Crystal structure and Hirshfeld analysis of (1aS,3aR,4aS,5aR)-15-acet­oxy­linden-7(11),8-trieno-12,8-lactone

Lu, Q.-Q.; Shi, X.-W.; Zhou, Y.-F.; Cui, X.-A.; Wang, H.

doi:10.1107/S2056989022004625

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 78| Part 6| June 2022| Pages 642-646

https://doi.org/10.1107/S2056989022004625

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Crystal structure and Hirshfeld analysis of (1aS,3aR,4aS,5aR)-15-acetoxylinden-7(11),8-trieno-12,8-lactone

Qiang-Qiang Lu,^a Xin-Wei Shi,^a ^* Ya-Fu Zhou,^a Xin-Ai Cui ^a and Hong Wang ^a

^aShaanxi Engineering Research Centre for Conservation and Utilization of Botanical Resources, Xi'an Botanical Garden of Shaanxi Province (Institute of Botany of Shaanxi Province), Xi'an 710061, People's Republic of China
^*Correspondence e-mail: sxw@ms.xab.ac.cn

Edited by A. Briceno, Venezuelan Institute of Scientific Research, Venezuela (Received 9 March 2022; accepted 2 May 2022; online 20 May 2022)

The structure of the title compound, C₁₇H₂₀O₄ [systematic name: (1aS,3aR,4aS,5aR)-15-(acetoxy)linden-7(11),8-trieno-12,8-lactone or (4aR,5S,5aR,6aS,6bR)-5-(acetoxymethyl)-4a,5,5a,6,6a,6b-hexahydro-3,6b-dimethylcyclopropa[2,3]indeno[5,6-b]furan-2(4H)-one, ent-chloranthalactone C], a natural product isolated from the whole plant Chloranthus japonicus Sieb., is a typical lindenane-type sesquiterpenoid. The molecule comprises a bicyclo[3.1.0]hexane ring (A/B system) bearing an acetoxymethyl (C-4) group, a bicyclo[4.3.0]nonane ring (B/C system) containing a double bond (C-8/9) and a chiral quaternary carbon (C-10), and a 7(11)-en-12,8-olide structural moiety on the cyclohexan-8-ene (C ring). In the tetracyclic skeleton, the 1,3-cyclopropane ring has a β-configuration, and atoms H-5 and H₃-14 have α- and β-orientations, respectively. In the crystal, the molecules are assembled into a two-dimensional network by weak O⋯H/H⋯O interactions. Hirshfeld surface analysis illustrates that the greatest contributions are from H⋯H (55.2%), O⋯H/H⋯O (34.6%) and C⋯H/H⋯C (8.9%) contacts.

Keywords: crystal structure; sesquiterpenes; polycyclic framework; Chloranthus japonicus.

CCDC reference: 2169817

1. Chemical context

Lindenanolides are precursors for various sesquiterpene dimer derivatives (Uchida et al., 1980 ; Wang et al., 2009 ; Shi et al., 2016 ). Inspired by the clinical application of artemisinin, these compounds have become a products library for screening antimalarial drugs (Dondorp et al., 2010 ; Zhou et al., 2017 ). The roots of Chloranthus japonicus (called Yinxiancao) were reported to exhibit antifungal and anti-inflammatory activities, and have been used as traditional Chinese medicine to treat malaria (Kawabata & Mizutani, 1989 ). Chloranthalactone C was characterized as an α,β,γ,δ-unsaturated γ-lactone and was converted into desacetyl enol lactone hydrate and ketoalcohol under moderate alkaline conditions (Uchida et al., 1980). Because of the unique stereostructure in lindenane, these lactone derivatives have been studied extensively and serve as precursors for screening cytotoxicity against mouse lymphosarcoma, liver cancer and human cervical cancer cells, the expression of cell adhesion molecules and the mode of antiplasmodial agents (Uchida et al., 1980; Zhang et al., 2012 ; Zhou et al., 2017). Based on the antiwiggler activity, we are currently searching for a biological pesticide preparation to inhibit flyblow breeding in vegetable production (Shi et al., 2016) and report here the structure of the title compound.

