Synthesis and crystal structure of 5,10-dihy­droxy-9-meth­oxy-2,2-dimethyl-12-(2-methyl­but-3-en-2-yl)-2H,6H-pyrano[3,2-b]xanthen-6-one

Saekee, A.; Kuhakarn, C.; Chakarawet, K.; Hongthong, S.

doi:10.1107/S2056989025001070

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Volume 81| Part 3| March 2025|

https://doi.org/10.1107/S2056989025001070

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Synthesis and crystal structure of 5,10-dihydroxy-9-methoxy-2,2-dimethyl-12-(2-methylbut-3-en-2-yl)-2H,6H-pyrano[3,2-b]xanthen-6-one

Amporn Saekee,^a Chutima Kuhakarn,^a Khetpakorn Chakarawet ^b ^*‡ and Sakchai Hongthong ^c ^*‡

^aDepartment of Chemistry and Center of Excellence for Innovation in Chemistry, (PERCH-CIC), Faculty of Science, Mahidol University, Bangkok 10400, Thailand, ^bDepartment of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400, Thailand, and ^cProgram in Chemistry, Faculty of Science and Technology, Rajabhat Rajanagarindra University, Chachoengsao 24000, Thailand
^*Correspondence e-mail: khetpakorn.cha@mahidol.ac.th, sakchai.hon@rru.ac.th

Edited by D. Chopra, Indian Institute of Science Education and Research Bhopal, India (Received 29 November 2024; accepted 6 February 2025; online 14 February 2025)

5,10-Dihydroxy-9-methoxy-2,2-dimethyl-12-(2-methylbut-3-en-2-yl)-2H,6H-pyrano[3,2-b]xanthen-6-one, C₂₄H₂₄O₆ (2), is a prenylated xanthone that was synthesized from 5,9,10-trihydroxy-2,2-dimethyl-12-(2-methylbut-3-en-2-yl)-2H,6H-pyrano[3,2-b]xanthen-6-one or macluraxanthone (1), a known compound isolated from Garcinia schomburgkiana Pierre. The present study describes the synthesis of compound 2 by methylation reaction of 1, and its crystallographic characterization. Compound 2 features a planar xanthone core and a bent pyrano ring adopting a half-boat conformation. An intermolecular O—H⋯O hydrogen bond between the hydroxyl hydrogen donor and the ketone acceptor organizes the molecules into a one-dimensional network along the b-axis direction. Perpendicular to this network, π–π stacking interactions form the three-dimensional supramolecular architecture. These two key intermolecular interactions are distinctly revealed in the Hirshfeld surface analysis.

Keywords: crystal structure; xanthone; natural products.

CCDC reference: 2421853

1. Chemical context

Pyranoxanthones have long been known for their natural occurrence, showing a broad spectrum of pharmacological and biological activities (Kondedeshmukh & Paradkar, 1994 ). In the past decade, this scaffold has been subjected to chemical structure identification and synthetic investigations. The pyranoxanthone core also brings a wide range of applications. For example, 1,2-dihydro-2-hydroxy-6-methoxy-3,3-dimethyl-3H,7H-pyrano[2,3-c]xanthen-7-one showed a potent cytotoxicity against leukemia L1210 cell line (Ghirtis et al., 2001 ). Because various substituents on pyranoxanthones cause different properties, the structure–activity relationships (SAR) play a pivotal role in the discovery of their biological activities.

5,10-Dihydroxy-9-methoxy-2,2-dimethyl-12-(2-methylbut-3-en-2-yl)-2H,6H-pyrano[3,2-b]xanthen-6-one (2) is a pyranoxanthone that was isolated from leaves and twigs of Garcinia speciosa. This compound showed weak inhibitory activity toward HIV-1 reverse transcriptase (Pailee et al., 2018 ). In addition, a parent analog 5,9,10-trihydroxy-2,2-dimethyl-12-(2-methylbut-3-en-2-yl)-2H,6H-pyrano[3,2-b]xanthen-6-one (1), also known as macluraxanthone, was isolated from the same plant (Sangsuwon & Jiratchariyakul, 2015 ). Compound 1 was first isolated from osage orange (Maclura pomifera) in 1964 (Wolfrom et al., 1964 ). Subsequently, it was also found in different parts of various plants such as Garcinia bancana (Rifaldi et al., 2024 ), and Cratoxylum soulattri (Mah et al., 2011 ). Recently, 1 was also isolated from fruits and twigs of Garcinia schomburgkiana, a Thai plant known locally as ‘Ma Dun’, with a considerable quantity (1.07% from fruits and 5.29% from twigs) (Sukkum et al., 2024 ). Prompted by the above results, we performed the synthesis of compounds 2 and 3 from macluraxanthone (1) via methylation reaction using dimethyl carbonate (DMC) as a methylating reagent in the presence of K₂CO₃ as a base, and polysorbate 80 as a phase transfer catalyst (Prakoso et al., 2016 ) as shown in Fig. 1. The identities of the products were confirmed by ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy and high-resolution electrospray ionization mass spectrometry (HR-ESI-MS). Based on the spectroscopic and spectrometry data and by comparison with the data reported in the literature (Pailee et al., 2018; Wolfrom et al., 1964), compounds 2 and 3 were determined as 5,10-dihydroxy-9-methoxy-2,2-dimethyl-12-(2-methylbut-3-en-2-yl)-2H,6H-pyrano[3,2-b]xanthen-6-one (2) and 5-hydroxy-9,10-dimethoxy-2,2-dimethyl-12-(2-methylbut-3-en-2-yl)-2H, 6H-pyrano[3,2-b]xanthen-6-one (3). The structure of 2 was further confirmed by single-crystal X-ray crystallography.

Figure 1
Methylation reaction of macluraxanthone (1) to produce xanthones 2 and 3.

2. Structural commentary

Compound 2 crystallizes in the monoclinic P2₁ space group with two independent molecules in the asymmetric unit (Z = 4). The structure of 2 shows the expected methylation of the hydroxyl group at O17 position (Fig. 2). The methyl group is coplanar with the core xanthone structure, with C8—C9—O17—C18 torsion angles of 3.8 (3) and −1.4 (3)° for the first and second molecules, respectively. The xanthone core structure (O11, C4A–C12A) is planar, while the pyrano ring (O1, C2–C4A, C12A) is bent, adopting a half-boat conformation with the C2 atom deviating out of the plane generated by the remaining 17 atoms (O1, O11, C3–C12A) by 0.456 (2) and 0.534 (2) Å, for the first and second molecules, respectively. This result supports the chemical structure that C2 is not conjugated with the aromatic system. The root-mean-square deviations of the molecular plane formed from these 17 atoms are 0.034 and 0.035 Å for the first and second molecules, respectively.

Figure 2
ORTEP view of compound 2 plotted as displacement ellipsoids at the 50% probability level. Two molecules comprise the asymmetric unit.

The structure of 2 features an intramolecular hydrogen bond (Table 1) between its carbonyl and the nearby hydroxyl group, with an O15⋯O16 distance of 2.530 (2) and 2.547 (2) Å for the first and second molecules in the asymmetric unit, respectively. This distance is considered relatively short for O⋯O distances involved in hydrogen bonding.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O15—H15⋯O16	0.84	1.78	2.530 (2)	147
O15_2—H15_2⋯O16_2	0.84	1.80	2.547 (2)	147
O19—H19⋯O16ⁱ	0.84	1.92	2.719 (2)	159
O19_2—H19_2⋯O16_2ⁱⁱ	0.84	1.92	2.704 (2)	156
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

3. Supramolecular features

An intermolecular hydrogen bond is found between O16 and O19 with an O⋯O distance of 2.719 (2) and 2.704 (2) Å (Table 1) for the first and second molecules in the asymmetric unit, respectively. This hydrogen bonding consolidates the molecular packing, which forms a one-dimensional network of 2 along the b-axis direction (Fig. 3). The methoxy group of 2 formed upon the methylation of 1 is not involved in any significant hydrogen-bonding interactions.

