(25R)-3β,16β-Diacet­oxy-23-acetyl-22,26-ep­oxy­cholesta-5,22-diene n-hexane 0.8-solvate

Hernández Linares, M.-G.; Carrasco-Carballo, A.; Guerrero-Luna, G.; Bernès, S.; Aguirre Hernández, G.

doi:10.1107/S2414314616006222

organic compounds

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ISSN: 2414-3146

Volume 1| Part 4| April 2016| x160622

doi:10.1107/S2414314616006222

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(25R)-3β,16β-Diacetoxy-23-acetyl-22,26-epoxycholesta-5,22-diene n-hexane 0.8-solvate

María-Guadalupe Hernández Linares,^a Alan Carrasco-Carballo,^a Gabriel Guerrero-Luna,^a Sylvain Bernès ^b ^* and Gerardo Aguirre Hernández ^c

^aLaboratorio de Investigación del Jardín Botánico, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, Edif. 113 Complejo de Ciencias CU, San Manuel, 72570 Puebla, Pue., Mexico, ^bInstituto de Física, Benemérita Universidad Autónoma de Puebla, Av. San Claudio y 18 Sur, 72570 Puebla, Pue., Mexico, and ^cCentro de Graduados e Investigación del Instituto Tecnológico de Tijuana, Apdo. Postal 1166, 22500 Tijuana, B.C., Mexico
^*Correspondence e-mail: sylvain_bernes@hotmail.com

Edited by P. Bombicz, Hungarian Academy of Sciences, Hungary (Received 31 January 2016; accepted 13 April 2016; online 19 April 2016)

In the title solvate, C₃₃H₄₈O₆·0.8C₆H₁₄, the steroid presents a conformation almost identical to that of its previously characterized benzene monosolvate [Sandoval-Ramírez et al. (1999 ). Tetrahedron Lett. 40, 5143–5146]. The n-hexane solvent of crystallization is agglomerated in channels parallel to [100] in the crystal. The solvent molecule is disordered over two sites in the asymmetric unit, with occupancies of 0.46 and 0.34. A minor disorder for the carbonyl O atom of the acetyl substituent at position 16 in the steroid was also introduced, with two sites having occupancies of 0.7 and 0.3.

Keywords: crystal structure; steroid; diosgenin; solvate.

CCDC reference: 1473880

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Chemical scheme

Structure description

The crystallization process for the title steroid afforded a hexane solvate (Fig. 1), which crystallizes in an orthorhombic cell close to that previously reported for the benzene monosolvate (Sandoval-Ramírez et al., 1999; Refcode HOSKAB in the CSD). In both structures, the steroidal molecule adopts the same conformation. HOSKAB was reported and deposited with the wrong configuration; however, after inversion, a fit with the steroid reported here gives an r.m.s. deviation between the two molecules of 0.058 Å (Macrae et al., 2008 ). The pyran ring C22–C26/O5 in the title structure also adopts the same twisted conformation found in related steroids bearing this ring (Sandoval-Ramírez et al., 1999; Castro-Méndez et al., 2002 ; Pérez-Díaz et al., 2010 ).

Figure 1
The structure of the title solvate, with displacement ellipsoids at the 30% probability level. Only one site for the disordered atom O4 has been retained. The inset represents the model used for the disordered solvent. The blue hexane molecule has a site occupancy factor of 0.46, and the red molecule has 0.34 occupancy.

Once the steroid is placed in the asymmetric unit, the refinement converges to R₁ = 0.073 (observed data), but ca 24% of the cell volume is unoccupied. Difference maps show that residual density is present in these voids, which may be modelled as two disordered n-hexane molecules, C101–C106 and C201–C206 (Fig. 1, inset). After refining occupancies for each part, the hexane content may be roughly estimated as 0.8 hexane per asymmetric unit, and the refinement converges to R₁ = 0.040. Alternatively, starting from the unsolvated model, the SQUEEZE procedure (Spek, 2015 ) retrieves a density of 76 electrons in the unit cell, within two voids of 423 Å³ (1.2 Å probe radius). Assuming that the solvent is hexane, these data correspond to a lower solvent content, ca 0.4 hexane per asymmetric unit. With the SQUEEZE-based data, the structure refinement converges to R₁ = 0.042.

The actual steroid:solvent stoichiometry for this crystal should thus be in the range 1:0.4 to 1:0.8, but the latter ratio was retained for the present report, which is based on diffraction data: after location of atoms C101–C206, the geometry in each part was restrained (see Refinement details section) and the structure refined with isotropic solvent. Occupancies for each part were then freely refined. In the last cycles, the solvent was refined with anisotropic displacement parameters, and site occupancies were fixed, in order to prevent correlations with thermal factors. In the final model, displacement for C atoms of hexane are rather large (Fig. 1), indicating that these disordered molecules interact poorly with the host molecules in the crystal. If, starting from this model, occupancies for solvent are decreased by 50%, residuals rise to R₁ = 0.049 for observed data and wR₂ = 0.137 for all data. On the other hand, the reported host:guest stoichiometry corresponds to the analysed single crystal, and solvent content may vary from crystal to crystal. The accurate stoichiometry and the reproducibility for a bulk preparation of this solvate remain unknown.

The model including coordinates for the solvent is severely disordered, as reflected in the high ADP's for atoms C101–C206. It is worth mentioning that attempts to include AcOEt as the solvent in the model were unsuccessful. It thus seems that this steroid is prone to interact with non-polar solvents, such as hexane and benzene. In the crystal, hexane is located in channels parallel to [100], and is arranged in such a way that a continuous electronic density is observed along the channels (Fig. 2). The n-hexane conformation includes for both molecules one cis torsion angle, C103—C104—C105—C106 = 8(7)°, and C202—C203—C204—C205 = −23 (8)°. This conformation is not common, compared to the full-trans conformer, but has been observed in many non-disordered solvate structures (e.g. Weberski et al., 2012 ; Soki et al., 2008 ). This bent conformation for n-hexane is reflected in the zigzag shape of the channels containing solvent molecules.

Figure 2
Part of the crystal structure for the title solvate. Five steroids are represented, one of which with a spacefill model. Channels parallel to [100] containing disordered n-hexane molecules are represented using the solvent accessible surface calculated using the non-solvated model (Macrae et al., 2008

). A probe radius of 1 Å was used, with a grid resolution of 0.25 Å.

Synthesis and crystallization

To a solution of diosgenin (2.0 g, 4.83 mmol) in acetic anhydride (10 ml) was added BF₃–OEt₂ (1.8 ml). The mixture was stirred for 10 min at room temperature. After 10 min, the mixture was poured into cold water (10 ml) and stirred for a further hour. The organic phase was neutralized with saturated NaHCO₃ solution (2 ×15 ml), DCM was added (15 ml) and the mixture washed with H₂O (2 ×10 ml). The organic phases were dried with Na₂SO₄ and evaporated under reduced pressure, affording a lacquer solid. This crude was purified by chromatography over silica gel (n-hexane:AcOEt, 85:15), giving the title epoxycholestene as a white solid (1.30 g, 75%). This compound was recrystallized from hexane solution, giving single crystals of the title solvate, m.p. 95–96 °C, [α_D] = −24 (c = 0.65, CHCl₃). Crystals are apparently air-stable for months, and were stored in a non-controlled atmosphere prior to crystallographic study. The IR spectrum of the crystallized compound shows better resolved absorption bands, compared to the crude lacquer, and vibrations in the range 681–832 cm⁻¹ confirm the presence of hexane in the crystals.