2. Structural commentary

The molecular structure of the title compound is shown in Scheme 1 and Fig. 1. This compound consists of a novel polycyclic framework embedded with a sterically congested cyclopentane ring (B), an unusual trans-5/6 ring junction and an angular methyl group. The chiral quaternary C atom at the 10-position is located on the same side of the B ring plane as the cyclopropane ring and the 4-acetoxymethyl and 5-hydrogen are positioned on the other side. The positions of the substituents can be described as having a β-configuration for the cyclopropane ring at the 1,3-positions, axial for the H atom at the 5-position and bisectional for the methyl H atom at the chiral quaternary C atom in the 10-position. Two cyclic olefinic bonds are located between atoms C2 and C3, and between atoms C4 and C5, and are attached to the cyclohexane (C) and cyclopentanolactone (D) rings, respectively. The torsion angles C9—C10—C11—C12 and C12—C10—C11—C6 of 115.2 (4) and −115.2 (4)°, respectively, describe the geometric metamerism of the junction between cyclopropane ring A and cyclopentane ring B. The difference in configuration of the oxygen-containing groups can be confirmed by the torsion angles C7—C9—C15—O3 and O1—C1—O2—C4, which were 179.9 (3) and −179.0 (4)°, respectively. The torsion angles C5—C6—C11—C12 and C2—C3—C8—C7 are the same at 155.5 (4)°, indicating the conformational stability of the A/B and C/D ring junctions. Also, the C2—C3—C4—C5 and C8—C3—C4—O2 torsion angles are 177.1 (4) and 177.2 (3)°, respectively, and the O2—C1—C2—C14 and C14—C2—C3—C4 torsion angles are 179.9 (3) and −178.9 (4)°, respectively, and describe the geometric characteristics of the C and D rings. In the title molecule, the central six-membered lindenane sesquiterpenoid ring has a half-chair conformation, with puckering parameters (Cremer & Pople, 1975 ; Luger & Bülow, 1983 ) of Q_T = 0.3387 (11) Å, θ = 49.11 (19)° and ψ = 167.3 (2)°. Furthermore, the C9—C7—C8—C3 and C5—C4—O2—C1 torsion angles [−178.6 (3) and −177.6 (4)°, respectively] indicate the geometric stability of the B/C and C/D ring junctions. In addition, the main A/B/C/D skeleton and the acetoxymethyl system (atoms C15–C17/O3/O4) are not coplanar, the torsion angles C15—O3—C16—C17 and C15—O3—C16—O4 being −175.9 (3) and 2.8 (6)°, respectively.

Figure 1
The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

In the crystal of the title compound, the molecules are linked via multiple C—H⋯O weak hydrogen bonds, generating two-dimensional (2D) layers propagating along the c-axis direction (Fig. 2 and Table 1). Details of the hydrogen-bonding interactions and the symmetry codes are given in Table 1.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O1ⁱ	0.97	2.81	3.481 (5)	127
C11—H11⋯O3ⁱⁱ	0.98	2.54	3.497 (5)	167
C13—H13C⋯O1ⁱⁱⁱ	0.96	2.60	3.499 (5)	157
C13—H13B⋯O4^iv	0.96	2.61	3.530 (6)	160
C14—H14A⋯O2ⁱ	0.96	2.76	3.530 (5)	138
C17—H17C⋯O3^v	0.96	2.86	3.478 (5)	124
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iv) x, y+1, z; (v) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
The packing of molecules in the crystal structure of the title compound, viewed along the c direction (C—H⋯O hydrogen bonds are shown as green dashed lines).

