	0.059*
C8	0.2019 (6)	0.5194 (3)	0.22517 (8)	0.0401 (9)
H8A	0.0581	0.5563	0.2263	0.048*
C9	0.1942 (7)	0.4054 (3)	0.24403 (8)	0.0407 (9)
H9A	0.3433	0.3747	0.2435	0.049*
C10	0.1368 (6)	0.4220 (3)	0.28035 (8)	0.0399 (9)
C11	0.0500 (8)	0.3165 (3)	0.22691 (8)	0.0541 (11)
H11A	−0.1018	0.3393	0.2291	0.065*
H11B	0.0672	0.2434	0.2378	0.065*
C12	0.1012 (8)	0.3000 (3)	0.19044 (8)	0.0512 (10)
H12A	0.2446	0.2654	0.1881	0.061*
H12B	−0.0054	0.2483	0.1810	0.061*
C13	0.0966 (6)	0.4144 (3)	0.17202 (8)	0.0416 (9)
C14	0.2562 (6)	0.4941 (3)	0.18971 (8)	0.0420 (9)
H14A	0.3964	0.4534	0.1901	0.050*
C15	0.2892 (7)	0.5955 (3)	0.16678 (8)	0.0514 (10)
H15A	0.4312	0.6307	0.1701	0.062*
H15B	0.1765	0.6529	0.1699	0.062*
C16	0.2734 (7)	0.5425 (3)	0.13298 (9)	0.0512 (10)
H16A	0.4154	0.5458	0.1220	0.061*
C17	0.2006 (7)	0.4161 (3)	0.13773 (8)	0.0461 (9)
H17A	0.3358	0.3714	0.1394	0.055*
C18	−0.1401 (7)	0.4620 (4)	0.17079 (9)	0.0553 (11)
H18A	−0.1888	0.4790	0.1923	0.083*
H18B	−0.2352	0.4059	0.1613	0.083*
H18C	−0.1428	0.5306	0.1580	0.083*
C19	−0.1077 (7)	0.4505 (4)	0.28506 (10)	0.0555 (11)
H19A	−0.1334	0.4713	0.3072	0.083*
H19B	−0.1946	0.3848	0.2796	0.083*
H19C	−0.1472	0.5133	0.2713	0.083*
C20	0.0747 (7)	0.3666 (4)	0.10827 (9)	0.0523 (11)
H20A	−0.0588	0.4121	0.1057	0.063*
C21	0.0044 (10)	0.2424 (4)	0.11267 (10)	0.0702 (14)
H21A	−0.0487	0.2129	0.0925	0.105*
H21B	−0.1096	0.2383	0.1286	0.105*
H21C	0.1273	0.1977	0.1197	0.105*
C22	0.2084 (7)	0.3810 (4)	0.07732 (9)	0.0532 (11)
C23	0.4321 (8)	0.3316 (5)	0.07675 (11)	0.0742 (15)
H23A	0.4272	0.2552	0.0860	0.089*
H23B	0.5266	0.3779	0.0903	0.089*
C24	0.5306 (10)	0.3247 (5)	0.04314 (11)	0.0932 (17)
H24A	0.6880	0.3160	0.0447	0.112*
H24B	0.4725	0.2586	0.0318	0.112*
C25	0.4765 (11)	0.4322 (6)	0.02468 (12)	0.100 (2)
H25B	0.5374	0.4966	0.0369	0.120*
C26	0.2343 (9)	0.4494 (6)	0.02311 (11)	0.0866 (18)
H26A	0.2065	0.5269	0.0158	0.104*
H26B	0.1757	0.3978	0.0069	0.104*
N27	0.1119 (7)	0.4310 (3)	0.05368 (8)	0.0667 (11)
C28	0.5800 (12)	0.4353 (8)	−0.00917 (14)	0.154 (3)
H28A	0.5630	0.5104	−0.0183	0.231*
H28B	0.5088	0.3802	−0.0228	0.231*
H28C	0.7328	0.4171	−0.0076	0.231*
O29	0.3393 (6)	0.4242 (3)	0.38095 (6)	0.0672 (9)
C30	0.5205 (13)	0.4595 (5)	0.39591 (13)	0.0914 (18)
O31	0.6858 (10)	0.4842 (6)	0.38218 (12)	0.146 (2)
C32	0.4835 (15)	0.4664 (5)	0.43195 (12)	0.125 (3)
H32A	0.6171	0.4883	0.4425	0.188*
H32B	0.4374	0.3930	0.4399	0.188*
H32C	0.3724	0.5222	0.4364	0.188*
O33	0.1085 (5)	0.6032 (2)	0.11426 (6)	0.0615 (8)
C34	0.1731 (12)	0.6719 (5)	0.09065 (13)	0.0834 (16)
O35	0.3619 (10)	0.6874 (5)	0.08384 (12)	0.136 (2)
C36	−0.0141 (13)	0.7238 (5)	0.07295 (13)	0.113 (2)
H36A	0.0358	0.7530	0.0525	0.169*
H36B	−0.0744	0.7852	0.0856	0.169*
H36C	−0.1243	0.6667	0.0693	0.169*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.065 (3)	0.0377 (19)	0.046 (2)	−0.005 (2)	0.006 (2)	0.0016 (16)
C2	0.068 (3)	0.049 (2)	0.047 (2)	−0.002 (3)	0.007 (2)	−0.0008 (18)
C3	0.055 (3)	0.062 (2)	0.040 (2)	0.005 (3)	0.002 (2)	−0.0019 (19)
C4	0.061 (3)	0.047 (2)	0.050 (2)	−0.002 (2)	−0.003 (2)	−0.0052 (18)
C5	0.044 (2)	0.0411 (19)	0.046 (2)	0.006 (2)	−0.0016 (19)	−0.0033 (17)
C6	0.048 (2)	0.047 (2)	0.053 (2)	−0.005 (2)	−0.008 (2)	−0.0023 (19)
C7	0.046 (2)	0.047 (2)	0.055 (2)	−0.009 (2)	0.001 (2)	−0.0009 (18)
C8	0.0333 (19)	0.0389 (18)	0.048 (2)	0.0029 (19)	0.0015 (18)	0.0025 (16)
C9	0.039 (2)	0.0395 (18)	0.0434 (19)	0.001 (2)	0.0023 (18)	0.0009 (16)
C10	0.034 (2)	0.043 (2)	0.0427 (19)	0.0019 (19)	0.0062 (17)	−0.0047 (16)