¹H-NMR (500 MHz, CDCl₃), δ: 5.35 (1H, d, J_6–7e = 4.5 Hz, H-6), 5.14 (1H, ddd, J_16–17 = J_16–15e = 7.5 and J_16–15a = 4.5 Hz, H-16), 4.59 (1H, m, H-3), 4.07 (1H, m, H-20), 3.48 (1H, dd, J_26e–25 = 3.5 and J_26e–26a=10.5 Hz, H-26_e), 3.41 (1H, dd, J_26a–25 = J_26a–26e = 10.5 Hz, H-26_a), 2.20 (3H, s, CH₃-23²), 2.02 (3H, s, CH₃CO₂-3), 1.84 (3H, s, CH₃CO₂-16), 1.18 (3H, d, J_21–20 = 6.0 Hz, CH₃-21), 1.03 (3H, s, CH₃-19), 0.97 (3H, d, J_27–25 = 6.0 Hz, CH₃-27), 0.92 (3H, s, CH₃-18). ¹³C-NMR (125 MHz, CDCl₃), δ: 197.9 (C-23¹), 171.1 (C-22), 170.4 (CH₃COO-3), 170.3 (CH₃COO-16), 139.6 (C-5), 122.1 (C-6), 106.8 (C-23), 74.9 (C-16), 73.7 (C-3), 71.4 (C-26), 55.8 (C-17), 54.2 (C-14), 49.9 (C-9), 42.1 (C-13), 39.6 (C-12), 37.9 (C-4), 36.8 (C-1), 36.4 (C-10), 34.8 (C-15), 32.7 (C-20), 31.5 (C-24), 31.5 (C-7), 31.3 (C-8), 29.6 (C-23²), 27.6 (C-2), 26.4 (C-25), 21.2 (CH₃COO-3), 21.0 (CH₃COO-16), 20.7 (C-11), 19.3 (C-21), 19.1 (C-19), 16.7 (C-27), 12.8 (C-18).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. For the disordered solvent, C—C bond lengths and 1,3-C⋯C distances were restrained to 1.53 (2) and 2.52 (3) Å, respectively. Moreover, C atoms were restrained with effective standard deviation of 0.1 Å² to have their U_ij components approximating an isotropic behaviour (ISOR command; Sheldrick, 2015 ). Site occupancies for molecules C101–C106 and C201–C206 were first refined, and then fixed in the final refinement cycles, to 0.46 and 0.34, respectively. A minor disorder in the steroidal molecule was also considered for the carbonyl O atom O4, disordered over two sites O4A and O4B, with occupancies 0.7 and 0.3, respectively. The absolute configuration expected for the steroid is in agreement with the refined Flack parameter, x = 0.09 (6).

Table 1
Experimental details

Crystal data
Chemical formula	C₃₃H₄₈O₆·0.8C₆H₁₄
M_r	609.65
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	294
a, b, c (Å)	11.64797 (17), 12.20869 (17), 25.7274 (4)
V (Å³)	3658.60 (9)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.58
Crystal size (mm)	0.45 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku SuperNova
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Americas Corporation, The Woodlands, TX, USA.]$ )
T_min, T_max	0.663, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	19071, 6767, 5885
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.106, 1.01
No. of reflections	6767
No. of parameters	477
No. of restraints	90
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.11
Absolute structure	Flack x determined using 2066 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.09 (6)
Computer programs: CrysAlis PRO (Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Americas Corporation, The Woodlands, TX, USA.]$ ), SHELXS2013 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015) and Mercury (Macrae et al., 2008).

Structural data

CCDC reference: 1473880

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616006222/zp4003sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616006222/zp4003Isup2.hkl

checkCIF report

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Experimental top

To a solution of diosgenin (2.0 g, 4.83 mmol) in acetic anhydride (10 ml) was added BF₃–OEt₂ (1.8 ml). The mixture was stirred for 10 min at room temperature. After 10 min, the mixture was poured into cold water (10 ml) and stirred for a further hour. The organic phase was neutralized with saturated NaHCO₃ solution (2 ×15 ml), DCM was added (15 ml) and the mixture washed with H₂O (2 ×10 ml). The organic phases were dried with Na₂SO₄ and evaporated under reduced pressure, affording a lacquer solid. This crude was purified by chromatography over silica gel (n-hexane:AcOEt, 85:15), giving the title epoxycholestene as a white solid (1.30 g, 75%). This compound was recrystallized from hexane, giving single crystals of the title solvate, m.p. 95–96 °C, [α_D] = -24 (c = 0.65, CHCl₃). Crystals are apparently air-stable for months, and were stored in a non-controlled atmosphere prior to crystallographic study. The IR spectrum of the crystallized compound shows better resolved absorption bands, compared to the crude lacquer, and vibrations in the range 681–832 cm^-1 confirm the presence of hexane in the crystals.

¹H-NMR (500 MHz, CDCl₃), δ: 5.35 (1H, d, J_{6–7 e} = 4.5 Hz, H-6), 5.14 (1H, ddd, J_16–17 = J_{16–15 e} = 7.5 and J_16–15_a = 4.5 Hz, H-16), 4.59 (1H, m, H-3), 4.07 (1H, m, H-20), 3.48 (1H, dd, J_{26 e-25} = 3.5 and J_{26 e-26}_a=10.5 Hz, H-26_e), 3.41 (1H, dd, J₂₆_a_-25 = J₂₆_a_{-26 e} = 10.5 Hz, H-26_a), 2.20 (3H, s, CH₃-23²), 2.02 (3H, s, CH₃CO₂-3), 1.84 (3H, s, CH₃CO₂-16), 1.18 (3H, d, J_21–20 = 6.0 Hz, CH₃-21), 1.03 (3H, s, CH₃-19), 0.97 (3H, d, J_27–25 = 6.0 Hz, CH₃-27), 0.92 (3H, s, CH₃-18). ¹³C-NMR (125 MHz, CDCl₃), δ: 197.9 (C-23¹), 171.1 (C-22), 170.4 (CH₃COO-3), 170.3 (CH₃COO-16), 139.6 (C-5), 122.1 (C-6), 106.8 (C-23), 74.9 (C-16), 73.7 (C-3), 71.4 (C-26), 55.8 (C-17), 54.2 (C-14), 49.9 (C-9), 42.1 (C-13), 39.6 (C-12), 37.9 (C-4), 36.8 (C-1), 36.4 (C-10), 34.8 (C-15), 32.7 (C-20), 31.5 (C-24), 31.5 (C-7), 31.3 (C-8), 29.6 (C-23²), 27.6 (C-2), 26.4 (C-25), 21.2 (CH₃COO-3), 21.0 (CH₃COO-16), 20.7 (C-11), 19.3 (C-21), 19.1 (C-19), 16.7 (C-27), 12.8 (C-18).

Structure description top

The crystallization process for the title steroid afforded a hexane solvate (Fig. 1), which crystallizes in an orthorhombic cell close to that previously reported for the benzene monosolvate (Sandoval-Ramírez et al., 1999; Refcode HOSKAB in the CSD). In both structures, the steroidal molecule adopts the same conformation. HOSKAB was reported and deposited with the wrong configuration; however, after inversion, a fit with the title steroid gives an r.m.s. deviation between the two molecules of 0.058 Å (Macrae et al., 2008). The pyran ring C22–C26/O5 in the title structure also adopts the same twisted conformation found in related steroids bearing this ring (Sandoval-Ramírez et al., 1999; Castro-Méndez et al., 2002; Pérez-Díaz et al., 2010).