Figure 3
Packing of 2 in the unit cell, consolidated by intermolecular hydrogen bonding. The unit cell is shown as a gray box where the c axis is parallel to the reader's view. The a and b axes and the origin center are labeled in the figure.

The planarity of the molecule facilitates molecular stacking in the structure. The first and second molecules in the asymmetric unit are aligned almost parallel to each other; the angle between the two molecular planes are 11.23 (4)°. The shortest C⋯C distance between the two molecules is 3.366 (3) Å, found between C4 of the first molecule and C11A of the second molecule, indicating possible π–π interactions (Fig. 4a). The π–π stackings run along the [10 $[\overline{1}]$ ] direction perpendicular to the intermolecular hydrogen-bonding network (Fig. 4b), altogether forming a three-dimensional supramolecular arrangement.

Figure 4
(a) Two molecules of 2 in the asymmetric unit viewed perpendicular to the pyranoxanthone rings to highlight π–π stacking. The pyranoxanthone core atoms of the first and second molecules are labeled in black and gray, respectively. (b) Stacking of 2 in the unit cell. The unit cell is shown as a gray box where the b axis is parallel to the reader's view. The a and c axes and the origin center are labeled in the figure.

4. Hirshfeld surface analysis

Hirshfeld surface analysis was performed to more accurately identify and quantify intermolecular interactions. The analysis was performed using CrystalExplorer 21.5 (Spackman et al., 2021 ). The three-dimensional Hirshfeld surface of 2 is plotted in Fig. 5a, including the two molecules of the asymmetric unit, mapped over normalized contact distance (d_norm) on a scale from −0.65 to 1.66 a.u. Blue, white, and red regions indicate contacts that are longer, equal, and shorter than the sum of van der Waals radii, respectively. The apparent red regions around O atoms indicate short contacts from intermolecular hydrogen bonding. Fig. 5b depicts a two-dimensional fingerprint plot of (d_i, d_e). Two sharp spikes in the fingerprint plot indicate the short intermolecular O—H⋯O hydrogen bonding interactions, which contribute 15.8% to the overall Hirshfeld surface area. A π–π planar stacking was also identified in the cyan-green region of the plot centered around d_i = d_e = 1.8 Å, contributing 8.7%. The surface corresponding to these C⋯C interactions spans over two of the four aromatic rings of 2, indicating that π–π stacking is impeded. The remaining major intermolecular interactions are H⋯H and C⋯H interactions, contributing 62.4 and 9.7%, respectively.

Figure 5
(a) Three-dimensional Hirshfeld surface representation of 2 plotted over d_norm and (b) two-dimensional fingerprint plot of 2 showing all interactions.

5. Database survey

A search for the pyranoxanthone core structure revealed five crystal structures in the Cambridge Structural Database (CSD version 5.45, last update November 2023; Groom et al., 2016 ). The structure of macluraxanthone (1) (QAYTOA; Fun et al., 2006 ) shows similar structural features including the bent pyrano ring and planar xanthone rings, but differs in the intermolecular packing: 1 engages in hydrogen-bonding interactions involving the O17 position, which is absent in 2 due to the methylation of this oxygen atom. A di-p-bromobenzenesulfonylated derivative was also reported (YIZPAZ; Boonnak et al., 2008 ), featuring a similar bent pyrano ring and planar xanthone rings. In addition, three other pyranoxanthone structures possessing different substituents on C12 were found in the database: CIXSIL (Kosela et al., 1999 ), MAPMIA (Chantrapromma et al., 2005 ), and CABFAP (Sukandar et al., 2016 ).

6. Synthesis and crystallization

The synthetic reaction was modified from a published procedure according to Prakoso et al. (2016). Briefly, a 50 mL round-bottom flask equipped with a magnetic stir bar was charged with 1 (0.13 mmol, 1 equiv.), K₂CO₃ (0.56 mmol, 4.3 equiv.), and polysorbate 80 (0.163 mmol, 1.25 equiv.). Then, dimethyl carbonate (DMC) (1.30 mmol, 10 equiv.) was added to the reaction mixture. After refluxing at 373 K for 5 h, the reaction mixture was quenched with aqueous acetic acid (20 mL) and extracted with dichloromethane (5 × 50 mL). The combined organic layers were washed with a saturated NaCl solution (20 mL) and dried over anhydrous Na₂SO₄. After removal of the solvent, the crude mixture was purified by column chromatography (acetone:hexane, 1:5 v/v, isocratic system) to afford compound 2 (48% yield), compound 3 (11% yield), and a recovered starting material (1) (36% yield).

5,10-Dihydroxy-9-methoxy-2,2-dimethyl-12-(2-methylbut-3-en-2-yl)-2H,6H-pyrano[3,2-b]xanthen-6-one (2): yellow solid, ¹H NMR (400 MHz, CDCl₃), δ 13.48 (s, 1H), 7.68 (d, J = 9.0 Hz,1H), 6.90 (d, J = 9.0 Hz, 1H), 6.69 (d, J = 10.0 Hz, 1H), 6.61 (s, 1H), 6.59 (dd, J = 16.0, 10.0 Hz, 1H), 5.54 (d, J = 10.0 Hz, 1H), 5.12 (dd, J = 16.0, 1.0 Hz, 1H), 5.09 (dd, J = 10.0, 1.0 Hz, 1H), 3.95 (s, 3H), 1.59 (s, 6H), 1.44 (s, 6H) ppm. ¹³C NMR (100 MHz, CDCl₃), δ 180.8, 159.1, 156.7, 154.9, 154.4, 151.5, 144.3, 133.5, 127.1, 116.8, 116.0, 114.2, 113.3, 108.4, 105.4, 104.6, 103.6, 78.2, 55.6, 41.3, 28.5, 27.1 ppm. HR-ESI-MS of 407.1482 [M–H]⁻ (calculated for C₂₄H₂₃O₆; 407.1500).

5-Hydroxy-9,10-dimethoxy-2,2-dimethyl-12-(2-methylbut-3-en-2-yl)-2H,6H-pyrano[3,2-b]xanthen-6-one (3): yellow solid, ¹H NMR (400 MHz, CDCl₃), δ 13.57 (s, 1H, OH), 7.90 (d, J = 8.0 Hz, 1H), 6.92 (d, J = 8.0 Hz, 1H), 6.68 (d, J = 9.6 Hz, 1H), 6.30 (dd, J = 12.1, 8.0 Hz, 1H), 5.52 (d, J = 9.6 Hz, 1H), 4.86 (dd, J = 17.0, 1.0 Hz, 1H), 4.78 (dd, J = 10.0, 1.0 Hz, 1H), 3.94 (s, 3H, OCH₃), 3.86 (s, 3H, OCH₃), 1.66 (s, 6H), 1.40 (s, 6H) ppm. ¹³C NMR (100 MHz, CDCl₃), δ 181.0, 159.4, 158.0, 156.5, 155.4, 150.8, 150.0, 136.4, 127.3, 121.4, 116.0, 114.9, 113.7, 108.6, 107.9, 105.2, 103.3, 78.2, 61.5, 55.4, 41.5, 31.9, 27.9 ppm. HR-ESI-MS of 445.1622 [M + Na]⁺ (calculated for C₂₅H₂₆O₆Na; 445.1622).