C11	0.070 (3)	0.046 (2)	0.047 (2)	−0.014 (2)	0.004 (2)	0.0030 (18)
C12	0.061 (3)	0.045 (2)	0.048 (2)	−0.007 (2)	0.004 (2)	−0.0001 (17)
C13	0.035 (2)	0.043 (2)	0.047 (2)	0.0028 (19)	0.0030 (17)	0.0015 (17)
C14	0.039 (2)	0.042 (2)	0.044 (2)	0.0002 (19)	0.0023 (18)	0.0005 (16)
C15	0.053 (2)	0.046 (2)	0.054 (2)	−0.010 (2)	0.006 (2)	0.0048 (18)
C16	0.048 (2)	0.056 (2)	0.050 (2)	−0.001 (2)	0.006 (2)	0.0066 (19)
C17	0.038 (2)	0.051 (2)	0.049 (2)	0.005 (2)	0.0003 (19)	0.0037 (18)
C18	0.042 (2)	0.070 (3)	0.055 (2)	0.003 (2)	0.000 (2)	−0.001 (2)
C19	0.043 (2)	0.072 (3)	0.051 (2)	0.001 (2)	0.004 (2)	−0.006 (2)
C20	0.046 (2)	0.061 (2)	0.050 (2)	−0.004 (2)	0.000 (2)	0.0012 (19)
C21	0.091 (4)	0.067 (3)	0.053 (3)	−0.017 (3)	−0.008 (3)	−0.002 (2)
C22	0.050 (2)	0.065 (3)	0.044 (2)	−0.002 (2)	−0.003 (2)	−0.002 (2)
C23	0.062 (3)	0.107 (4)	0.054 (3)	0.018 (3)	0.009 (2)	0.002 (3)
C24	0.078 (4)	0.130 (5)	0.072 (3)	0.020 (4)	0.021 (3)	0.006 (4)
C25	0.088 (5)	0.141 (6)	0.071 (3)	−0.003 (5)	0.029 (3)	0.018 (4)
C26	0.081 (4)	0.126 (5)	0.053 (3)	0.007 (4)	0.015 (3)	0.014 (3)
N27	0.064 (2)	0.086 (3)	0.049 (2)	0.004 (2)	0.0016 (19)	0.0088 (19)
C28	0.116 (6)	0.249 (10)	0.097 (4)	0.020 (7)	0.057 (4)	0.048 (5)
O29	0.080 (2)	0.0762 (19)	0.0449 (15)	−0.006 (2)	−0.0108 (17)	−0.0026 (14)
C30	0.108 (5)	0.100 (4)	0.067 (3)	−0.021 (4)	−0.038 (4)	−0.006 (3)
O31	0.114 (4)	0.215 (6)	0.110 (4)	−0.079 (5)	−0.034 (3)	0.005 (3)
C32	0.190 (8)	0.120 (4)	0.066 (3)	−0.030 (6)	−0.054 (4)	−0.013 (3)
O33	0.068 (2)	0.0625 (17)	0.0541 (16)	0.0057 (18)	0.0025 (16)	0.0157 (14)
C34	0.104 (5)	0.065 (3)	0.081 (3)	0.006 (4)	0.017 (4)	0.019 (3)
O35	0.127 (4)	0.136 (4)	0.145 (4)	−0.010 (4)	0.034 (4)	0.086 (3)
C36	0.154 (6)	0.106 (4)	0.078 (4)	0.041 (5)	−0.005 (4)	0.031 (3)

Geometric parameters (Å, º)

C1—C2	1.544 (5)	C17—C20	1.552 (5)
C1—C10	1.546 (5)	C17—H17A	0.9800
C1—H1A	0.9700	C18—H18A	0.9600
C1—H1B	0.9700	C18—H18B	0.9600
C2—C3	1.500 (6)	C18—H18C	0.9600
C2—H2A	0.9700	C19—H19A	0.9600
C2—H2B	0.9700	C19—H19B	0.9600
C3—O29	1.456 (4)	C19—H19C	0.9600
C3—C4	1.513 (5)	C20—C21	1.523 (6)
C3—H3D	0.9800	C20—C22	1.527 (5)
C4—C5	1.517 (5)	C20—H20A	0.9800
C4—H4A	0.9700	C21—H21A	0.9600
C4—H4B	0.9700	C21—H21B	0.9600
C5—C6	1.329 (5)	C21—H21C	0.9600
C5—C10	1.529 (5)	C22—N27	1.282 (5)
C6—C7	1.494 (5)	C22—C23	1.484 (6)
C6—H6A	0.9300	C23—C24	1.516 (6)
C7—C8	1.527 (5)	C23—H23A	0.9700
C7—H7A	0.9700	C23—H23B	0.9700
C7—H7B	0.9700	C24—C25	1.506 (8)
C8—C14	1.532 (5)	C24—H24A	0.9700
C8—C9	1.543 (5)	C24—H24B	0.9700
C8—H8A	0.9800	C25—C26	1.495 (8)
C9—C11	1.536 (5)	C25—C28	1.536 (7)
C9—C10	1.554 (5)	C25—H25B	0.9800
C9—H9A	0.9800	C26—N27	1.484 (6)
C10—C19	1.544 (6)	C26—H26A	0.9700
C11—C12	1.551 (5)	C26—H26B	0.9700
C11—H11A	0.9700	C28—H28A	0.9600
C11—H11B	0.9700	C28—H28B	0.9600
C12—C13	1.537 (5)	C28—H28C	0.9600
C12—H12A	0.9700	O29—C30	1.334 (7)
C12—H12B	0.9700	C30—O31	1.194 (8)
C13—C14	1.534 (5)	C30—C32	1.509 (7)
C13—C18	1.551 (6)	C32—H32A	0.9600
C13—C17	1.554 (5)	C32—H32B	0.9600
C14—C15	1.530 (5)	C32—H32C	0.9600
C14—H14A	0.9800	O33—C34	1.323 (6)
C15—C16	1.531 (5)	C34—O35	1.202 (8)
C15—H15A	0.9700	C34—C36	1.488 (9)
C15—H15B	0.9700	C36—H36A	0.9600
C16—O33	1.455 (5)	C36—H36B	0.9600
C16—C17	1.554 (5)	C36—H36C	0.9600
C16—H16A	0.9800
C2—C1—C10	114.8 (3)	O33—C16—H16A	110.4
C2—C1—H1A	108.6	C15—C16—H16A	110.4
C10—C1—H1A	108.6	C17—C16—H16A	110.4
C2—C1—H1B	108.6	C20—C17—C13	120.5 (3)
C10—C1—H1B	108.6	C20—C17—C16	113.4 (3)