Once the steroid is placed in the asymmetric unit, the refinement converges to R₁ = 0.073 (observed data), but ca 24% of the cell volume is unoccupied. Difference maps show that residual density is present in these voids, which may be modeled as two disordered n-hexane molecules, C101–C106 and C201–C206 (Fig. 1, inset). After refining occupancies for each part, the hexane content may be roughly estimated as 0.8 hexane per asymmetric unit, and the refinement converges to R₁ = 0.040. Alternatively, starting from the unsolvated model, the SQUEEZE procedure (Spek, 2015) retrieves a density of 76 electrons in the unit cell, within two voids of 423 Å³ (1.2 Å probe radius). Assuming that the lattice solvent is hexane, these data correspond to a lower solvent content, ca 0.4 hexane per asymmetric unit. With the SQUEEZE-based data, the structure refinement converges to R₁ = 0.042.

The model including coordinates for lattice solvent is severely disordered, as reflected in the high ADP's for atoms C101–C206. It is worth mentioning that attempts to include AcOEt as lattice solvent in the model were unsuccessful. It thus seems that this steroid is prone to interact with non-polar solvents, such as hexane and benzene. In the crystal, hexane is located in channels parallel to [100], and is arranged in such a way that a continuous electronic density is observed along the channels (Fig. 2). The n-hexane conformation includes for both molecules one cis torsion angle, C103—C104—C105—C106 = 8(7)°, and C202—C203—C204—C205 = -23 (8)°. This conformation is not common, compared to the full-trans conformer, but has been observed in many non-disordered solvate structures (e.g. Weberski et al., 2012; Soki et al., 2008). This bent conformation for n-hexane is reflected in the zigzag shape of the channels containing solvent molecules.

Computing details top

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures top

	Fig. 1. The structure of the title solvate, with displacement ellipsoids at the 30% probability level. Only one site for the disordered atom O4 has been retained. The inset represents the model used for the disordered solvent. The blue hexane molecule has a site occupancy factor of 0.46, and the red molecule has 0.34 occupancy.
	Fig. 2. Part of the crystal structure for the title solvate. Five steroids are represented, one of which with a spacefill model. Channels parallel to [100] containing disordered n-hexane molecules are represented using the solvent accessible surface calculated using the non-solvated model (Macrae et al., 2008). A probe radius of 1 Å was used, with a grid resolution of 0.25 Å.

(25R)-3β,16β-Diacetoxy-23-acetyl-22,26-epoxycholesta-5,22-diene n-hexane 0.8-solvate top

Crystal data top

C₃₃H₄₈O₆·0.8C₆H₁₄	D_x = 1.107 Mg m⁻³
M_r = 609.65	Melting point: 368 K
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54184 Å
a = 11.64797 (17) Å	Cell parameters from 10211 reflections
b = 12.20869 (17) Å	θ = 1.7–71.1°
c = 25.7274 (4) Å	µ = 0.58 mm⁻¹
V = 3658.60 (9) Å³	T = 294 K
Z = 4	Irregular, colourless
F(000) = 1336	0.45 × 0.30 × 0.20 mm

Data collection top

Rigaku SuperNova diffractometer	6767 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	5885 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.020
Detector resolution: 5.1980 pixels mm^-1	θ_max = 71.7°, θ_min = 3.4°
ω scans	h = −14→14
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	k = −14→12
T_min = 0.663, T_max = 1.000	l = −31→28
19071 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.040	w = 1/[σ²(F_o²) + (0.0616P)² + 0.1048P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.106	(Δ/σ)_max = 0.001
S = 1.01	Δρ_max = 0.15 e Å⁻³
6767 reflections	Δρ_min = −0.11 e Å⁻³
477 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
90 restraints	Extinction coefficient: 0.00090 (16)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack x determined using 2066 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.09 (6)

Crystal data top

C₃₃H₄₈O₆·0.8C₆H₁₄	V = 3658.60 (9) Å³
M_r = 609.65	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 11.64797 (17) Å	µ = 0.58 mm⁻¹
b = 12.20869 (17) Å	T = 294 K
c = 25.7274 (4) Å	0.45 × 0.30 × 0.20 mm