Single crystals of 2 were obtained as yellow blocks from vapor diffusion of n-hexane into an acetone solution.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All non-hydrogen atoms were refined anisotropically. The vinyl group of the second molecule was found to be disordered; refinement was accomplished by modeling over two positions. The occupancy of each disordered component was initially refined freely, and converged to a 0.53:0.47 occupancy ratio. Thus, the occupancy of both components was subsequently constrained to 0.5. The anisotropic displacement refinement of the disordered atoms was stabilized by the application of enhanced rigid bond restraints. Hydrogen atoms bonded to carbon were included in calculated positions and refined using a riding model. Hydrogen atoms bound to O atoms were located in the difference-Fourier map, and refined semi-freely with the help of distance restraints.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₄H₂₄O₆
M_r	408.43
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	101
a, b, c (Å)	10.6205 (3), 14.8160 (4), 12.7073 (3)
β (°)	96.209 (1)
V (Å³)	1987.81 (9)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.80
Crystal size (mm)	0.18 × 0.11 × 0.06

Data collection
Diffractometer	Bruker D8 QUEST PHOTON III C7
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.703, 0.753
No. of measured, independent and observed [I > 2σ(I)] reflections	32650, 7256, 6891
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.079, 1.06
No. of reflections	7256
No. of parameters	581
No. of restraints	253
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.25
Absolute structure	Flack x determined using 3110 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.00 (5)
Computer programs: APEX2 and SAINT (Bruker, 2016 ), SHELXT2015 (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2421853

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025001070/dx2063sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025001070/dx2063Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025001070/dx2063Isup3.mol

Supporting information file. DOI: https://doi.org/10.1107/S2056989025001070/dx2063Isup4.cml

checkCIF report

Computing details top

5,10-Dihydroxy-9-methoxy-2,2-dimethyl-12-(2-methylbut-3-en-2-yl)-2H,6H-pyrano[3,2-b]xanthen-6-one top

Crystal data top

C₂₄H₂₄O₆	F(000) = 864
M_r = 408.43	D_x = 1.365 Mg m⁻³
Monoclinic, P2₁	Cu Kα radiation, λ = 1.54178 Å
a = 10.6205 (3) Å	Cell parameters from 9895 reflections
b = 14.8160 (4) Å	θ = 4.6–68.5°
c = 12.7073 (3) Å	µ = 0.80 mm⁻¹
β = 96.209 (1)°	T = 101 K
V = 1987.81 (9) Å³	Block, clear light yellow
Z = 4	0.18 × 0.11 × 0.06 mm

Data collection top

Bruker D8 QUEST PHOTON III C7 diffractometer	6891 reflections with I > 2σ(I)
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	R_int = 0.042
ω and φ scans	θ_max = 68.6°, θ_min = 4.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −11→12
T_min = 0.703, T_max = 0.753	k = −17→17
32650 measured reflections	l = −15→15
7256 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0448P)² + 0.2292P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.079	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.20 e Å⁻³
7256 reflections	Δρ_min = −0.24 e Å⁻³
581 parameters	Absolute structure: Flack x determined using 3110 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
253 restraints	Absolute structure parameter: 0.00 (5)
Primary atom site location: dual