H1A—C1—H1B	107.5	C13—C17—C16	104.2 (3)
C3—C2—C1	108.6 (3)	C20—C17—H17A	105.9
C3—C2—H2A	110.0	C13—C17—H17A	105.9
C1—C2—H2A	110.0	C16—C17—H17A	105.9
C3—C2—H2B	110.0	C13—C18—H18A	109.5
C1—C2—H2B	110.0	C13—C18—H18B	109.5
H2A—C2—H2B	108.3	H18A—C18—H18B	109.5
O29—C3—C2	107.3 (3)	C13—C18—H18C	109.5
O29—C3—C4	108.9 (3)	H18A—C18—H18C	109.5
C2—C3—C4	110.1 (3)	H18B—C18—H18C	109.5
O29—C3—H3D	110.2	C10—C19—H19A	109.5
C2—C3—H3D	110.2	C10—C19—H19B	109.5
C4—C3—H3D	110.2	H19A—C19—H19B	109.5
C3—C4—C5	111.3 (3)	C10—C19—H19C	109.5
C3—C4—H4A	109.4	H19A—C19—H19C	109.5
C5—C4—H4A	109.4	H19B—C19—H19C	109.5
C3—C4—H4B	109.4	C21—C20—C22	110.8 (3)
C5—C4—H4B	109.4	C21—C20—C17	113.7 (3)
H4A—C4—H4B	108.0	C22—C20—C17	110.5 (3)
C6—C5—C4	121.0 (3)	C21—C20—H20A	107.2
C6—C5—C10	122.5 (3)	C22—C20—H20A	107.2
C4—C5—C10	116.5 (3)	C17—C20—H20A	107.2
C5—C6—C7	125.7 (4)	C20—C21—H21A	109.5
C5—C6—H6A	117.1	C20—C21—H21B	109.5
C7—C6—H6A	117.1	H21A—C21—H21B	109.5
C6—C7—C8	113.1 (3)	C20—C21—H21C	109.5
C6—C7—H7A	109.0	H21A—C21—H21C	109.5
C8—C7—H7A	109.0	H21B—C21—H21C	109.5
C6—C7—H7B	109.0	N27—C22—C23	126.1 (4)
C8—C7—H7B	109.0	N27—C22—C20	116.2 (4)
H7A—C7—H7B	107.8	C23—C22—C20	117.6 (4)
C7—C8—C14	110.7 (3)	C22—C23—C24	113.6 (4)
C7—C8—C9	110.1 (3)	C22—C23—H23A	108.8
C14—C8—C9	108.9 (3)	C24—C23—H23A	108.8
C7—C8—H8A	109.1	C22—C23—H23B	108.8
C14—C8—H8A	109.1	C24—C23—H23B	108.8
C9—C8—H8A	109.1	H23A—C23—H23B	107.7
C11—C9—C8	111.6 (3)	C25—C24—C23	109.4 (5)
C11—C9—C10	113.6 (3)	C25—C24—H24A	109.8
C8—C9—C10	112.8 (3)	C23—C24—H24A	109.8
C11—C9—H9A	106.1	C25—C24—H24B	109.8
C8—C9—H9A	106.1	C23—C24—H24B	109.8
C10—C9—H9A	106.1	H24A—C24—H24B	108.2
C5—C10—C19	107.8 (3)	C26—C25—C24	110.6 (6)
C5—C10—C1	108.6 (3)	C26—C25—C28	111.4 (5)
C19—C10—C1	109.8 (3)	C24—C25—C28	113.0 (6)
C5—C10—C9	110.1 (3)	C26—C25—H25B	107.2
C19—C10—C9	111.6 (3)	C24—C25—H25B	107.2
C1—C10—C9	108.9 (3)	C28—C25—H25B	107.2
C9—C11—C12	114.5 (3)	N27—C26—C25	116.3 (4)
C9—C11—H11A	108.6	N27—C26—H26A	108.2
C12—C11—H11A	108.6	C25—C26—H26A	108.2
C9—C11—H11B	108.6	N27—C26—H26B	108.2
C12—C11—H11B	108.6	C25—C26—H26B	108.2
H11A—C11—H11B	107.6	H26A—C26—H26B	107.4
C13—C12—C11	111.7 (3)	C22—N27—C26	118.9 (4)
C13—C12—H12A	109.3	C25—C28—H28A	109.5
C11—C12—H12A	109.3	C25—C28—H28B	109.5
C13—C12—H12B	109.3	H28A—C28—H28B	109.5
C11—C12—H12B	109.3	C25—C28—H28C	109.5
H12A—C12—H12B	107.9	H28A—C28—H28C	109.5
C14—C13—C12	106.2 (3)	H28B—C28—H28C	109.5
C14—C13—C18	113.0 (3)	C30—O29—C3	117.0 (4)
C12—C13—C18	110.2 (3)	O31—C30—O29	123.8 (5)
C14—C13—C17	99.6 (3)	O31—C30—C32	125.7 (6)
C12—C13—C17	117.1 (3)	O29—C30—C32	110.5 (6)
C18—C13—C17	110.3 (3)	C30—C32—H32A	109.5
C15—C14—C8	118.1 (3)	C30—C32—H32B	109.5
C15—C14—C13	105.0 (3)	H32A—C32—H32B	109.5
C8—C14—C13	115.8 (3)	C30—C32—H32C	109.5
C15—C14—H14A	105.6	H32A—C32—H32C	109.5
C8—C14—H14A	105.6	H32B—C32—H32C	109.5
C13—C14—H14A	105.6	C34—O33—C16	118.7 (4)
C14—C15—C16	104.1 (3)	O35—C34—O33	123.4 (6)
C14—C15—H15A	110.9	O35—C34—C36	124.2 (6)
C16—C15—H15A	110.9	O33—C34—C36	112.3 (6)
C14—C15—H15B	110.9	C34—C36—H36A	109.5
C16—C15—H15B	110.9	C34—C36—H36B	109.5
H15A—C15—H15B	109.0	H36A—C36—H36B	109.5
O33—C16—C15	109.4 (3)	C34—C36—H36C	109.5
O33—C16—C17	109.4 (3)	H36A—C36—H36C	109.5
C15—C16—C17	106.7 (3)	H36B—C36—H36C	109.5
C10—C1—C2—C3	−57.9 (5)	C12—C13—C14—C8	−60.6 (4)
C1—C2—C3—O29	179.3 (3)	C18—C13—C14—C8	60.3 (4)
C1—C2—C3—C4	61.0 (4)	C17—C13—C14—C8	177.3 (3)
O29—C3—C4—C5	−175.8 (3)	C8—C14—C15—C16	−164.1 (3)
C2—C3—C4—C5	−58.4 (5)	C13—C14—C15—C16	−33.3 (4)