Data collection top

Rigaku SuperNova diffractometer	6767 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	5885 reflections with I > 2σ(I)
T_min = 0.663, T_max = 1.000	R_int = 0.020
19071 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.106	Δρ_max = 0.15 e Å⁻³
S = 1.01	Δρ_min = −0.11 e Å⁻³
6767 reflections	Absolute structure: Flack x determined using 2066 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
477 parameters	Absolute structure parameter: 0.09 (6)
90 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.0960 (2)	0.3162 (2)	−0.14991 (9)	0.0593 (6)
H1A	0.1179	0.3838	−0.1327	0.071*
H1B	0.1618	0.2676	−0.1492	0.071*
C2	0.0657 (2)	0.3415 (2)	−0.20665 (9)	0.0658 (6)
H2A	0.0030	0.3938	−0.2079	0.079*
H2B	0.1315	0.3739	−0.2239	0.079*
C3	0.0314 (2)	0.2386 (2)	−0.23421 (8)	0.0603 (6)
H3A	0.0972	0.1888	−0.2363	0.072*
C4	−0.0677 (2)	0.1820 (2)	−0.20711 (9)	0.0634 (6)
H4A	−0.0822	0.1121	−0.2238	0.076*
H4B	−0.1363	0.2264	−0.2106	0.076*
C5	−0.04301 (19)	0.1632 (2)	−0.14994 (9)	0.0541 (5)
C6	−0.0558 (2)	0.0648 (2)	−0.12974 (9)	0.0628 (6)
H6A	−0.0785	0.0086	−0.1519	0.075*
C7	−0.0365 (3)	0.0368 (2)	−0.07381 (9)	0.0662 (7)
H7A	0.0360	−0.0015	−0.0703	0.079*
H7B	−0.0970	−0.0118	−0.0621	0.079*
C8	−0.03482 (19)	0.13903 (18)	−0.03968 (8)	0.0503 (5)
H8A	−0.1132	0.1677	−0.0372	0.060*
C9	0.04179 (17)	0.22702 (18)	−0.06467 (8)	0.0469 (5)
H9A	0.1166	0.1925	−0.0706	0.056*
C10	−0.00335 (18)	0.26254 (18)	−0.11905 (8)	0.0488 (5)
C11	0.0635 (2)	0.32403 (19)	−0.02824 (8)	0.0563 (6)
H11A	−0.0056	0.3684	−0.0269	0.068*
H11B	0.1239	0.3689	−0.0430	0.068*
C12	0.0976 (2)	0.2932 (2)	0.02766 (9)	0.0551 (5)
H12A	0.1735	0.2605	0.0274	0.066*
H12B	0.1008	0.3589	0.0488	0.066*
C13	0.01193 (17)	0.21232 (16)	0.05185 (8)	0.0448 (4)
C14	0.0082 (2)	0.11360 (17)	0.01492 (8)	0.0500 (5)
H14A	0.0879	0.0894	0.0109	0.060*
C15	−0.0515 (3)	0.0249 (2)	0.04625 (9)	0.0656 (7)
H15A	−0.0337	−0.0473	0.0327	0.079*
H15B	−0.1341	0.0351	0.0461	0.079*
C16	−0.0024 (2)	0.04006 (17)	0.10084 (8)	0.0537 (5)
H16A	0.0571	−0.0151	0.1072	0.064*
C17	0.05149 (18)	0.15607 (18)	0.10319 (8)	0.0480 (5)
H17A	0.1347	0.1460	0.1003	0.058*
C18	−0.1067 (2)	0.2655 (2)	0.05906 (9)	0.0577 (6)
H18A	−0.1364	0.2872	0.0258	0.087*
H18B	−0.0996	0.3287	0.0810	0.087*
H18C	−0.1580	0.2138	0.0748	0.087*
C19	−0.1025 (2)	0.3444 (2)	−0.11385 (9)	0.0671 (7)
H19A	−0.1390	0.3537	−0.1470	0.101*
H19B	−0.0732	0.4136	−0.1021	0.101*
H19C	−0.1574	0.3172	−0.0892	0.101*
C20	0.03072 (19)	0.21759 (17)	0.15443 (8)	0.0515 (5)
H20A	−0.0518	0.2322	0.1573	0.062*
C21	0.0939 (3)	0.32813 (19)	0.15666 (10)	0.0680 (7)
H21A	0.0831	0.3607	0.1903	0.102*
H21B	0.0638	0.3760	0.1304	0.102*
H21C	0.1744	0.3167	0.1507	0.102*
C22	0.06676 (18)	0.15316 (18)	0.20189 (8)	0.0508 (5)
C23	0.0169 (2)	0.15302 (19)	0.24931 (8)	0.0533 (5)
C24	0.0759 (2)	0.0987 (2)	0.29503 (9)	0.0597 (6)
H24A	0.0695	0.1456	0.3253	0.072*
H24B	0.0375	0.0301	0.3029	0.072*
C25	0.2011 (2)	0.0766 (2)	0.28404 (10)	0.0630 (6)
H25A	0.2418	0.1468	0.2836	0.076*
C26	0.2101 (2)	0.0263 (2)	0.23068 (10)	0.0700 (7)
H26A	0.2900	0.0102	0.2231	0.084*
H26B	0.1678	−0.0421	0.2300	0.084*
C27	0.2561 (3)	0.0042 (3)	0.32510 (12)	0.0888 (9)
H27A	0.3369	−0.0020	0.3183	0.133*
H27B	0.2217	−0.0672	0.3241	0.133*
H27C	0.2446	0.0361	0.3588	0.133*
C28	0.0022 (3)	0.1973 (2)	−0.32408 (10)	0.0747 (7)
C29	−0.0428 (4)	0.2421 (3)	−0.37442 (12)	0.1170 (15)
H29A	−0.0289	0.1902	−0.4018	0.175*
H29B	−0.0044	0.3096	−0.3823	0.175*
H29C	−0.1238	0.2551	−0.3714	0.175*
C30	−0.1137 (3)	−0.0708 (2)	0.15718 (11)	0.0731 (7)
C31	−0.2033 (3)	−0.0710 (3)	0.19839 (12)	0.0910 (9)
H31A	−0.2010	−0.1394	0.2168	0.137*
H31B	−0.2775	−0.0619	0.1828	0.137*
H31C	−0.1893	−0.0119	0.2222	0.137*
C32	−0.0957 (2)	0.2042 (2)	0.25880 (10)	0.0671 (7)
C33	−0.1545 (3)	0.1791 (3)	0.30966 (11)	0.0949 (11)
H33A	−0.2336	0.2008	0.3077	0.142*
H33B	−0.1174	0.2185	0.3372	0.142*
H33C	−0.1501	0.1019	0.3165	0.142*
O1	−0.00373 (18)	0.27141 (14)	−0.28652 (7)	0.0729 (5)
O2	0.0358 (3)	0.10678 (19)	−0.31779 (9)	0.1093 (9)
O3	−0.09271 (14)	0.02925 (12)	0.13953 (6)	0.0584 (4)
O4A	−0.0784 (7)	−0.1523 (5)	0.1346 (2)	0.106 (2)	0.7
O4B	−0.0395 (14)	−0.1374 (12)	0.1589 (5)	0.106 (4)	0.3
O5	0.16551 (14)	0.09843 (14)	0.19159 (6)	0.0634 (4)
O6	−0.1443 (2)	0.2660 (2)	0.22891 (8)	0.1006 (8)
C101	0.286 (3)	−0.111 (2)	0.0273 (17)	0.293 (18)	0.46
H10C	0.3148	−0.0639	0.0542	0.440*	0.46
H10D	0.2331	−0.0710	0.0059	0.440*	0.46
H10E	0.3490	−0.1363	0.0063	0.440*	0.46
C102	0.227 (3)	−0.205 (4)	0.0508 (12)	0.307 (16)	0.46
H10I	0.1780	−0.1793	0.0786	0.369*	0.46
H10J	0.2842	−0.2534	0.0662	0.369*	0.46
C103	0.156 (5)	−0.271 (4)	0.0135 (17)	0.51 (5)	0.46
H10K	0.0984	−0.2226	−0.0015	0.616*	0.46
H10L	0.2050	−0.2953	−0.0146	0.616*	0.46
C104	0.097 (4)	−0.368 (3)	0.0355 (15)	0.42 (4)	0.46
H10M	0.1251	−0.4287	0.0152	0.500*	0.46
H10N	0.1301	−0.3763	0.0698	0.500*	0.46
C105	−0.026 (4)	−0.3922 (18)	0.0431 (12)	0.29 (2)	0.46
H10O	−0.0353	−0.3978	0.0805	0.354*	0.46
H10P	−0.0357	−0.4659	0.0298	0.354*	0.46
C106	−0.132 (4)	−0.330 (4)	0.025 (2)	0.44 (4)	0.46
H10F	−0.1576	−0.2812	0.0514	0.665*	0.46
H10G	−0.1925	−0.3819	0.0170	0.665*	0.46
H10H	−0.1141	−0.2896	−0.0062	0.665*	0.46
C201	0.333 (4)	−0.081 (3)	−0.014 (2)	0.28 (2)	0.34
H20B	0.3018	−0.0096	−0.0199	0.423*	0.34
H20C	0.3818	−0.1015	−0.0423	0.423*	0.34
H20D	0.3761	−0.0813	0.0178	0.423*	0.34
C202	0.236 (4)	−0.162 (3)	−0.0096 (18)	0.31 (3)	0.34
H20H	0.1738	−0.1298	0.0098	0.367*	0.34
H20I	0.2083	−0.1798	−0.0441	0.367*	0.34
C203	0.274 (3)	−0.264 (3)	0.016 (2)	0.267 (19)	0.34
H20J	0.3068	−0.2456	0.0500	0.321*	0.34
H20K	0.3327	−0.2988	−0.0043	0.321*	0.34
C204	0.174 (3)	−0.345 (3)	0.025 (2)	0.30 (3)	0.34
H20L	0.1731	−0.3992	−0.0029	0.365*	0.34
H20M	0.1829	−0.3828	0.0577	0.365*	0.34
C205	0.064 (4)	−0.278 (4)	0.024 (3)	0.52 (6)	0.34
H20N	0.0573	−0.2432	0.0580	0.621*	0.34
H20O	0.0742	−0.2198	−0.0011	0.621*	0.34
C206	−0.049 (4)	−0.334 (6)	0.013 (4)	0.60 (8)	0.34
H20E	−0.0720	−0.3175	−0.0223	0.904*	0.34
H20F	−0.1062	−0.3089	0.0365	0.904*	0.34
H20G	−0.0396	−0.4120	0.0162	0.904*	0.34