Special details top

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

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.48934 (14)	0.63254 (10)	0.88990 (12)	0.0157 (3)
C2	0.56134 (19)	0.68143 (15)	0.97693 (17)	0.0171 (4)
C3	0.5962 (2)	0.77380 (14)	0.94037 (18)	0.0178 (4)
H3	0.672019	0.801826	0.970704	0.021*
C4	0.5213 (2)	0.81629 (15)	0.86586 (17)	0.0172 (4)
H4	0.539570	0.876651	0.847378	0.021*
C4A	0.4109 (2)	0.77029 (14)	0.81235 (17)	0.0153 (4)
C5	0.3218 (2)	0.81468 (14)	0.74379 (16)	0.0151 (4)
C6	0.13155 (19)	0.81253 (14)	0.61298 (16)	0.0153 (4)
C6A	0.03222 (19)	0.75829 (14)	0.55740 (17)	0.0150 (4)
C7	−0.0620 (2)	0.79472 (15)	0.48401 (16)	0.0174 (4)
H7	−0.063051	0.857719	0.470036	0.021*
C8	−0.1531 (2)	0.73982 (15)	0.43193 (17)	0.0179 (4)
H8	−0.216283	0.764913	0.381753	0.021*
C9	−0.15260 (19)	0.64708 (14)	0.45291 (16)	0.0159 (4)
C10	−0.0607 (2)	0.60890 (14)	0.52692 (16)	0.0144 (4)
C10A	0.03125 (19)	0.66544 (14)	0.57792 (16)	0.0141 (4)
O11	0.11980 (13)	0.62404 (9)	0.64739 (12)	0.0151 (3)
C11A	0.21661 (18)	0.67169 (14)	0.70155 (16)	0.0134 (4)
C12	0.30334 (19)	0.62308 (14)	0.77021 (16)	0.0141 (4)
C12A	0.39954 (19)	0.67621 (14)	0.82519 (16)	0.0137 (4)
C13	0.6763 (2)	0.62260 (16)	1.00704 (18)	0.0211 (5)
H13A	0.648844	0.563562	1.030848	0.032*
H13B	0.731042	0.651523	1.064320	0.032*
H13C	0.723247	0.614643	0.945423	0.032*
C14	0.4786 (2)	0.68963 (16)	1.06809 (17)	0.0216 (5)
H14A	0.399911	0.721312	1.043275	0.032*
H14B	0.524359	0.723596	1.126368	0.032*
H14C	0.458469	0.629226	1.092904	0.032*
O15	0.33355 (14)	0.90468 (10)	0.73218 (12)	0.0197 (3)
H15	0.275792	0.923517	0.687151	0.029*
O16	0.14017 (14)	0.89588 (10)	0.59763 (12)	0.0206 (3)
O17	−0.23789 (14)	0.58673 (10)	0.40592 (12)	0.0196 (3)
C18	−0.3305 (2)	0.62000 (16)	0.32450 (18)	0.0217 (5)
H18A	−0.287542	0.645740	0.266961	0.033*
H18B	−0.381849	0.666699	0.353953	0.033*
H18C	−0.385346	0.570258	0.296996	0.033*
O19	−0.05738 (13)	0.51996 (10)	0.55172 (11)	0.0170 (3)
H19	−0.098952	0.490660	0.503133	0.026*
C5A	0.2222 (2)	0.76596 (15)	0.68675 (17)	0.0150 (4)
C20	0.30221 (18)	0.51977 (14)	0.79184 (16)	0.0155 (4)
C21	0.4241 (2)	0.47936 (15)	0.76007 (18)	0.0208 (4)
H21	0.445444	0.494286	0.691477	0.025*
C22	0.5035 (2)	0.42587 (17)	0.8174 (2)	0.0270 (5)
H22A	0.577 (3)	0.404 (2)	0.790 (2)	0.036 (8)*
H22B	0.495 (3)	0.413 (2)	0.890 (3)	0.044 (9)*
C23	0.28615 (19)	0.50328 (14)	0.90934 (17)	0.0178 (4)
H23A	0.279587	0.438304	0.922085	0.027*
H23B	0.209051	0.533413	0.927059	0.027*
H23C	0.359603	0.527643	0.953612	0.027*
C24	0.1957 (2)	0.46614 (15)	0.72720 (19)	0.0239 (5)
H24A	0.202985	0.473601	0.651468	0.036*
H24B	0.113204	0.488743	0.743273	0.036*
H24C	0.203356	0.402044	0.745839	0.036*
O1_2	−0.00836 (14)	0.37560 (10)	0.13071 (12)	0.0194 (3)
C2_2	−0.0698 (2)	0.33552 (15)	0.03272 (17)	0.0191 (4)
C3_2	−0.0966 (2)	0.23753 (16)	0.05003 (18)	0.0205 (5)
H3_2	−0.168920	0.209760	0.012961	0.025*
C4_2	−0.0189 (2)	0.18992 (15)	0.11731 (17)	0.0188 (4)
H4_2	−0.031187	0.126751	0.123982	0.023*
C4A_2	0.08530 (19)	0.23455 (15)	0.18108 (17)	0.0162 (4)
C5_2	0.17783 (19)	0.18563 (15)	0.24207 (16)	0.0157 (4)
C5A_2	0.27205 (19)	0.23093 (15)	0.30899 (16)	0.0152 (4)
C6_2	0.36855 (19)	0.18113 (14)	0.37328 (16)	0.0149 (4)
C6A_2	0.46335 (19)	0.23343 (14)	0.43777 (17)	0.0155 (4)
C7_2	0.5642 (2)	0.19459 (15)	0.50217 (17)	0.0171 (4)
H7_2	0.573853	0.130840	0.503783	0.021*
C8_2	0.6496 (2)	0.24795 (15)	0.56324 (17)	0.0179 (4)
H8_2	0.717202	0.220815	0.607165	0.021*
C9_2	0.6371 (2)	0.34219 (15)	0.56086 (17)	0.0166 (4)
C10_2	0.5381 (2)	0.38304 (14)	0.49622 (16)	0.0149 (4)
C10A_2	0.45264 (19)	0.32757 (14)	0.43611 (16)	0.0142 (4)
O11_2	0.35792 (13)	0.37211 (9)	0.37575 (11)	0.0154 (3)
C11A_2	0.26721 (19)	0.32619 (15)	0.31288 (16)	0.0149 (4)
C12_2	0.17537 (19)	0.37960 (15)	0.25460 (17)	0.0174 (5)
C12A_2	0.08667 (19)	0.32959 (14)	0.18777 (17)	0.0162 (4)
C13_2	0.0193 (2)	0.34614 (17)	−0.05354 (18)	0.0243 (5)
H13A_2	0.035750	0.410378	−0.064317	0.037*
H13B_2	−0.020293	0.319796	−0.119763	0.037*
H13C_2	0.099284	0.315045	−0.031762	0.037*
C14_2	−0.1887 (2)	0.39184 (16)	0.00810 (19)	0.0231 (5)
H14A_2	−0.242199	0.385921	0.065903	0.035*
H14B_2	−0.235384	0.370661	−0.058027	0.035*
H14C_2	−0.165275	0.455306	0.000533	0.035*
O15_2	0.17522 (14)	0.09498 (10)	0.23611 (12)	0.0188 (3)
H15_2	0.235733	0.073547	0.276462	0.028*
O16_2	0.36869 (14)	0.09641 (10)	0.37326 (11)	0.0185 (3)
O17_2	0.71448 (13)	0.40131 (10)	0.61783 (12)	0.0185 (3)
C18_2	0.8165 (2)	0.36517 (16)	0.68843 (17)	0.0202 (5)
H18A_2	0.873047	0.330205	0.647938	0.030*
H18B_2	0.782263	0.325871	0.740454	0.030*
H18C_2	0.864000	0.414731	0.725168	0.030*
O19_2	0.52116 (14)	0.47341 (10)	0.48892 (12)	0.0197 (3)
H19_2	0.570615	0.499177	0.535563	0.030*
C20_2	0.1758 (2)	0.48402 (14)	0.26600 (18)	0.0209 (5)
C21_2	0.0906 (4)	0.5329 (3)	0.1751 (4)	0.0166 (8)	0.5
H21_2	0.101463	0.518775	0.103741	0.020*	0.5
C21B_2	0.0423 (5)	0.5244 (3)	0.2329 (5)	0.0271 (11)	0.5
H21B_2	−0.028598	0.496895	0.259544	0.032*	0.5
C22_2	0.004 (2)	0.5934 (16)	0.1942 (15)	0.030 (3)	0.5
H22A_2	−0.008289	0.608386	0.265074	0.037*	0.5
H22B_2	−0.046065	0.621701	0.136995	0.037*	0.5
C22B_2	0.022 (2)	0.5936 (15)	0.1710 (15)	0.045 (4)	0.5