C3—C4—C5—C6	−128.0 (4)	C14—C15—C16—O33	125.7 (3)
C3—C4—C5—C10	51.5 (5)	C14—C15—C16—C17	7.5 (4)
C4—C5—C6—C7	−178.7 (4)	C14—C13—C17—C20	−168.0 (3)
C10—C5—C6—C7	1.9 (6)	C12—C13—C17—C20	78.1 (4)
C5—C6—C7—C8	11.2 (6)	C18—C13—C17—C20	−49.0 (5)
C6—C7—C8—C14	−160.7 (3)	C14—C13—C17—C16	−39.4 (3)
C6—C7—C8—C9	−40.4 (4)	C12—C13—C17—C16	−153.2 (3)
C7—C8—C9—C11	−171.4 (3)	C18—C13—C17—C16	79.7 (4)
C14—C8—C9—C11	−49.9 (4)	O33—C16—C17—C20	34.9 (4)
C7—C8—C9—C10	59.3 (4)	C15—C16—C17—C20	153.1 (3)
C14—C8—C9—C10	−179.2 (3)	O33—C16—C17—C13	−98.0 (3)
C6—C5—C10—C19	−106.6 (4)	C15—C16—C17—C13	20.2 (4)
C4—C5—C10—C19	74.0 (4)	C13—C17—C20—C21	−56.1 (5)
C6—C5—C10—C1	134.5 (4)	C16—C17—C20—C21	179.6 (4)
C4—C5—C10—C1	−45.0 (4)	C13—C17—C20—C22	178.6 (3)
C6—C5—C10—C9	15.3 (5)	C16—C17—C20—C22	54.2 (4)
C4—C5—C10—C9	−164.1 (3)	C21—C20—C22—N27	106.5 (5)
C2—C1—C10—C5	48.2 (5)	C17—C20—C22—N27	−126.6 (4)
C2—C1—C10—C19	−69.5 (5)	C21—C20—C22—C23	−70.7 (5)
C2—C1—C10—C9	168.1 (3)	C17—C20—C22—C23	56.2 (5)
C11—C9—C10—C5	−173.9 (3)	N27—C22—C23—C24	−10.7 (7)
C8—C9—C10—C5	−45.6 (4)	C20—C22—C23—C24	166.2 (4)
C11—C9—C10—C19	−54.2 (4)	C22—C23—C24—C25	41.0 (7)
C8—C9—C10—C19	74.0 (4)	C23—C24—C25—C26	−57.2 (7)
C11—C9—C10—C1	67.1 (4)	C23—C24—C25—C28	177.1 (5)
C8—C9—C10—C1	−164.6 (3)	C24—C25—C26—N27	44.7 (8)
C8—C9—C11—C12	50.0 (5)	C28—C25—C26—N27	171.2 (5)
C10—C9—C11—C12	178.9 (3)	C23—C22—N27—C26	−4.1 (7)
C9—C11—C12—C13	−53.5 (5)	C20—C22—N27—C26	179.0 (4)
C11—C12—C13—C14	54.9 (5)	C25—C26—N27—C22	−13.5 (8)
C11—C12—C13—C18	−67.8 (4)	C2—C3—O29—C30	151.0 (4)
C11—C12—C13—C17	165.0 (3)	C4—C3—O29—C30	−89.8 (5)
C7—C8—C14—C15	−54.5 (4)	C3—O29—C30—O31	0.7 (9)
C9—C8—C14—C15	−175.6 (4)	C3—O29—C30—C32	179.2 (4)
C7—C8—C14—C13	179.8 (3)	C15—C16—O33—C34	107.5 (4)
C9—C8—C14—C13	58.7 (4)	C17—C16—O33—C34	−136.0 (4)
C12—C13—C14—C15	167.1 (3)	C16—O33—C34—O35	−0.3 (8)
C18—C13—C14—C15	−71.9 (4)	C16—O33—C34—C36	177.6 (4)
C17—C13—C14—C15	45.1 (3)

(II) (22S,25R)-16β-hydroxy-22,26-epiminocholesta-5-ene-3β-yl acetate

Crystal data

C29H47NO3	F(000) = 1008
Mr = 457.68	Dx = 1.153 Mg m^−3
Monoclinic, C2	Melting point: 488 K
Hall symbol: C 2y	Mo Kα radiation, λ = 0.71073 Å
a = 10.026 (2) Å	Cell parameters from 56 reflections
b = 7.4403 (14) Å	θ = 4.0–12.5°
c = 35.508 (6) Å	µ = 0.07 mm^−1
β = 95.512 (18)°	T = 296 K
V = 2636.4 (9) Å^3	Plate, colourless
Z = 4	0.60 × 0.40 × 0.18 mm

Data collection

Bruker P4 diffractometer	Rint = 0.043
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.3°
Graphite monochromator	h = −11→5
ω scans	k = −1→8
4449 measured reflections	l = −42→42
2526 independent reflections	3 standard reflections every 97 reflections
2236 reflections with I > 2σ(I)	intensity decay: 2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0823P)^2 + 0.9528P] where P = (Fo^2 + 2Fc^2)/3
2526 reflections	(Δ/σ)max < 0.001
322 parameters	Δρmax = 0.16 e Å^−3
5 restraints	Δρmin = −0.28 e Å^−3

Special details

Experimental. m.p. 488–490 K (Lit. 484.5–486; Kusano et al., 1970; Bird et al. 1979). [α]_D = -71.5° (c. 0.89, CHCl₃) [Lit. -67.1°, c. 1.08, CHCl₃; Kusano et al., 1970; -67.7°, c. 0.87, CHCl₃; Bird et al. 1979]. (Sato et al., 1957)]. ¹H-NMR, δ: 5.36 (1H, d, J=4.4 Hz, H-6), 5.19 (1H, m, H-16), 4.59 (1H, m, H-3), 3.61 (1H, dd, J=16.8 Hz, J=4.7 Hz, H-26 e), 2.96 (1H, dd, J=16.8 Hz, J=9.9 Hz, H-26a), 2.56 (1H, m, H-20), 2.03 (3H, s, CH₃COO-3), 1.98 (3H, s, CH₃COO-16), 1.10 (3H, d, J=6.8 Hz, H-21), 1.02 (3H, s, H-19), 0.89 (3H, s, H-18), 0.87 (3H, d, J=6.4 Hz, H-27). ¹³C-NMR, δ: 36.7 (C-1), 27.7 (C-2), 73.8 (C-3), 37.9 (C-4), 139.6 (C-5), 122.2 (C-6), 31.5 (C-7), 31.2 (C-8), 49.7 (C-9), 36.4 (C-10), 20.6 (C-11), 39.4 (C-12), 41.9 (C-13), 54.1 (C-14), 34.5 (C-15), 75.0 (C-16), 56.2 (C-17), 12.8 (C-18), 19.2 (C-19), 40.7 (C-20), 18.7 (C-21), 173.6 (C-22), 28.2 (C-23), 27.8 (C-24), 27.2 (C-25), 55.6 (C-26), 19.0 (C-27), 170.2 (CH₃COO-16), 170.4 (CH₃COO-3).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.3492 (3)	0.4864 (5)	0.35479 (8)	0.0493 (8)