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0628 (13)	0.0644 (14)	0.0507 (12)	−0.0102 (12)	0.0027 (11)	0.0054 (11)
C2	0.0828 (16)	0.0650 (15)	0.0497 (12)	−0.0087 (14)	0.0082 (12)	0.0072 (12)
C3	0.0723 (15)	0.0647 (14)	0.0438 (11)	0.0051 (12)	0.0018 (10)	0.0098 (11)
C4	0.0687 (14)	0.0737 (16)	0.0478 (12)	−0.0062 (13)	−0.0075 (11)	0.0009 (12)
C5	0.0523 (11)	0.0646 (14)	0.0455 (11)	−0.0043 (11)	0.0004 (9)	0.0021 (10)
C6	0.0794 (16)	0.0605 (14)	0.0485 (12)	−0.0132 (13)	0.0006 (11)	−0.0048 (11)
C7	0.0938 (18)	0.0540 (13)	0.0507 (13)	−0.0121 (13)	0.0000 (12)	0.0008 (11)
C8	0.0556 (11)	0.0518 (12)	0.0435 (11)	−0.0056 (10)	0.0012 (9)	0.0017 (10)
C9	0.0445 (9)	0.0512 (11)	0.0450 (10)	0.0020 (9)	0.0018 (8)	0.0043 (9)
C10	0.0485 (10)	0.0537 (12)	0.0442 (10)	0.0022 (10)	0.0022 (8)	0.0041 (9)
C11	0.0664 (13)	0.0550 (13)	0.0475 (11)	−0.0102 (11)	−0.0017 (10)	0.0069 (10)
C12	0.0598 (12)	0.0577 (13)	0.0479 (11)	−0.0088 (11)	−0.0033 (10)	0.0035 (10)
C13	0.0451 (10)	0.0464 (11)	0.0427 (10)	0.0017 (9)	0.0003 (8)	0.0035 (9)
C14	0.0559 (11)	0.0492 (11)	0.0450 (11)	0.0008 (10)	0.0038 (9)	0.0034 (9)
C15	0.0924 (18)	0.0519 (13)	0.0524 (13)	−0.0123 (13)	0.0015 (13)	0.0033 (11)
C16	0.0640 (12)	0.0478 (11)	0.0494 (12)	0.0065 (11)	0.0076 (10)	0.0044 (10)
C17	0.0473 (10)	0.0513 (11)	0.0453 (11)	0.0042 (9)	0.0020 (9)	0.0039 (9)
C18	0.0545 (12)	0.0680 (15)	0.0508 (12)	0.0119 (11)	−0.0013 (10)	0.0030 (11)
C19	0.0675 (14)	0.0796 (17)	0.0541 (13)	0.0201 (14)	−0.0013 (11)	0.0066 (13)
C20	0.0586 (12)	0.0519 (12)	0.0439 (11)	0.0088 (10)	−0.0002 (9)	0.0033 (9)
C21	0.0969 (19)	0.0523 (13)	0.0546 (13)	0.0006 (14)	−0.0073 (13)	−0.0002 (11)
C22	0.0537 (11)	0.0494 (11)	0.0493 (11)	0.0044 (10)	0.0000 (9)	0.0036 (10)
C23	0.0592 (12)	0.0545 (12)	0.0462 (11)	0.0026 (11)	−0.0024 (9)	0.0010 (10)
C24	0.0725 (14)	0.0600 (13)	0.0467 (11)	0.0003 (12)	−0.0038 (11)	0.0050 (11)
C25	0.0677 (14)	0.0560 (13)	0.0653 (14)	0.0014 (12)	−0.0151 (12)	0.0077 (12)
C26	0.0734 (16)	0.0723 (16)	0.0643 (15)	0.0201 (14)	−0.0021 (13)	0.0139 (13)
C27	0.103 (2)	0.087 (2)	0.0760 (18)	0.0138 (18)	−0.0292 (17)	0.0129 (16)
C28	0.109 (2)	0.0649 (16)	0.0504 (13)	−0.0007 (17)	0.0046 (14)	−0.0018 (12)
C29	0.195 (4)	0.105 (3)	0.0506 (16)	0.000 (3)	−0.008 (2)	0.0054 (17)
C30	0.090 (2)	0.0578 (15)	0.0709 (17)	−0.0037 (15)	0.0106 (15)	0.0163 (14)
C31	0.103 (2)	0.085 (2)	0.084 (2)	−0.0164 (19)	0.0232 (18)	0.0194 (17)
C32	0.0706 (15)	0.0810 (17)	0.0498 (12)	0.0131 (14)	0.0009 (12)	−0.0039 (13)
C33	0.0777 (18)	0.139 (3)	0.0684 (18)	0.020 (2)	0.0171 (15)	0.0072 (19)
O1	0.1068 (13)	0.0673 (10)	0.0445 (8)	0.0106 (11)	−0.0007 (9)	0.0058 (8)
O2	0.173 (3)	0.0748 (14)	0.0803 (14)	0.0225 (16)	−0.0116 (15)	−0.0131 (11)
O3	0.0677 (9)	0.0522 (9)	0.0552 (9)	0.0003 (8)	0.0112 (8)	0.0089 (7)
O4A	0.169 (6)	0.0501 (19)	0.099 (4)	−0.003 (3)	0.043 (3)	0.002 (3)
O4B	0.128 (10)	0.065 (7)	0.125 (11)	0.030 (7)	0.042 (8)	0.040 (7)
O5	0.0620 (9)	0.0723 (10)	0.0560 (9)	0.0210 (8)	0.0059 (7)	0.0161 (8)
O6	0.1014 (15)	0.1323 (19)	0.0680 (12)	0.0602 (15)	0.0140 (11)	0.0117 (13)
C101	0.21 (3)	0.154 (19)	0.52 (6)	0.004 (18)	−0.05 (3)	0.02 (3)
C102	0.24 (3)	0.35 (5)	0.33 (4)	0.08 (4)	0.06 (3)	0.02 (4)
C103	0.62 (9)	0.47 (9)	0.45 (6)	0.11 (7)	−0.36 (7)	0.06 (6)
C104	0.71 (10)	0.28 (4)	0.26 (3)	−0.14 (6)	0.22 (5)	−0.05 (3)
C105	0.51 (7)	0.139 (14)	0.23 (3)	0.01 (3)	0.11 (4)	−0.031 (15)
C106	0.50 (8)	0.37 (7)	0.46 (7)	−0.25 (6)	−0.01 (7)	−0.04 (6)
C201	0.27 (4)	0.16 (2)	0.41 (6)	−0.05 (3)	0.07 (4)	0.04 (3)
C202	0.34 (5)	0.25 (4)	0.32 (5)	−0.01 (4)	−0.12 (5)	−0.08 (4)
C203	0.26 (4)	0.19 (3)	0.35 (5)	0.07 (3)	−0.04 (4)	−0.07 (3)
C204	0.18 (3)	0.37 (6)	0.37 (6)	0.01 (4)	−0.04 (3)	0.16 (5)
C205	0.80 (13)	0.32 (6)	0.44 (9)	0.25 (8)	−0.04 (9)	−0.21 (6)
C206	0.81 (15)	0.43 (9)	0.56 (11)	−0.17 (10)	0.23 (10)	0.22 (8)