H22C_2	0.091559	0.622425	0.143254	0.054*	0.5
H22D_2	−0.061284	0.615457	0.153394	0.054*	0.5
C23_2	0.1694 (3)	0.51099 (16)	0.3812 (2)	0.0372 (6)
H23A_2	0.095065	0.483015	0.407163	0.056*
H23B_2	0.162826	0.576792	0.386166	0.056*
H23C_2	0.246221	0.490474	0.424207	0.056*
C24_2	0.2965 (3)	0.52333 (17)	0.2285 (2)	0.0374 (7)
H24A_2	0.370556	0.499658	0.272679	0.056*
H24B_2	0.294861	0.589264	0.234377	0.056*
H24C_2	0.301451	0.506234	0.154607	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0154 (7)	0.0140 (7)	0.0165 (7)	0.0001 (5)	−0.0043 (6)	0.0001 (6)
C2	0.0139 (10)	0.0208 (11)	0.0155 (10)	−0.0014 (8)	−0.0040 (8)	−0.0021 (8)
C3	0.0141 (10)	0.0176 (11)	0.0214 (11)	−0.0031 (8)	0.0008 (8)	−0.0047 (9)
C4	0.0164 (10)	0.0151 (10)	0.0204 (11)	−0.0022 (8)	0.0029 (8)	−0.0013 (8)
C4A	0.0165 (10)	0.0150 (11)	0.0147 (10)	−0.0012 (8)	0.0034 (8)	−0.0013 (8)
C5	0.0171 (11)	0.0126 (10)	0.0157 (10)	−0.0015 (8)	0.0027 (8)	0.0010 (8)
C6	0.0162 (11)	0.0160 (11)	0.0138 (10)	0.0002 (8)	0.0027 (8)	0.0009 (8)
C6A	0.0178 (11)	0.0136 (10)	0.0135 (10)	0.0000 (8)	0.0020 (8)	0.0008 (8)
C7	0.0199 (11)	0.0154 (10)	0.0166 (10)	0.0013 (8)	0.0007 (8)	0.0027 (8)
C8	0.0174 (10)	0.0190 (11)	0.0166 (10)	0.0039 (9)	−0.0012 (8)	0.0022 (9)
C9	0.0146 (10)	0.0190 (11)	0.0137 (10)	−0.0003 (8)	0.0006 (8)	−0.0023 (8)
C10	0.0185 (10)	0.0124 (10)	0.0125 (9)	−0.0001 (8)	0.0031 (8)	0.0003 (8)
C10A	0.0149 (10)	0.0170 (10)	0.0103 (9)	0.0039 (8)	0.0008 (8)	0.0025 (8)
O11	0.0162 (7)	0.0119 (7)	0.0159 (7)	−0.0006 (5)	−0.0044 (6)	0.0023 (6)
C11A	0.0132 (10)	0.0150 (10)	0.0120 (10)	−0.0001 (7)	0.0014 (8)	−0.0006 (8)
C12	0.0176 (10)	0.0123 (11)	0.0127 (10)	−0.0002 (7)	0.0033 (8)	0.0006 (8)
C12A	0.0136 (10)	0.0156 (10)	0.0120 (10)	0.0009 (8)	0.0019 (8)	0.0003 (8)
C13	0.0175 (11)	0.0241 (12)	0.0207 (11)	0.0009 (8)	−0.0031 (8)	0.0003 (9)
C14	0.0208 (11)	0.0247 (12)	0.0189 (11)	0.0000 (9)	0.0003 (8)	−0.0001 (9)
O15	0.0224 (8)	0.0119 (7)	0.0229 (8)	−0.0022 (6)	−0.0056 (6)	0.0038 (6)
O16	0.0248 (8)	0.0127 (8)	0.0229 (8)	−0.0007 (6)	−0.0039 (6)	0.0046 (6)
O17	0.0195 (7)	0.0172 (8)	0.0200 (7)	−0.0002 (6)	−0.0074 (6)	−0.0005 (6)
C18	0.0191 (11)	0.0229 (12)	0.0212 (11)	0.0021 (9)	−0.0071 (9)	−0.0022 (9)
O19	0.0199 (7)	0.0125 (7)	0.0172 (7)	−0.0009 (6)	−0.0048 (6)	−0.0003 (6)
C5A	0.0163 (10)	0.0147 (11)	0.0142 (10)	0.0002 (8)	0.0029 (8)	0.0015 (8)
C20	0.0166 (10)	0.0115 (10)	0.0176 (10)	0.0005 (8)	−0.0019 (8)	0.0023 (8)
C21	0.0263 (11)	0.0154 (10)	0.0214 (11)	−0.0004 (8)	0.0057 (9)	0.0002 (9)
C22	0.0248 (12)	0.0244 (12)	0.0327 (14)	0.0077 (10)	0.0062 (10)	0.0020 (10)
C23	0.0170 (10)	0.0157 (10)	0.0208 (10)	0.0014 (8)	0.0020 (8)	0.0043 (8)
C24	0.0288 (12)	0.0119 (10)	0.0282 (12)	−0.0028 (9)	−0.0093 (9)	0.0043 (9)
O1_2	0.0175 (7)	0.0180 (8)	0.0207 (8)	0.0011 (6)	−0.0062 (6)	0.0006 (6)
C2_2	0.0154 (10)	0.0232 (11)	0.0174 (10)	−0.0022 (8)	−0.0036 (8)	0.0022 (9)
C3_2	0.0146 (10)	0.0245 (11)	0.0215 (11)	−0.0059 (9)	−0.0023 (8)	−0.0008 (9)
C4_2	0.0168 (10)	0.0176 (11)	0.0217 (11)	−0.0039 (8)	0.0010 (8)	0.0006 (9)
C4A_2	0.0149 (10)	0.0192 (11)	0.0145 (10)	−0.0037 (8)	0.0020 (8)	−0.0002 (8)
C5_2	0.0180 (11)	0.0136 (10)	0.0157 (10)	−0.0024 (8)	0.0034 (8)	0.0014 (8)
C5A_2	0.0165 (10)	0.0157 (11)	0.0135 (10)	−0.0008 (8)	0.0019 (8)	0.0006 (8)
C6_2	0.0175 (10)	0.0141 (10)	0.0136 (10)	−0.0001 (8)	0.0039 (8)	0.0006 (8)
C6A_2	0.0167 (10)	0.0161 (11)	0.0139 (10)	0.0011 (8)	0.0027 (8)	0.0007 (8)
C7_2	0.0183 (10)	0.0139 (10)	0.0187 (11)	0.0012 (8)	0.0002 (8)	0.0025 (8)
C8_2	0.0166 (10)	0.0177 (11)	0.0186 (11)	0.0033 (8)	−0.0022 (8)	0.0031 (9)
C9_2	0.0153 (10)	0.0190 (11)	0.0152 (10)	−0.0025 (8)	0.0005 (8)	−0.0016 (8)
C10_2	0.0180 (10)	0.0124 (10)	0.0143 (10)	0.0006 (8)	0.0018 (8)	0.0009 (8)
C10A_2	0.0150 (10)	0.0155 (10)	0.0122 (10)	0.0021 (8)	0.0010 (8)	0.0020 (8)
O11_2	0.0163 (7)	0.0126 (7)	0.0162 (7)	0.0004 (5)	−0.0044 (6)	−0.0002 (6)
C11A_2	0.0157 (11)	0.0139 (10)	0.0149 (10)	−0.0022 (8)	0.0004 (8)	−0.0009 (8)
C12_2	0.0167 (10)	0.0133 (11)	0.0212 (11)	0.0010 (8)	−0.0020 (9)	0.0003 (8)
C12A_2	0.0143 (10)	0.0178 (11)	0.0160 (10)	0.0023 (8)	−0.0002 (8)	0.0028 (8)
C13_2	0.0185 (11)	0.0297 (13)	0.0241 (12)	−0.0011 (9)	−0.0007 (9)	0.0055 (10)
C14_2	0.0175 (10)	0.0281 (13)	0.0227 (11)	0.0018 (9)	−0.0030 (9)	0.0050 (10)
O15_2	0.0218 (8)	0.0120 (7)	0.0212 (8)	−0.0009 (6)	−0.0042 (6)	0.0014 (6)
O16_2	0.0227 (8)	0.0118 (7)	0.0199 (7)	0.0007 (6)	−0.0029 (6)	0.0018 (6)
O17_2	0.0183 (7)	0.0152 (7)	0.0198 (8)	0.0003 (6)	−0.0072 (6)	−0.0008 (6)
C18_2	0.0170 (10)	0.0211 (11)	0.0207 (11)	0.0010 (8)	−0.0067 (8)	0.0006 (9)
O19_2	0.0236 (8)	0.0113 (7)	0.0219 (8)	0.0003 (6)	−0.0083 (6)	−0.0015 (6)
C20_2	0.0211 (11)	0.0114 (10)	0.0281 (12)	0.0010 (8)	−0.0068 (9)	−0.0004 (9)
C21_2	0.021 (2)	0.010 (2)	0.018 (2)	−0.0030 (18)	0.0004 (18)	0.0042 (16)
C21B_2	0.022 (2)	0.019 (2)	0.038 (3)	0.0019 (19)	−0.008 (2)	−0.002 (2)
C22_2	0.028 (4)	0.027 (5)	0.035 (5)	0.012 (3)	−0.003 (4)	−0.001 (4)
C22B_2	0.046 (10)	0.022 (5)	0.059 (10)	0.004 (5)	−0.027 (7)	0.006 (6)
C23_2	0.0562 (16)	0.0155 (11)	0.0456 (16)	0.0025 (11)	0.0319 (13)	−0.0015 (11)
C24_2	0.0649 (18)	0.0137 (11)	0.0394 (15)	−0.0023 (11)	0.0315 (14)	0.0024 (10)