H1A	0.3637	0.6013	0.3429	0.059*
H1B	0.2635	0.4405	0.3439	0.059*
C2	0.3420 (4)	0.5172 (6)	0.39751 (9)	0.0556 (9)
H2A	0.4237	0.5739	0.4085	0.067*
H2B	0.2672	0.5955	0.4015	0.067*
C3	0.3240 (4)	0.3378 (7)	0.41594 (8)	0.0582 (10)
H3A	0.2414	0.2812	0.4046	0.070*
C4	0.4414 (4)	0.2165 (6)	0.41110 (8)	0.0526 (9)
H4A	0.4289	0.1023	0.4235	0.063*
H4B	0.5230	0.2709	0.4228	0.063*
C5	0.4541 (3)	0.1857 (5)	0.36919 (8)	0.0400 (7)
C6	0.4564 (3)	0.0213 (5)	0.35583 (8)	0.0430 (7)
H6A	0.4516	−0.0728	0.3729	0.052*
C7	0.4663 (3)	−0.0263 (4)	0.31507 (8)	0.0415 (7)
H7A	0.3803	−0.0713	0.3042	0.050*
H7B	0.5315	−0.1219	0.3138	0.050*
C8	0.5072 (3)	0.1329 (4)	0.29156 (8)	0.0322 (6)
H8A	0.6041	0.1512	0.2963	0.039*
C9	0.4344 (3)	0.3048 (4)	0.30230 (8)	0.0340 (6)
H9A	0.3384	0.2790	0.2978	0.041*
C10	0.4608 (3)	0.3546 (4)	0.34505 (8)	0.0355 (7)
C11	0.4619 (3)	0.4599 (4)	0.27563 (8)	0.0411 (7)
H11A	0.5549	0.4957	0.2806	0.049*
H11B	0.4070	0.5618	0.2813	0.049*
C12	0.4339 (3)	0.4148 (4)	0.23327 (8)	0.0400 (7)
H12A	0.3384	0.3970	0.2273	0.048*
H12B	0.4608	0.5157	0.2184	0.048*
C13	0.5082 (3)	0.2463 (4)	0.22219 (8)	0.0323 (6)
C14	0.4717 (3)	0.0967 (4)	0.24964 (8)	0.0321 (6)
H14A	0.3737	0.0884	0.2463	0.038*
C15	0.5217 (3)	−0.0747 (4)	0.23263 (8)	0.0390 (7)
H15A	0.4726	−0.1781	0.2405	0.047*
H15B	0.6164	−0.0922	0.2402	0.047*
C16	0.4971 (3)	−0.0476 (5)	0.18999 (8)	0.0388 (7)
H16A	0.4218	−0.1233	0.1801	0.047*
C17	0.4575 (3)	0.1549 (4)	0.18397 (7)	0.0340 (7)
H17A	0.3595	0.1585	0.1826	0.041*
C18	0.6609 (3)	0.2811 (5)	0.22415 (9)	0.0436 (7)
H18A	0.6961	0.2955	0.2501	0.057*
H18B	0.6772	0.3884	0.2103	0.057*
H18C	0.7040	0.1811	0.2133	0.057*
C19	0.5992 (3)	0.4420 (5)	0.35438 (9)	0.0487 (8)
H19A	0.6169	0.4549	0.3813	0.063*
H19B	0.6001	0.5582	0.3427	0.063*
H19C	0.6668	0.3675	0.3450	0.063*
C20	0.4954 (3)	0.2416 (5)	0.14645 (8)	0.0413 (7)
H20A	0.5933	0.2377	0.1469	0.050*
C21	0.4533 (4)	0.4399 (5)	0.14372 (9)	0.0549 (9)
H21A	0.4606	0.4828	0.1185	0.071*
H21B	0.5107	0.5095	0.1613	0.071*
H21C	0.3622	0.4514	0.1496	0.071*
C22	0.4367 (3)	0.1437 (5)	0.10979 (8)	0.0453 (8)
H22A	0.4347	0.2320	0.0893	0.054*
C23	0.2956 (3)	0.0745 (6)	0.11040 (9)	0.0515 (9)
H23A	0.2362	0.1743	0.1143	0.062*
H23B	0.2922	−0.0082	0.1314	0.062*
C24	0.2469 (4)	−0.0210 (7)	0.07371 (10)	0.0623 (11)
H24A	0.1590	−0.0720	0.0759	0.075*
H24B	0.2389	0.0653	0.0531	0.075*
C25	0.3422 (5)	−0.1684 (6)	0.06483 (10)	0.0653 (11)
H25A	0.3459	−0.2563	0.0855	0.078*
C26	0.4811 (4)	−0.0895 (7)	0.06371 (10)	0.0642 (11)
H26A	0.5433	−0.1841	0.0584	0.077*
H26B	0.4798	−0.0016	0.0435	0.077*
N27	0.5267 (3)	−0.0035 (5)	0.09981 (8)	0.0550 (8)
H27	0.612 (4)	0.034 (7)	0.0961 (11)	0.072*
C28	0.2974 (6)	−0.2665 (9)	0.02789 (13)	0.0989 (17)
H28A	0.2100	−0.3174	0.0294	0.129*
H28B	0.3599	−0.3606	0.0239	0.129*
H28C	0.2940	−0.1830	0.0072	0.129*
O29	0.3162 (3)	0.3628 (6)	0.45665 (7)	0.0779 (10)
C30	0.1997 (5)	0.3354 (7)	0.47000 (10)	0.0682 (12)
O31A	0.112 (2)	0.251 (5)	0.4525 (3)	0.111 (8)	0.47 (4)