Geometric parameters (Å, º) top

C1—C2	1.533 (3)	C25—C26	1.507 (4)
C1—C10	1.549 (3)	C25—C27	1.519 (4)
C1—H1A	0.9700	C25—H25A	0.9800
C1—H1B	0.9700	C26—O5	1.434 (3)
C2—C3	1.498 (4)	C26—H26A	0.9700
C2—H2A	0.9700	C26—H26B	0.9700
C2—H2B	0.9700	C27—H27A	0.9600
C3—O1	1.462 (3)	C27—H27B	0.9600
C3—C4	1.515 (4)	C27—H27C	0.9600
C3—H3A	0.9800	C28—O2	1.183 (3)
C4—C5	1.516 (3)	C28—O1	1.326 (3)
C4—H4A	0.9700	C28—C29	1.500 (4)
C4—H4B	0.9700	C29—H29A	0.9600
C5—C6	1.317 (3)	C29—H29B	0.9600
C5—C10	1.522 (3)	C29—H29C	0.9600
C6—C7	1.496 (3)	C30—O4B	1.188 (15)
C6—H6A	0.9300	C30—O4A	1.224 (7)
C7—C8	1.526 (3)	C30—O3	1.326 (3)
C7—H7A	0.9700	C30—C31	1.488 (4)
C7—H7B	0.9700	C31—H31A	0.9600
C8—C14	1.523 (3)	C31—H31B	0.9600
C8—C9	1.537 (3)	C31—H31C	0.9600
C8—H8A	0.9800	C32—O6	1.217 (3)
C9—C11	1.531 (3)	C32—C33	1.509 (4)
C9—C10	1.556 (3)	C33—H33A	0.9600
C9—H9A	0.9800	C33—H33B	0.9600
C10—C19	1.533 (3)	C33—H33C	0.9600
C11—C12	1.539 (3)	C101—C102	1.47 (2)
C11—H11A	0.9700	C101—H10C	0.9600
C11—H11B	0.9700	C101—H10D	0.9600
C12—C13	1.535 (3)	C101—H10E	0.9600
C12—H12A	0.9700	C102—C103	1.50 (2)
C12—H12B	0.9700	C102—H10I	0.9700
C13—C14	1.535 (3)	C102—H10J	0.9700
C13—C18	1.537 (3)	C103—C104	1.48 (2)
C13—C17	1.558 (3)	C103—H10K	0.9700
C14—C15	1.518 (3)	C103—H10L	0.9700
C14—H14A	0.9800	C104—C105	1.47 (2)
C15—C16	1.527 (3)	C104—H10M	0.9700
C15—H15A	0.9700	C104—H10N	0.9700
C15—H15B	0.9700	C105—C106	1.53 (3)
C16—O3	1.454 (3)	C105—H10O	0.9700
C16—C17	1.551 (3)	C105—H10P	0.9700
C16—H16A	0.9800	C106—H10F	0.9600
C17—C20	1.536 (3)	C106—H10G	0.9600
C17—H17A	0.9800	C106—H10H	0.9600
C18—H18A	0.9600	C201—C202	1.50 (2)
C18—H18B	0.9600	C201—H20B	0.9600
C18—H18C	0.9600	C201—H20C	0.9600
C19—H19A	0.9600	C201—H20D	0.9600
C19—H19B	0.9600	C202—C203	1.48 (2)
C19—H19C	0.9600	C202—H20H	0.9700
C20—C22	1.512 (3)	C202—H20I	0.9700
C20—C21	1.538 (3)	C203—C204	1.54 (2)
C20—H20A	0.9800	C203—H20J	0.9700
C21—H21A	0.9600	C203—H20K	0.9700
C21—H21B	0.9600	C204—C205	1.52 (3)
C21—H21C	0.9600	C204—H20L	0.9700
C22—C23	1.351 (3)	C204—H20M	0.9700
C22—O5	1.356 (3)	C205—C206	1.52 (3)
C23—C32	1.472 (4)	C205—H20N	0.9700
C23—C24	1.515 (3)	C205—H20O	0.9700
C24—C25	1.510 (4)	C206—H20E	0.9600
C24—H24A	0.9700	C206—H20F	0.9600
C24—H24B	0.9700	C206—H20G	0.9600