Geometric parameters (Å, º) top

O1—C2	1.466 (2)	C2_2—C13_2	1.531 (3)
O1—C12A	1.355 (2)	C2_2—C14_2	1.518 (3)
C2—C3	1.504 (3)	C3_2—H3_2	0.9500
C2—C13	1.515 (3)	C3_2—C4_2	1.325 (3)
C2—C14	1.533 (3)	C4_2—H4_2	0.9500
C3—H3	0.9500	C4_2—C4A_2	1.458 (3)
C3—C4	1.328 (3)	C4A_2—C5_2	1.388 (3)
C4—H4	0.9500	C4A_2—C12A_2	1.411 (3)
C4—C4A	1.459 (3)	C5_2—C5A_2	1.411 (3)
C4A—C5	1.382 (3)	C5_2—O15_2	1.345 (3)
C4A—C12A	1.410 (3)	C5A_2—C6_2	1.443 (3)
C5—O15	1.349 (3)	C5A_2—C11A_2	1.413 (3)
C5—C5A	1.414 (3)	C6_2—C6A_2	1.452 (3)
C6—C6A	1.448 (3)	C6_2—O16_2	1.255 (3)
C6—O16	1.255 (3)	C6A_2—C7_2	1.399 (3)
C6—C5A	1.445 (3)	C6A_2—C10A_2	1.399 (3)
C6A—C7	1.400 (3)	C7_2—H7_2	0.9500
C6A—C10A	1.401 (3)	C7_2—C8_2	1.377 (3)
C7—H7	0.9500	C8_2—H8_2	0.9500
C7—C8	1.378 (3)	C8_2—C9_2	1.403 (3)
C8—H8	0.9500	C9_2—C10_2	1.400 (3)
C8—C9	1.400 (3)	C9_2—O17_2	1.356 (3)
C9—C10	1.399 (3)	C10_2—C10A_2	1.390 (3)
C9—O17	1.364 (3)	C10_2—O19_2	1.353 (3)
C10—C10A	1.393 (3)	C10A_2—O11_2	1.367 (2)
C10—O19	1.354 (3)	O11_2—C11A_2	1.365 (2)
C10A—O11	1.364 (2)	C11A_2—C12_2	1.403 (3)
O11—C11A	1.370 (2)	C12_2—C12A_2	1.409 (3)
C11A—C12	1.398 (3)	C12_2—C20_2	1.554 (3)
C11A—C5A	1.411 (3)	C13_2—H13A_2	0.9800
C12—C12A	1.413 (3)	C13_2—H13B_2	0.9800
C12—C20	1.555 (3)	C13_2—H13C_2	0.9800
C13—H13A	0.9800	C14_2—H14A_2	0.9800
C13—H13B	0.9800	C14_2—H14B_2	0.9800
C13—H13C	0.9800	C14_2—H14C_2	0.9800
C14—H14A	0.9800	O15_2—H15_2	0.8400
C14—H14B	0.9800	O17_2—C18_2	1.434 (2)
C14—H14C	0.9800	C18_2—H18A_2	0.9800
O15—H15	0.8400	C18_2—H18B_2	0.9800
O17—C18	1.435 (3)	C18_2—H18C_2	0.9800
C18—H18A	0.9800	O19_2—H19_2	0.8400
C18—H18B	0.9800	C20_2—C21_2	1.566 (5)
C18—H18C	0.9800	C20_2—C21B_2	1.555 (5)
O19—H19	0.8400	C20_2—C23_2	1.526 (3)
C20—C21	1.520 (3)	C20_2—C24_2	1.530 (3)
C20—C23	1.540 (3)	C21_2—H21_2	0.9500
C20—C24	1.544 (3)	C21_2—C22_2	1.33 (2)
C21—H21	0.9500	C21B_2—H21B_2	0.9500
C21—C22	1.317 (3)	C21B_2—C22B_2	1.29 (2)
C22—H22A	0.95 (3)	C22_2—H22A_2	0.9500
C22—H22B	0.95 (3)	C22_2—H22B_2	0.9500
C23—H23A	0.9800	C22B_2—H22C_2	0.9500
C23—H23B	0.9800	C22B_2—H22D_2	0.9500
C23—H23C	0.9800	C23_2—H23A_2	0.9800
C24—H24A	0.9800	C23_2—H23B_2	0.9800
C24—H24B	0.9800	C23_2—H23C_2	0.9800
C24—H24C	0.9800	C24_2—H24A_2	0.9800
O1_2—C2_2	1.467 (3)	C24_2—H24B_2	0.9800
O1_2—C12A_2	1.360 (2)	C24_2—H24C_2	0.9800
C2_2—C3_2	1.500 (3)

C12A—O1—C2	119.84 (16)	C3_2—C2_2—C14_2	113.27 (18)
O1—C2—C3	110.01 (17)	C14_2—C2_2—C13_2	111.13 (19)
O1—C2—C13	104.27 (17)	C2_2—C3_2—H3_2	120.2
O1—C2—C14	108.31 (17)	C4_2—C3_2—C2_2	119.6 (2)
C3—C2—C13	112.53 (18)	C4_2—C3_2—H3_2	120.2
C3—C2—C14	109.97 (18)	C3_2—C4_2—H4_2	120.0
C13—C2—C14	111.53 (18)	C3_2—C4_2—C4A_2	120.0 (2)
C2—C3—H3	119.9	C4A_2—C4_2—H4_2	120.0
C4—C3—C2	120.21 (19)	C5_2—C4A_2—C4_2	121.5 (2)
C4—C3—H3	119.9	C5_2—C4A_2—C12A_2	119.04 (19)
C3—C4—H4	120.0	C12A_2—C4A_2—C4_2	119.2 (2)
C3—C4—C4A	120.0 (2)	C4A_2—C5_2—C5A_2	120.08 (19)
C4A—C4—H4	120.0	O15_2—C5_2—C4A_2	118.74 (18)
C5—C4A—C4	122.18 (19)	O15_2—C5_2—C5A_2	121.18 (19)
C5—C4A—C12A	118.84 (19)	C5_2—C5A_2—C6_2	120.81 (19)
C12A—C4A—C4	118.82 (19)	C5_2—C5A_2—C11A_2	118.03 (19)
C4A—C5—C5A	120.23 (19)	C11A_2—C5A_2—C6_2	121.15 (19)
O15—C5—C4A	118.31 (19)	C5A_2—C6_2—C6A_2	116.97 (18)
O15—C5—C5A	121.45 (19)	O16_2—C6_2—C5A_2	120.81 (19)
O16—C6—C6A	122.13 (19)	O16_2—C6_2—C6A_2	122.22 (19)
O16—C6—C5A	121.07 (19)	C7_2—C6A_2—C6_2	123.42 (19)
C5A—C6—C6A	116.79 (18)	C10A_2—C6A_2—C6_2	118.25 (19)
C7—C6A—C6	122.78 (19)	C10A_2—C6A_2—C7_2	118.3 (2)
C7—C6A—C10A	118.93 (19)	C6A_2—C7_2—H7_2	119.7
C10A—C6A—C6	118.30 (18)	C8_2—C7_2—C6A_2	120.6 (2)
C6A—C7—H7	119.8	C8_2—C7_2—H7_2	119.7
C8—C7—C6A	120.4 (2)	C7_2—C8_2—H8_2	119.9
C8—C7—H7	119.8	C7_2—C8_2—C9_2	120.3 (2)
C7—C8—H8	120.0	C9_2—C8_2—H8_2	119.9