C32A	0.1995 (10)	0.3592 (14)	0.51267 (11)	0.082 (6)	0.47 (4)
H32A	0.1092	0.3765	0.5188	0.106*	0.47 (4)
H32B	0.2526	0.4622	0.5207	0.106*	0.47 (4)
H32C	0.2366	0.2540	0.5253	0.106*	0.47 (4)
O31B	0.0989 (11)	0.337 (3)	0.44926 (13)	0.102 (5)	0.53 (4)
C32B	0.2252 (10)	0.3606 (17)	0.51282 (12)	0.110 (7)	0.53 (4)
H32D	0.2419	0.4853	0.5184	0.142*	0.53 (4)
H32E	0.3017	0.2907	0.5223	0.142*	0.53 (4)
H32F	0.1481	0.3216	0.5247	0.142*	0.53 (4)
O33	0.6154 (2)	−0.1028 (4)	0.17336 (6)	0.0516 (6)
H33	0.590 (4)	−0.103 (7)	0.1484 (11)	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0595 (19)	0.055 (2)	0.0339 (15)	0.0155 (18)	0.0060 (13)	−0.0070 (15)
C2	0.062 (2)	0.068 (2)	0.0380 (16)	0.013 (2)	0.0085 (14)	−0.0116 (18)
C3	0.064 (2)	0.081 (3)	0.0304 (16)	−0.014 (2)	0.0131 (14)	−0.0153 (18)
C4	0.075 (2)	0.053 (2)	0.0311 (15)	−0.0055 (19)	0.0093 (14)	0.0018 (15)
C5	0.0408 (15)	0.045 (2)	0.0342 (15)	−0.0024 (14)	0.0042 (12)	0.0018 (14)
C6	0.0532 (19)	0.0393 (18)	0.0370 (15)	−0.0056 (15)	0.0074 (13)	0.0087 (14)
C7	0.0579 (18)	0.0304 (16)	0.0366 (15)	−0.0027 (15)	0.0059 (13)	−0.0001 (13)
C8	0.0323 (13)	0.0302 (15)	0.0342 (14)	0.0005 (12)	0.0037 (11)	0.0018 (12)
C9	0.0396 (15)	0.0315 (15)	0.0315 (14)	0.0000 (12)	0.0057 (11)	−0.0018 (12)
C10	0.0368 (15)	0.0396 (17)	0.0304 (13)	0.0012 (13)	0.0040 (11)	−0.0020 (13)
C11	0.0614 (18)	0.0266 (15)	0.0362 (15)	0.0047 (15)	0.0097 (13)	−0.0016 (13)
C12	0.0556 (18)	0.0315 (16)	0.0335 (14)	0.0063 (14)	0.0068 (12)	0.0009 (13)
C13	0.0343 (14)	0.0306 (15)	0.0327 (13)	0.0007 (12)	0.0066 (11)	0.0011 (12)
C14	0.0327 (13)	0.0276 (15)	0.0366 (14)	−0.0041 (12)	0.0067 (11)	−0.0020 (12)
C15	0.0477 (17)	0.0301 (16)	0.0399 (15)	0.0035 (13)	0.0071 (12)	0.0004 (13)
C16	0.0418 (15)	0.0365 (17)	0.0395 (15)	−0.0002 (14)	0.0115 (12)	−0.0028 (13)
C17	0.0351 (14)	0.0360 (16)	0.0324 (14)	−0.0021 (13)	0.0107 (11)	−0.0019 (13)
C18	0.0415 (16)	0.0441 (19)	0.0462 (16)	−0.0082 (14)	0.0093 (12)	0.0025 (15)
C19	0.0525 (18)	0.053 (2)	0.0404 (15)	−0.0121 (17)	0.0025 (13)	−0.0029 (16)
C20	0.0502 (17)	0.0423 (18)	0.0332 (14)	−0.0012 (15)	0.0129 (12)	0.0030 (14)
C21	0.080 (2)	0.045 (2)	0.0417 (17)	0.002 (2)	0.0168 (16)	0.0074 (16)
C22	0.0568 (18)	0.0469 (19)	0.0338 (15)	0.0047 (16)	0.0127 (13)	0.0003 (15)
C23	0.0529 (18)	0.063 (2)	0.0393 (16)	0.0057 (17)	0.0052 (14)	−0.0076 (17)
C24	0.070 (2)	0.076 (3)	0.0398 (16)	−0.005 (2)	0.0007 (15)	−0.0012 (19)
C25	0.097 (3)	0.056 (2)	0.0423 (18)	−0.003 (2)	0.0021 (18)	−0.0071 (18)
C26	0.081 (3)	0.070 (3)	0.0431 (17)	0.015 (2)	0.0145 (17)	−0.0118 (19)
N27	0.0556 (16)	0.070 (2)	0.0405 (14)	0.0086 (17)	0.0121 (12)	−0.0102 (15)
C28	0.133 (4)	0.095 (4)	0.068 (3)	−0.009 (4)	0.006 (3)	−0.032 (3)
O29	0.091 (2)	0.111 (3)	0.0349 (12)	−0.022 (2)	0.0214 (12)	−0.0196 (15)
C30	0.086 (3)	0.075 (3)	0.048 (2)	0.010 (3)	0.030 (2)	0.005 (2)
O31A	0.090 (8)	0.19 (2)	0.053 (5)	−0.052 (10)	0.010 (5)	0.008 (6)
C32A	0.095 (9)	0.120 (16)	0.033 (7)	−0.013 (10)	0.023 (5)	−0.007 (8)
O31B	0.080 (6)	0.167 (13)	0.066 (5)	0.032 (6)	0.035 (5)	0.035 (6)
C32B	0.190 (15)	0.070 (11)	0.084 (11)	0.022 (10)	0.089 (10)	0.009 (9)
O33	0.0564 (13)	0.0569 (16)	0.0434 (11)	0.0175 (12)	0.0141 (10)	−0.0042 (12)

Geometric parameters (Å, º)

C1—C2	1.543 (4)	C17—H17A	0.9800
C1—C10	1.551 (4)	C18—H18A	0.9600
C1—H1A	0.9700	C18—H18B	0.9600
C1—H1B	0.9700	C18—H18C	0.9600
C2—C3	1.505 (6)	C19—H19A	0.9600
C2—H2A	0.9700	C19—H19B	0.9600
C2—H2B	0.9700	C19—H19C	0.9600
C3—O29	1.467 (4)	C20—C21	1.536 (5)