C2—C1—C10	113.7 (2)	C25—C24—H24B	109.3
C2—C1—H1A	108.8	C23—C24—H24B	109.3
C10—C1—H1A	108.8	H24A—C24—H24B	107.9
C2—C1—H1B	108.8	C26—C25—C24	108.1 (2)
C10—C1—H1B	108.8	C26—C25—C27	111.6 (2)
H1A—C1—H1B	107.7	C24—C25—C27	112.4 (2)
C3—C2—C1	110.0 (2)	C26—C25—H25A	108.2
C3—C2—H2A	109.7	C24—C25—H25A	108.2
C1—C2—H2A	109.7	C27—C25—H25A	108.2
C3—C2—H2B	109.7	O5—C26—C25	111.3 (2)
C1—C2—H2B	109.7	O5—C26—H26A	109.4
H2A—C2—H2B	108.2	C25—C26—H26A	109.4
O1—C3—C2	106.27 (19)	O5—C26—H26B	109.4
O1—C3—C4	109.6 (2)	C25—C26—H26B	109.4
C2—C3—C4	111.6 (2)	H26A—C26—H26B	108.0
O1—C3—H3A	109.8	C25—C27—H27A	109.5
C2—C3—H3A	109.8	C25—C27—H27B	109.5
C4—C3—H3A	109.8	H27A—C27—H27B	109.5
C3—C4—C5	111.77 (19)	C25—C27—H27C	109.5
C3—C4—H4A	109.3	H27A—C27—H27C	109.5
C5—C4—H4A	109.3	H27B—C27—H27C	109.5
C3—C4—H4B	109.3	O2—C28—O1	123.7 (3)
C5—C4—H4B	109.3	O2—C28—C29	125.0 (3)
H4A—C4—H4B	107.9	O1—C28—C29	111.2 (3)
C6—C5—C4	119.9 (2)	C28—C29—H29A	109.5
C6—C5—C10	123.7 (2)	C28—C29—H29B	109.5
C4—C5—C10	116.4 (2)	H29A—C29—H29B	109.5
C5—C6—C7	124.8 (2)	C28—C29—H29C	109.5
C5—C6—H6A	117.6	H29A—C29—H29C	109.5
C7—C6—H6A	117.6	H29B—C29—H29C	109.5
C6—C7—C8	111.6 (2)	O4B—C30—O3	120.6 (8)
C6—C7—H7A	109.3	O4A—C30—O3	121.6 (4)
C8—C7—H7A	109.3	O4B—C30—C31	118.9 (7)
C6—C7—H7B	109.3	O4A—C30—C31	124.9 (4)
C8—C7—H7B	109.3	O3—C30—C31	112.0 (3)
H7A—C7—H7B	108.0	C30—C31—H31A	109.5
C14—C8—C7	111.60 (18)	C30—C31—H31B	109.5
C14—C8—C9	109.69 (17)	H31A—C31—H31B	109.5
C7—C8—C9	109.76 (17)	C30—C31—H31C	109.5
C14—C8—H8A	108.6	H31A—C31—H31C	109.5
C7—C8—H8A	108.6	H31B—C31—H31C	109.5
C9—C8—H8A	108.6	O6—C32—C23	124.9 (2)
C11—C9—C8	112.35 (17)	O6—C32—C33	117.5 (3)
C11—C9—C10	112.98 (18)	C23—C32—C33	117.5 (2)
C8—C9—C10	111.99 (17)	C32—C33—H33A	109.5
C11—C9—H9A	106.3	C32—C33—H33B	109.5
C8—C9—H9A	106.3	H33A—C33—H33B	109.5
C10—C9—H9A	106.3	C32—C33—H33C	109.5
C5—C10—C19	109.64 (19)	H33A—C33—H33C	109.5
C5—C10—C1	107.22 (18)	H33B—C33—H33C	109.5
C19—C10—C1	109.38 (19)	C28—O1—C3	118.0 (2)
C5—C10—C9	110.49 (18)	C30—O3—C16	116.84 (19)
C19—C10—C9	110.96 (17)	C22—O5—C26	118.21 (17)
C1—C10—C9	109.05 (17)	C102—C101—C106ⁱ	104 (3)
C9—C11—C12	115.15 (18)	C102—C101—H10C	109.5
C9—C11—H11A	108.5	C106ⁱ—C101—H10C	126.5
C12—C11—H11A	108.5	C102—C101—H10D	109.5
C9—C11—H11B	108.5	C106ⁱ—C101—H10D	96.7
C12—C11—H11B	108.5	H10C—C101—H10D	109.5
H11A—C11—H11B	107.5	C102—C101—H10E	109.5
C13—C12—C11	111.63 (18)	H10C—C101—H10E	109.5
C13—C12—H12A	109.3	H10D—C101—H10E	109.5
C11—C12—H12A	109.3	C101—C102—C103	114 (3)
C13—C12—H12B	109.3	C101—C102—H10I	108.7
C11—C12—H12B	109.3	C103—C102—H10I	108.7
H12A—C12—H12B	108.0	C101—C102—H10J	108.7
C12—C13—C14	105.79 (17)	C103—C102—H10J	108.7
C12—C13—C18	111.18 (18)	H10I—C102—H10J	107.6
C14—C13—C18	112.38 (17)	C104—C103—C102	116 (3)
C12—C13—C17	115.77 (17)	C104—C103—H10K	108.3
C14—C13—C17	100.78 (15)	C102—C103—H10K	108.3
C18—C13—C17	110.45 (17)	C104—C103—H10L	108.3
C15—C14—C8	118.96 (19)	C102—C103—H10L	108.3
C15—C14—C13	104.12 (17)	H10K—C103—H10L	107.4
C8—C14—C13	114.83 (17)	C105—C104—C103	132 (3)
C15—C14—H14A	106.0	C105—C104—H10M	104.3
C8—C14—H14A	106.0	C103—C104—H10M	104.3
C13—C14—H14A	106.0	C105—C104—H10N	104.3
C14—C15—C16	103.34 (19)	C103—C104—H10N	104.3
C14—C15—H15A	111.1	H10M—C104—H10N	105.6
C16—C15—H15A	111.1	C104—C105—C106	130 (3)
C14—C15—H15B	111.1	C104—C105—H10O	104.7
C16—C15—H15B	111.1	C106—C105—H10O	104.7
H15A—C15—H15B	109.1	C104—C105—H10P	104.7
O3—C16—C15	110.4 (2)	C106—C105—H10P	104.7
O3—C16—C17	110.43 (17)	H10O—C105—H10P	105.7
C15—C16—C17	107.33 (18)	C105—C106—H10F	109.5
O3—C16—H16A	109.6	C105—C106—H10G	109.5
C15—C16—H16A	109.6	H10F—C106—H10G	109.5
C17—C16—H16A	109.6	C105—C106—H10H	109.5
C20—C17—C16	114.60 (17)	H10F—C106—H10H	109.5
C20—C17—C13	117.73 (17)	H10G—C106—H10H	109.5
C16—C17—C13	104.46 (17)	C202—C201—H20B	109.5
C20—C17—H17A	106.4	C202—C201—H20C	109.5
C16—C17—H17A	106.4	H20B—C201—H20C	109.5
C13—C17—H17A	106.4	C202—C201—H20D	109.5
C13—C18—H18A	109.5	H20B—C201—H20D	109.5
C13—C18—H18B	109.5	H20C—C201—H20D	109.5
H18A—C18—H18B	109.5	C203—C202—C201	112 (3)
C13—C18—H18C	109.5	C203—C202—H20H	109.3
H18A—C18—H18C	109.5	C201—C202—H20H	109.3
H18B—C18—H18C	109.5	C203—C202—H20I	109.3
C10—C19—H19A	109.5	C201—C202—H20I	109.3
C10—C19—H19B	109.5	H20H—C202—H20I	108.0
H19A—C19—H19B	109.5	C202—C203—C204	113 (2)
C10—C19—H19C	109.5	C202—C203—H20J	109.1
H19A—C19—H19C	109.5	C204—C203—H20J	109.1
H19B—C19—H19C	109.5	C202—C203—H20K	109.1
C22—C20—C17	113.26 (17)	C204—C203—H20K	109.1
C22—C20—C21	107.06 (18)	H20J—C203—H20K	107.8
C17—C20—C21	112.67 (18)	C205—C204—C203	107 (3)
C22—C20—H20A	107.9	C205—C204—H20L	110.4
C17—C20—H20A	107.9	C203—C204—H20L	110.4
C21—C20—H20A	107.9	C205—C204—H20M	110.4
C20—C21—H21A	109.5	C203—C204—H20M	110.4
C20—C21—H21B	109.5	H20L—C204—H20M	108.6
H21A—C21—H21B	109.5	C206—C205—C204	119 (3)
C20—C21—H21C	109.5	C206—C205—H20N	107.5
H21A—C21—H21C	109.5	C204—C205—H20N	107.5
H21B—C21—H21C	109.5	C206—C205—H20O	107.5
C23—C22—O5	122.72 (19)	C204—C205—H20O	107.5
C23—C22—C20	127.61 (19)	H20N—C205—H20O	107.0
O5—C22—C20	109.51 (17)	C205—C206—H20E	109.5
C22—C23—C32	122.1 (2)	C205—C206—H20F	109.5
C22—C23—C24	120.4 (2)	H20E—C206—H20F	109.5
C32—C23—C24	117.4 (2)	C205—C206—H20G	109.5
C25—C24—C23	111.8 (2)	H20E—C206—H20G	109.5
C25—C24—H24A	109.3	H20F—C206—H20G	109.5
C23—C24—H24A	109.3