C7—C8—C9	120.0 (2)	C10_2—C9_2—C8_2	120.43 (19)
C9—C8—H8	120.0	O17_2—C9_2—C8_2	125.52 (19)
C10—C9—C8	120.86 (19)	O17_2—C9_2—C10_2	114.05 (18)
O17—C9—C8	124.86 (19)	C10A_2—C10_2—C9_2	118.09 (19)
O17—C9—C10	114.27 (18)	O19_2—C10_2—C9_2	123.63 (19)
C10A—C10—C9	118.21 (18)	O19_2—C10_2—C10A_2	118.28 (18)
O19—C10—C9	123.27 (19)	C10_2—C10A_2—C6A_2	122.27 (19)
O19—C10—C10A	118.52 (18)	O11_2—C10A_2—C6A_2	122.90 (19)
C10—C10A—C6A	121.54 (18)	O11_2—C10A_2—C10_2	114.82 (18)
O11—C10A—C6A	122.95 (18)	C11A_2—O11_2—C10A_2	121.19 (17)
O11—C10A—C10	115.51 (18)	O11_2—C11A_2—C5A_2	119.48 (18)
C10A—O11—C11A	121.40 (16)	O11_2—C11A_2—C12_2	115.73 (18)
O11—C11A—C12	117.14 (18)	C12_2—C11A_2—C5A_2	124.78 (19)
O11—C11A—C5A	118.90 (18)	C11A_2—C12_2—C12A_2	113.75 (19)
C12—C11A—C5A	123.95 (19)	C11A_2—C12_2—C20_2	121.16 (18)
C11A—C12—C12A	114.45 (18)	C12A_2—C12_2—C20_2	125.09 (19)
C11A—C12—C20	126.87 (18)	O1_2—C12A_2—C4A_2	117.76 (19)
C12A—C12—C20	118.67 (18)	O1_2—C12A_2—C12_2	117.83 (19)
O1—C12A—C4A	118.63 (18)	C12_2—C12A_2—C4A_2	124.3 (2)
O1—C12A—C12	117.26 (18)	C2_2—C13_2—H13A_2	109.5
C4A—C12A—C12	124.03 (19)	C2_2—C13_2—H13B_2	109.5
C2—C13—H13A	109.5	C2_2—C13_2—H13C_2	109.5
C2—C13—H13B	109.5	H13A_2—C13_2—H13B_2	109.5
C2—C13—H13C	109.5	H13A_2—C13_2—H13C_2	109.5
H13A—C13—H13B	109.5	H13B_2—C13_2—H13C_2	109.5
H13A—C13—H13C	109.5	C2_2—C14_2—H14A_2	109.5
H13B—C13—H13C	109.5	C2_2—C14_2—H14B_2	109.5
C2—C14—H14A	109.5	C2_2—C14_2—H14C_2	109.5
C2—C14—H14B	109.5	H14A_2—C14_2—H14B_2	109.5
C2—C14—H14C	109.5	H14A_2—C14_2—H14C_2	109.5
H14A—C14—H14B	109.5	H14B_2—C14_2—H14C_2	109.5
H14A—C14—H14C	109.5	C5_2—O15_2—H15_2	109.5
H14B—C14—H14C	109.5	C9_2—O17_2—C18_2	117.80 (17)
C5—O15—H15	109.5	O17_2—C18_2—H18A_2	109.5
C9—O17—C18	117.48 (16)	O17_2—C18_2—H18B_2	109.5
O17—C18—H18A	109.5	O17_2—C18_2—H18C_2	109.5
O17—C18—H18B	109.5	H18A_2—C18_2—H18B_2	109.5
O17—C18—H18C	109.5	H18A_2—C18_2—H18C_2	109.5
H18A—C18—H18B	109.5	H18B_2—C18_2—H18C_2	109.5
H18A—C18—H18C	109.5	C10_2—O19_2—H19_2	109.5
H18B—C18—H18C	109.5	C12_2—C20_2—C21_2	113.4 (2)
C10—O19—H19	109.5	C12_2—C20_2—C21B_2	111.4 (2)
C5—C5A—C6	119.86 (19)	C23_2—C20_2—C12_2	110.50 (19)
C11A—C5A—C5	118.49 (19)	C23_2—C20_2—C21_2	120.3 (2)
C11A—C5A—C6	121.62 (19)	C23_2—C20_2—C21B_2	91.4 (3)
C21—C20—C12	108.51 (16)	C23_2—C20_2—C24_2	108.9 (2)
C21—C20—C23	112.43 (17)	C24_2—C20_2—C12_2	110.11 (18)
C21—C20—C24	104.60 (18)	C24_2—C20_2—C21_2	91.8 (2)
C23—C20—C12	109.34 (16)	C24_2—C20_2—C21B_2	122.7 (3)
C23—C20—C24	106.41 (17)	C20_2—C21_2—H21_2	118.8
C24—C20—C12	115.57 (17)	C22_2—C21_2—C20_2	122.4 (9)
C20—C21—H21	116.5	C22_2—C21_2—H21_2	118.8
C22—C21—C20	127.0 (2)	C20_2—C21B_2—H21B_2	118.2
C22—C21—H21	116.5	C22B_2—C21B_2—C20_2	123.6 (12)
C21—C22—H22A	120.5 (18)	C22B_2—C21B_2—H21B_2	118.2
C21—C22—H22B	122.2 (19)	C21_2—C22_2—H22A_2	120.0
H22A—C22—H22B	117 (3)	C21_2—C22_2—H22B_2	120.0
C20—C23—H23A	109.5	H22A_2—C22_2—H22B_2	120.0
C20—C23—H23B	109.5	C21B_2—C22B_2—H22C_2	120.0
C20—C23—H23C	109.5	C21B_2—C22B_2—H22D_2	120.0
H23A—C23—H23B	109.5	H22C_2—C22B_2—H22D_2	120.0
H23A—C23—H23C	109.5	C20_2—C23_2—H23A_2	109.5
H23B—C23—H23C	109.5	C20_2—C23_2—H23B_2	109.5
C20—C24—H24A	109.5	C20_2—C23_2—H23C_2	109.5
C20—C24—H24B	109.5	H23A_2—C23_2—H23B_2	109.5
C20—C24—H24C	109.5	H23A_2—C23_2—H23C_2	109.5
H24A—C24—H24B	109.5	H23B_2—C23_2—H23C_2	109.5
H24A—C24—H24C	109.5	C20_2—C24_2—H24A_2	109.5
H24B—C24—H24C	109.5	C20_2—C24_2—H24B_2	109.5
C12A_2—O1_2—C2_2	119.05 (16)	C20_2—C24_2—H24C_2	109.5
O1_2—C2_2—C3_2	109.96 (18)	H24A_2—C24_2—H24B_2	109.5
O1_2—C2_2—C13_2	108.29 (17)	H24A_2—C24_2—H24C_2	109.5
O1_2—C2_2—C14_2	103.65 (17)	H24B_2—C24_2—H24C_2	109.5
C3_2—C2_2—C13_2	110.26 (19)