C3—C4	1.506 (6)	C20—C22	1.557 (4)
C3—H3A	0.9800	C20—H20A	0.9800
C4—C5	1.523 (4)	C21—H21A	0.9600
C4—H4A	0.9700	C21—H21B	0.9600
C4—H4B	0.9700	C21—H21C	0.9600
C5—C6	1.313 (5)	C22—N27	1.483 (5)
C5—C10	1.526 (5)	C22—C23	1.508 (5)
C6—C7	1.502 (4)	C22—H22A	0.9800
C6—H6A	0.9300	C23—C24	1.522 (5)
C7—C8	1.527 (4)	C23—H23A	0.9700
C7—H7A	0.9700	C23—H23B	0.9700
C7—H7B	0.9700	C24—C25	1.507 (6)
C8—C14	1.521 (4)	C24—H24A	0.9700
C8—C9	1.539 (4)	C24—H24B	0.9700
C8—H8A	0.9800	C25—C26	1.515 (6)
C9—C11	1.534 (4)	C25—C28	1.531 (6)
C9—C10	1.560 (4)	C25—H25A	0.9800
C9—H9A	0.9800	C26—N27	1.466 (4)
C10—C19	1.539 (4)	C26—H26A	0.9700
C11—C12	1.540 (4)	C26—H26B	0.9700
C11—H11A	0.9700	N27—H27	0.92 (4)
C11—H11B	0.9700	C28—H28A	0.9600
C12—C13	1.529 (4)	C28—H28B	0.9600
C12—H12A	0.9700	C28—H28C	0.9600
C12—H12B	0.9700	O29—C30	1.318 (5)
C13—C14	1.547 (4)	C30—O31B	1.192 (7)
C13—C18	1.547 (4)	C30—O31A	1.205 (8)
C13—C17	1.558 (4)	C30—C32A	1.526 (5)
C14—C15	1.517 (4)	C30—C32B	1.529 (4)
C14—H14A	0.9800	C32A—H32A	0.9600
C15—C16	1.524 (4)	C32A—H32B	0.9600
C15—H15A	0.9700	C32A—H32C	0.9600
C15—H15B	0.9700	C32B—H32D	0.9600
C16—O33	1.435 (4)	C32B—H32E	0.9600
C16—C17	1.568 (5)	C32B—H32F	0.9600
C16—H16A	0.9800	O33—H33	0.90 (4)
C17—C20	1.559 (4)
C2—C1—C10	114.6 (3)	C15—C16—H16A	109.1
C2—C1—H1A	108.6	C17—C16—H16A	109.1
C10—C1—H1A	108.6	C13—C17—C20	118.5 (3)
C2—C1—H1B	108.6	C13—C17—C16	104.1 (2)
C10—C1—H1B	108.6	C20—C17—C16	115.7 (2)
H1A—C1—H1B	107.6	C13—C17—H17A	105.8
C3—C2—C1	108.3 (3)	C20—C17—H17A	105.8
C3—C2—H2A	110.0	C16—C17—H17A	105.8
C1—C2—H2A	110.0	C13—C18—H18A	109.5
C3—C2—H2B	110.0	C13—C18—H18B	109.5
C1—C2—H2B	110.0	H18A—C18—H18B	109.5
H2A—C2—H2B	108.4	C13—C18—H18C	109.5
O29—C3—C2	109.6 (3)	H18A—C18—H18C	109.5
O29—C3—C4	107.7 (3)	H18B—C18—H18C	109.5
C2—C3—C4	110.7 (3)	C10—C19—H19A	109.5
O29—C3—H3A	109.6	C10—C19—H19B	109.5
C2—C3—H3A	109.6	H19A—C19—H19B	109.5
C4—C3—H3A	109.6	C10—C19—H19C	109.5
C3—C4—C5	109.9 (3)	H19A—C19—H19C	109.5
C3—C4—H4A	109.7	H19B—C19—H19C	109.5
C5—C4—H4A	109.7	C21—C20—C22	108.5 (3)
C3—C4—H4B	109.7	C21—C20—C17	111.3 (3)
C5—C4—H4B	109.7	C22—C20—C17	114.7 (3)
H4A—C4—H4B	108.2	C21—C20—H20A	107.3
C6—C5—C4	119.9 (3)	C22—C20—H20A	107.3
C6—C5—C10	124.1 (3)	C17—C20—H20A	107.3
C4—C5—C10	115.9 (3)	C20—C21—H21A	109.5
C5—C6—C7	124.9 (3)	C20—C21—H21B	109.5
C5—C6—H6A	117.5	H21A—C21—H21B	109.5
C7—C6—H6A	117.5	C20—C21—H21C	109.5
C6—C7—C8	112.9 (3)	H21A—C21—H21C	109.5
C6—C7—H7A	109.0	H21B—C21—H21C	109.5
C8—C7—H7A	109.0	N27—C22—C23	110.2 (3)
C6—C7—H7B	109.0	N27—C22—C20	110.8 (3)
C8—C7—H7B	109.0	C23—C22—C20	115.3 (2)
H7A—C7—H7B	107.8	N27—C22—H22A	106.7
C14—C8—C7	110.4 (2)	C23—C22—H22A	106.7
C14—C8—C9	108.5 (2)	C20—C22—H22A	106.7
C7—C8—C9	110.5 (2)	C22—C23—C24	111.8 (3)
C14—C8—H8A	109.1	C22—C23—H23A	109.3
C7—C8—H8A	109.1	C24—C23—H23A	109.3
C9—C8—H8A	109.1	C22—C23—H23B	109.3
C11—C9—C8	110.8 (2)	C24—C23—H23B	109.3
C11—C9—C10	113.5 (2)	H23A—C23—H23B	107.9
C8—C9—C10	113.5 (2)	C25—C24—C23	111.2 (3)
C11—C9—H9A	106.1	C25—C24—H24A	109.4
C8—C9—H9A	106.1	C23—C24—H24A	109.4
C10—C9—H9A	106.1	C25—C24—H24B	109.4
C5—C10—C19	108.3 (2)	C23—C24—H24B	109.4
C5—C10—C1	108.9 (2)	H24A—C24—H24B	108.0
C19—C10—C1	109.8 (3)	C24—C25—C26	109.1 (4)
C5—C10—C9	109.8 (3)	C24—C25—C28	112.7 (4)
C19—C10—C9	112.0 (2)	C26—C25—C28	110.9 (4)
C1—C10—C9	108.0 (2)	C24—C25—H25A	108.0
C9—C11—C12	114.4 (3)	C26—C25—H25A	108.0
C9—C11—H11A	108.7	C28—C25—H25A	108.0
C12—C11—H11A	108.7	N27—C26—C25	110.9 (3)
C9—C11—H11B	108.7	N27—C26—H26A	109.5