C10—C1—C2—C3	−58.5 (3)	O3—C16—C17—C20	19.7 (2)
C1—C2—C3—O1	176.0 (2)	C15—C16—C17—C20	140.0 (2)
C1—C2—C3—C4	56.6 (3)	O3—C16—C17—C13	−110.59 (18)
O1—C3—C4—C5	−170.4 (2)	C15—C16—C17—C13	9.7 (2)
C2—C3—C4—C5	−53.0 (3)	C12—C13—C17—C20	85.2 (2)
C3—C4—C5—C6	−128.3 (3)	C14—C13—C17—C20	−161.23 (18)
C3—C4—C5—C10	51.4 (3)	C18—C13—C17—C20	−42.2 (2)
C4—C5—C6—C7	−178.7 (2)	C12—C13—C17—C16	−146.38 (18)
C10—C5—C6—C7	1.7 (4)	C14—C13—C17—C16	−32.8 (2)
C5—C6—C7—C8	16.8 (4)	C18—C13—C17—C16	86.2 (2)
C6—C7—C8—C14	−168.6 (2)	C16—C17—C20—C22	53.6 (2)
C6—C7—C8—C9	−46.8 (3)	C13—C17—C20—C22	177.03 (18)
C14—C8—C9—C11	−47.4 (2)	C16—C17—C20—C21	175.31 (19)
C7—C8—C9—C11	−170.39 (19)	C13—C17—C20—C21	−61.3 (3)
C14—C8—C9—C10	−175.84 (17)	C17—C20—C22—C23	−145.6 (2)
C7—C8—C9—C10	61.2 (2)	C21—C20—C22—C23	89.6 (3)
C6—C5—C10—C19	−111.6 (3)	C17—C20—C22—O5	38.9 (2)
C4—C5—C10—C19	68.7 (3)	C21—C20—C22—O5	−85.9 (2)
C6—C5—C10—C1	129.8 (2)	O5—C22—C23—C32	−174.2 (2)
C4—C5—C10—C1	−49.9 (3)	C20—C22—C23—C32	10.9 (4)
C6—C5—C10—C9	11.0 (3)	O5—C22—C23—C24	5.4 (4)
C4—C5—C10—C9	−168.65 (18)	C20—C22—C23—C24	−169.5 (2)
C2—C1—C10—C5	53.1 (3)	C22—C23—C24—C25	15.4 (3)
C2—C1—C10—C19	−65.7 (3)	C32—C23—C24—C25	−164.9 (2)
C2—C1—C10—C9	172.8 (2)	C23—C24—C25—C26	−46.1 (3)
C11—C9—C10—C5	−170.04 (18)	C23—C24—C25—C27	−169.6 (2)
C8—C9—C10—C5	−42.0 (2)	C24—C25—C26—O5	60.1 (3)
C11—C9—C10—C19	−48.2 (3)	C27—C25—C26—O5	−175.8 (2)
C8—C9—C10—C19	79.9 (2)	C22—C23—C32—O6	−13.3 (4)
C11—C9—C10—C1	72.3 (2)	C24—C23—C32—O6	167.0 (3)
C8—C9—C10—C1	−159.58 (18)	C22—C23—C32—C33	167.4 (3)
C8—C9—C11—C12	46.7 (3)	C24—C23—C32—C33	−12.3 (3)
C10—C9—C11—C12	174.63 (19)	O2—C28—O1—C3	−1.2 (5)
C9—C11—C12—C13	−52.4 (3)	C29—C28—O1—C3	176.9 (3)
C11—C12—C13—C14	56.5 (2)	C2—C3—O1—C28	155.7 (3)
C11—C12—C13—C18	−65.8 (2)	C4—C3—O1—C28	−83.5 (3)
C11—C12—C13—C17	167.13 (19)	O4B—C30—O3—C16	29.4 (9)
C7—C8—C14—C15	−55.4 (3)	O4A—C30—O3—C16	−15.8 (6)
C9—C8—C14—C15	−177.3 (2)	C31—C30—O3—C16	177.1 (2)
C7—C8—C14—C13	−179.72 (19)	C15—C16—O3—C30	88.5 (3)
C9—C8—C14—C13	58.4 (2)	C17—C16—O3—C30	−153.0 (2)
C12—C13—C14—C15	165.85 (18)	C23—C22—O5—C26	8.4 (3)
C18—C13—C14—C15	−72.6 (2)	C20—C22—O5—C26	−175.9 (2)
C17—C13—C14—C15	44.9 (2)	C25—C26—O5—C22	−42.1 (3)
C12—C13—C14—C8	−62.4 (2)	C101—C102—C103—C104	179 (4)
C18—C13—C14—C8	59.2 (2)	C102—C103—C104—C105	114 (5)
C17—C13—C14—C8	176.73 (17)	C103—C104—C105—C106	8 (7)
C8—C14—C15—C16	−168.6 (2)	C201—C202—C203—C204	176 (5)
C13—C14—C15—C16	−39.2 (2)	C202—C203—C204—C205	−23 (8)
C14—C15—C16—O3	138.11 (19)	C203—C204—C205—C206	159 (7)
C14—C15—C16—C17	17.7 (2)

Symmetry code: (i) x+1/2, −y−1/2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20A···O6	0.98	2.17	2.859 (3)	126
C26—H26B···O6ⁱⁱ	0.97	2.59	3.431 (4)	146
C33—H33B···O4Bⁱⁱⁱ	0.96	2.54	3.283 (15)	135

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

Experimental details

Crystal data
Chemical formula	C₃₃H₄₈O₆·0.8C₆H₁₄
M_r	609.65
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	294
a, b, c (Å)	11.64797 (17), 12.20869 (17), 25.7274 (4)
V (Å³)	3658.60 (9)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.58
Crystal size (mm)	0.45 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku SuperNova
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)
T_min, T_max	0.663, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	19071, 6767, 5885
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.106, 1.01
No. of reflections	6767
No. of parameters	477
No. of restraints	90
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.11
Absolute structure	Flack x determined using 2066 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Absolute structure parameter	0.09 (6)

Computer programs: CrysAlis PRO (Rigaku Oxford Diffraction, 2015), SHELXS2013 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), Mercury (Macrae et al., 2008).

Acknowledgements

This work was supported by CONACyT grant RET-250025 to MGHL. We thank VIEP–BUAP for financial support, and CONACyT for the scholarships to GGL (573785) and ACC.

References

Castro-Méndez, A., Sandoval-Ramírez, J. & Bernès, S. (2002). Acta Cryst. E58, o606–o608. Web of Science CSD CrossRef IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Pérez-Díaz, J. O. H., Vega-Baez, J. L., Sandoval-Ramírez, J., Meza-Reyes, S., Montiel-Smith, S., Farfán, N. & Santillan, R. (2010). Steroids, 75, 1127–1136. PubMed Google Scholar
Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Americas Corporation, The Woodlands, TX, USA. Google Scholar
Sandoval-Ramírez, J., Castro-Méndez, A., Meza-Reyes, S., Reyes-Vázquez, F., Santillán, R. & Farfán, N. (1999). Tetrahedron Lett. 40, 5143–5146. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Soki, F., Neudörfl, J.-M. & Goldfuss, B. (2008). J. Organomet. Chem. 693, 2139–2146. Web of Science CSD CrossRef CAS Google Scholar
Spek, A. L. (2015). Acta Cryst. C71, 9–18. Web of Science CrossRef IUCr Journals Google Scholar
Weberski, M. P. Jr, Chen, C., Delferro, M., Zuccaccia, C., Macchioni, A. & Marks, T. J. (2012). Organometallics, 31, 3773–3789. CSD CrossRef CAS Google Scholar

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Volume 1| Part 4| April 2016| x160622

doi:10.1107/S2414314616006222

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(25R)-3β,16β-Diacet­­oxy-23-acetyl-22,26-ep­­oxy­cholesta-5,22-diene n-hexane 0.8-solvate

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

(25R)-3β,16β-Diacetoxy-23-acetyl-22,26-epoxycholesta-5,22-diene n-hexane 0.8-solvate