O1—C2—C3—C4	30.5 (3)	C2_2—C3_2—C4_2—C4A_2	5.5 (3)
C2—O1—C12A—C4A	26.1 (3)	C3_2—C4_2—C4A_2—C5_2	−171.6 (2)
C2—O1—C12A—C12	−157.12 (17)	C3_2—C4_2—C4A_2—C12A_2	13.6 (3)
C2—C3—C4—C4A	−5.6 (3)	C4_2—C4A_2—C5_2—C5A_2	−175.24 (18)
C3—C4—C4A—C5	171.99 (19)	C4_2—C4A_2—C5_2—O15_2	4.6 (3)
C3—C4—C4A—C12A	−12.6 (3)	C4_2—C4A_2—C12A_2—O1_2	−2.2 (3)
C4—C4A—C5—O15	−4.6 (3)	C4_2—C4A_2—C12A_2—C12_2	173.6 (2)
C4—C4A—C5—C5A	174.56 (18)	C4A_2—C5_2—C5A_2—C6_2	179.70 (18)
C4—C4A—C12A—O1	2.4 (3)	C4A_2—C5_2—C5A_2—C11A_2	1.1 (3)
C4—C4A—C12A—C12	−174.12 (19)	C5_2—C4A_2—C12A_2—O1_2	−177.14 (18)
C4A—C5—C5A—C6	−178.24 (18)	C5_2—C4A_2—C12A_2—C12_2	−1.3 (3)
C4A—C5—C5A—C11A	−0.1 (3)	C5_2—C5A_2—C6_2—C6A_2	178.57 (18)
C5—C4A—C12A—O1	177.93 (18)	C5_2—C5A_2—C6_2—O16_2	−2.0 (3)
C5—C4A—C12A—C12	1.4 (3)	C5_2—C5A_2—C11A_2—O11_2	−179.13 (17)
C6—C6A—C7—C8	178.87 (18)	C5_2—C5A_2—C11A_2—C12_2	−0.2 (3)
C6—C6A—C10A—C10	−179.52 (18)	C5A_2—C6_2—C6A_2—C7_2	−178.49 (19)
C6—C6A—C10A—O11	−0.3 (3)	C5A_2—C6_2—C6A_2—C10A_2	2.1 (3)
C6A—C6—C5A—C5	180.00 (17)	C5A_2—C11A_2—C12_2—C12A_2	−1.3 (3)
C6A—C6—C5A—C11A	1.9 (3)	C5A_2—C11A_2—C12_2—C20_2	178.5 (2)
C6A—C7—C8—C9	0.6 (3)	C6_2—C5A_2—C11A_2—O11_2	2.3 (3)
C6A—C10A—O11—C11A	−0.3 (3)	C6_2—C5A_2—C11A_2—C12_2	−178.76 (19)
C7—C6A—C10A—C10	0.2 (3)	C6_2—C6A_2—C7_2—C8_2	−178.62 (18)
C7—C6A—C10A—O11	179.41 (18)	C6_2—C6A_2—C10A_2—C10_2	179.21 (18)
C7—C8—C9—C10	0.3 (3)	C6_2—C6A_2—C10A_2—O11_2	−0.7 (3)
C7—C8—C9—O17	−179.88 (18)	C6A_2—C7_2—C8_2—C9_2	−0.6 (3)
C8—C9—C10—C10A	−1.0 (3)	C6A_2—C10A_2—O11_2—C11A_2	0.0 (3)
C8—C9—C10—O19	178.67 (19)	C7_2—C6A_2—C10A_2—C10_2	−0.2 (3)
C8—C9—O17—C18	3.8 (3)	C7_2—C6A_2—C10A_2—O11_2	179.82 (18)
C9—C10—C10A—C6A	0.7 (3)	C7_2—C8_2—C9_2—C10_2	−0.2 (3)
C9—C10—C10A—O11	−178.59 (17)	C7_2—C8_2—C9_2—O17_2	179.52 (19)
C10—C9—O17—C18	−176.38 (17)	C8_2—C9_2—C10_2—C10A_2	0.7 (3)
C10—C10A—O11—C11A	178.99 (16)	C8_2—C9_2—C10_2—O19_2	−179.11 (19)
C10A—C6A—C7—C8	−0.8 (3)	C8_2—C9_2—O17_2—C18_2	−1.4 (3)
C10A—O11—C11A—C12	−179.40 (16)	C9_2—C10_2—C10A_2—C6A_2	−0.5 (3)
C10A—O11—C11A—C5A	1.7 (3)	C9_2—C10_2—C10A_2—O11_2	179.42 (17)
O11—C11A—C12—C12A	−178.88 (16)	C10_2—C9_2—O17_2—C18_2	178.34 (17)
O11—C11A—C12—C20	0.2 (3)	C10_2—C10A_2—O11_2—C11A_2	−179.90 (16)
O11—C11A—C5A—C5	179.38 (17)	C10A_2—C6A_2—C7_2—C8_2	0.8 (3)
O11—C11A—C5A—C6	−2.5 (3)	C10A_2—O11_2—C11A_2—C5A_2	−0.8 (3)
C11A—C12—C12A—O1	−177.53 (16)	C10A_2—O11_2—C11A_2—C12_2	−179.85 (17)
C11A—C12—C12A—C4A	−1.0 (3)	O11_2—C11A_2—C12_2—C12A_2	177.64 (17)
C11A—C12—C20—C21	119.1 (2)	O11_2—C11A_2—C12_2—C20_2	−2.5 (3)
C11A—C12—C20—C23	−117.9 (2)	C11A_2—C5A_2—C6_2—C6A_2	−2.9 (3)
C11A—C12—C20—C24	2.1 (3)	C11A_2—C5A_2—C6_2—O16_2	176.54 (19)
C12—C11A—C5A—C5	0.5 (3)	C11A_2—C12_2—C12A_2—O1_2	177.95 (17)
C12—C11A—C5A—C6	178.64 (18)	C11A_2—C12_2—C12A_2—C4A_2	2.1 (3)
C12—C20—C21—C22	129.5 (2)	C11A_2—C12_2—C20_2—C21_2	164.8 (3)
C12A—O1—C2—C3	−41.4 (2)	C11A_2—C12_2—C20_2—C21B_2	−156.8 (3)
C12A—O1—C2—C13	−162.25 (16)	C11A_2—C12_2—C20_2—C23_2	−56.8 (3)
C12A—O1—C2—C14	78.9 (2)	C11A_2—C12_2—C20_2—C24_2	63.6 (3)
C12A—C4A—C5—O15	179.98 (18)	C12_2—C20_2—C21_2—C22_2	128.5 (13)
C12A—C4A—C5—C5A	−0.8 (3)	C12_2—C20_2—C21B_2—C22B_2	−133.2 (12)
C12A—C12—C20—C21	−61.8 (2)	C12A_2—O1_2—C2_2—C3_2	44.4 (2)
C12A—C12—C20—C23	61.1 (2)	C12A_2—O1_2—C2_2—C13_2	−76.1 (2)
C12A—C12—C20—C24	−178.89 (18)	C12A_2—O1_2—C2_2—C14_2	165.80 (17)
C13—C2—C3—C4	146.3 (2)	C12A_2—C4A_2—C5_2—C5A_2	−0.5 (3)
C14—C2—C3—C4	−88.7 (2)	C12A_2—C4A_2—C5_2—O15_2	179.34 (18)
O15—C5—C5A—C6	0.9 (3)	C12A_2—C12_2—C20_2—C21_2	−15.3 (4)
O15—C5—C5A—C11A	179.09 (18)	C12A_2—C12_2—C20_2—C21B_2	23.0 (4)
O16—C6—C6A—C7	−0.9 (3)	C12A_2—C12_2—C20_2—C23_2	123.1 (2)
O16—C6—C6A—C10A	178.77 (19)	C12A_2—C12_2—C20_2—C24_2	−116.5 (2)
O16—C6—C5A—C5	0.7 (3)	C13_2—C2_2—C3_2—C4_2	86.9 (3)
O16—C6—C5A—C11A	−177.38 (19)	C14_2—C2_2—C3_2—C4_2	−147.9 (2)
O17—C9—C10—C10A	179.24 (17)	O15_2—C5_2—C5A_2—C6_2	−0.1 (3)
O17—C9—C10—O19	−1.1 (3)	O15_2—C5_2—C5A_2—C11A_2	−178.65 (18)
O19—C10—C10A—C6A	−178.94 (18)	O16_2—C6_2—C6A_2—C7_2	2.1 (3)
O19—C10—C10A—O11	1.8 (3)	O16_2—C6_2—C6A_2—C10A_2	−177.35 (19)
C5A—C6—C6A—C7	179.82 (18)	O17_2—C9_2—C10_2—C10A_2	−179.01 (17)
C5A—C6—C6A—C10A	−0.5 (3)	O17_2—C9_2—C10_2—O19_2	1.1 (3)
C5A—C11A—C12—C12A	0.0 (3)	O19_2—C10_2—C10A_2—C6A_2	179.34 (19)
C5A—C11A—C12—C20	179.06 (19)	O19_2—C10_2—C10A_2—O11_2	−0.7 (3)
C20—C12—C12A—O1	3.3 (3)	C20_2—C12_2—C12A_2—O1_2	−1.9 (3)
C20—C12—C12A—C4A	179.87 (18)	C20_2—C12_2—C12A_2—C4A_2	−177.8 (2)
C23—C20—C21—C22	8.5 (3)	C23_2—C20_2—C21_2—C22_2	−5.5 (13)
C24—C20—C21—C22	−106.6 (3)	C23_2—C20_2—C21B_2—C22B_2	114.1 (12)
O1_2—C2_2—C3_2—C4_2	−32.4 (3)	C24_2—C20_2—C21_2—C22_2	−118.7 (13)
C2_2—O1_2—C12A_2—C4A_2	−28.2 (3)	C24_2—C20_2—C21B_2—C22B_2	0.5 (13)
C2_2—O1_2—C12A_2—C12_2	155.71 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O15—H15···O16	0.84	1.78	2.530 (2)	147
O15_2—H15_2···O16_2	0.84	1.80	2.547 (2)	147
O19—H19···O16ⁱ	0.84	1.92	2.719 (2)	159
O19_2—H19_2···O16_2ⁱⁱ	0.84	1.92	2.704 (2)	156

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

Footnotes

‡KC and SH contributed equally as corresponding authors.

Acknowledgements

The authors thank the Center of Excellence for Innovation in Chemistry (PERCH-CIC), Mahidol University, Thailand, for the use of spectroscopic instruments, and the Faculty of Science, Mahidol University, for the use of the X-ray diffractometer. SH thanks the Faculty of Science and Technology, Rajabhat Rajanagarindra University, Thailand, for laboratory facilities support.

Funding information

Funding for this research was provided by: Rajabhat Rajanagarindra University, Thailand.

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