C12—C11—H11B	108.7	C25—C26—H26A	109.5
H11A—C11—H11B	107.6	N27—C26—H26B	109.5
C13—C12—C11	112.5 (2)	C25—C26—H26B	109.5
C13—C12—H12A	109.1	H26A—C26—H26B	108.1
C11—C12—H12A	109.1	C22—N27—C26	112.7 (3)
C13—C12—H12B	109.1	C26—N27—H27	103 (3)
C11—C12—H12B	109.1	C22—N27—H27	114 (3)
H12A—C12—H12B	107.8	C25—C28—H28A	109.5
C12—C13—C14	106.1 (2)	C25—C28—H28B	109.5
C12—C13—C18	110.8 (3)	H28A—C28—H28B	109.5
C14—C13—C18	112.7 (2)	C25—C28—H28C	109.5
C12—C13—C17	117.1 (2)	H28A—C28—H28C	109.5
C14—C13—C17	99.1 (2)	H28B—C28—H28C	109.5
C18—C13—C17	110.6 (2)	C30—O29—C3	117.9 (3)
C15—C14—C8	118.9 (2)	O31B—C30—O29	120.3 (7)
C15—C14—C13	104.2 (2)	O31A—C30—O29	121.6 (9)
C8—C14—C13	116.3 (2)	O31A—C30—C32A	120.1 (7)
C15—C14—H14A	105.4	O29—C30—C32A	115.2 (5)
C8—C14—H14A	105.4	O31B—C30—C32B	131.7 (7)
C13—C14—H14A	105.4	O29—C30—C32B	105.6 (4)
C14—C15—C16	104.9 (2)	C30—C32A—H32A	109.5
C14—C15—H15A	110.8	C30—C32A—H32B	109.5
C16—C15—H15A	110.8	C30—C32A—H32C	109.5
C14—C15—H15B	110.8	C30—C32B—H32D	109.5
C16—C15—H15B	110.8	C30—C32B—H32E	109.5
H15A—C15—H15B	108.9	H32D—C32B—H32E	109.5
O33—C16—C15	108.1 (2)	C30—C32B—H32F	109.5
O33—C16—C17	115.3 (3)	H32D—C32B—H32F	109.5
C15—C16—C17	106.1 (2)	H32E—C32B—H32F	109.5
O33—C16—H16A	109.1	C16—O33—H33	104 (3)
C10—C1—C2—C3	−56.5 (4)	C17—C13—C14—C15	46.5 (3)
C1—C2—C3—O29	−179.8 (3)	C12—C13—C14—C8	−58.9 (3)
C1—C2—C3—C4	61.5 (4)	C18—C13—C14—C8	62.5 (3)
O29—C3—C4—C5	179.9 (3)	C17—C13—C14—C8	179.4 (2)
C2—C3—C4—C5	−60.2 (4)	C8—C14—C15—C16	−167.3 (2)
C3—C4—C5—C6	−125.3 (4)	C13—C14—C15—C16	−35.9 (3)
C3—C4—C5—C10	53.7 (4)	C14—C15—C16—O33	134.4 (3)
C4—C5—C6—C7	179.0 (3)	C14—C15—C16—C17	10.2 (3)
C10—C5—C6—C7	0.1 (5)	C12—C13—C17—C20	77.3 (3)
C5—C6—C7—C8	13.8 (5)	C14—C13—C17—C20	−169.3 (2)
C6—C7—C8—C14	−161.3 (2)	C18—C13—C17—C20	−50.8 (4)
C6—C7—C8—C9	−41.3 (3)	C12—C13—C17—C16	−152.4 (2)
C14—C8—C9—C11	−52.1 (3)	C14—C13—C17—C16	−39.1 (3)
C7—C8—C9—C11	−173.2 (2)	C18—C13—C17—C16	79.4 (3)
C14—C8—C9—C10	178.9 (2)	O33—C16—C17—C13	−100.9 (3)
C7—C8—C9—C10	57.8 (3)	C15—C16—C17—C13	18.7 (3)
C6—C5—C10—C19	−108.4 (4)	O33—C16—C17—C20	31.0 (4)
C4—C5—C10—C19	72.7 (3)	C15—C16—C17—C20	150.5 (2)
C6—C5—C10—C1	132.2 (3)	C13—C17—C20—C21	−54.7 (4)
C4—C5—C10—C1	−46.7 (3)	C16—C17—C20—C21	−179.4 (3)
C6—C5—C10—C9	14.2 (4)	C13—C17—C20—C22	−178.3 (3)
C4—C5—C10—C9	−164.7 (2)	C16—C17—C20—C22	56.9 (3)
C2—C1—C10—C5	48.2 (4)	C21—C20—C22—N27	148.0 (3)
C2—C1—C10—C19	−70.3 (4)	C17—C20—C22—N27	−86.9 (3)
C2—C1—C10—C9	167.3 (3)	C21—C20—C22—C23	−86.0 (4)
C11—C9—C10—C5	−170.5 (2)	C17—C20—C22—C23	39.1 (4)
C8—C9—C10—C5	−42.8 (3)	N27—C22—C23—C24	−53.0 (4)
C11—C9—C10—C19	−50.1 (4)	C20—C22—C23—C24	−179.3 (3)
C8—C9—C10—C19	77.5 (3)	C22—C23—C24—C25	54.5 (5)
C11—C9—C10—C1	71.0 (3)	C23—C24—C25—C26	−55.8 (4)
C8—C9—C10—C1	−161.4 (3)	C23—C24—C25—C28	−179.5 (4)
C8—C9—C11—C12	52.1 (3)	C24—C25—C26—N27	58.1 (4)
C10—C9—C11—C12	−178.9 (2)	C28—C25—C26—N27	−177.1 (4)
C9—C11—C12—C13	−54.0 (3)	C25—C26—N27—C22	−59.3 (5)
C11—C12—C13—C14	53.1 (3)	C23—C22—N27—C26	56.1 (4)
C11—C12—C13—C18	−69.5 (3)	C20—C22—N27—C26	−175.1 (3)
C11—C12—C13—C17	162.5 (2)	C2—C3—O29—C30	109.9 (4)
C7—C8—C14—C15	−53.7 (3)	C4—C3—O29—C30	−129.5 (4)
C9—C8—C14—C15	−175.0 (2)	C3—O29—C30—O31B	−18.9 (14)
C7—C8—C14—C13	−179.6 (2)	C3—O29—C30—O31A	18 (2)
C9—C8—C14—C13	59.2 (3)	C3—O29—C30—C32A	178.6 (5)
C12—C13—C14—C15	168.2 (2)	C3—O29—C30—C32B	176.8 (6)
C18—C13—C14—C15	−70.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O33—H33···N27	0.90 (4)	1.93 (4)	2.777 (4)	157 (5)