4. Hirshfeld surface analysis

Hirshfeld surface analysis was performed and the associated fingerprint plots, providing a 2D view of the intermolecular interactions within the molecular crystals, were generated using CrystalExplorer (Version 21.5; Spackman et al., 2021 ), with a standard resolution of the three-dimensional (3D) d_norm surfaces plotted over a fixed colour scale of −0.1253 (red) to 1.4046 (blue) arbitrary units (Fig. 3). The intense red spots symbolize short contacts and negative d_norm values on the surface are related to the presence of C—H⋯O hydrogen bonds in the crystal structure. This result corresponds to the results obtained from the solid crystalline structure with the formation of hydrogen bonds. Weak C⋯H/H⋯C contacts are shown by dim red spots (Fig. 4). The 2D fingerprint plots for the H⋯H, H⋯O/O⋯H, and H⋯C/C⋯H contacts are shown in Fig. 5. H⋯H interactions play an integral role in the overall crystal packing, contributing 55.2%, and are located in the middle region of the fingerprint plot. The most significant H⋯O/O⋯H contacts contribute 34.6% to the Hirshfeld surface and the proportion of weak H⋯C/C⋯H contacts is 8.9%.

Figure 3
Front view of the 3D Hirshfeld surface of the title compound mapped over d_norm in the range from −0.1253 to 1.4046 arbitrary units.

Figure 4
Hirshfeld surface mapped over d_norm for the molecules of the title compound showing: (a) H⋯O/O⋯H contacts (front), (b) H⋯O/O⋯H contacts (profile), (c) H⋯O/O⋯H contacts (back) and (d) C⋯H/H⋯C contacts (back). H atoms not involved in bonding have been omitted for clarity.

Figure 5
The 2D fingerprint plots of the title compound, showing (a) all interactions, and delineated into (b) H⋯H, (c) O⋯H/H⋯O and (d) C⋯H/H⋯C interactions. The d_e and d_i values represent the distances (in Å) from a point on the Hirshfeld surface to the nearest atoms inside and outside the surface, respectively.

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.43, last update November 2021; Groom et al., 2016 ) for the same carbon ring skeleton as the title compound yielded only one molecule, 5-[(tert-butyldimethylsilyl)oxy]-3,6b-dimethyl-4a,5,5a,6,6a,6b-hexahydrocyclopropa[2,3]indeno[5,6-b]furan-2(4H)-one (CCDC reference 804060; Qian & Zhao, 2011 ), which has a (tert-butyldimethylsilyl)oxy group attached to ring A of the carbon skeleton.

6. Isolation and crystallization

The title sesquiterpenoid was isolated as a colourless solid from the EtOAc soluble fraction of C. japonicus by chromatography over silica gel, and eluted with a mixture of ethyl acetate and hexane (1:20 to 5:1 v/v gradient) to yield the title compound. Crystals were obtained after recrystallization from acetone or chloroform–methanol (6:1 v/v) at room temperature by slow evaporation over a period of a few days. ¹H NMR (500 MHz, chloroform-d): δ 6.22 (1H, s, H-9), 4.20 (2H, d, J = 6.1 Hz, H-11), 2.63 (1H, d, J = 13.0 Hz), 2.30–2.21 (2H, m), 2.09 (3H, s, OCOCH₃), 1.87 (3H, br s, H-13), 1.73 (1H, tt, J = 10.1, 4.9 Hz), 1.53 (1H, td, J = 8.1, 3.8 Hz), 1.30 (1H, ddd, J = 11.9, 8.0, 3.7 Hz), 0.91 (1H, dd, J = 3.8, 2.1 Hz), 0.89 (3H, s, H-15), 0.83 (1H, td, J = 8.4, 6.0 Hz). ¹³C NMR (125 MHz, chloroform-d): δ 171.34 (OCOCH₃ or C-12), 171.31 (OCOCH₃ or C-12), 149.69 (C-8), 148.41 (C-7), 122.47 (C-11), 120.13 (C-9), 66.23 (C-15), 60.45 (C-5), 43.11 (C-4), 42.15 (C-10), 27.47 (C-1), 22.87 (C-6), 22.48 (C-3), 21.25 (OCOCH₃ or C-14), 21.21 (OCOCH₃ or C-14), 17.15 (C-2), 8.83 (C-13).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were positioned geometrically (C—H = 0.96–0.98 Å) and refined as riding, with U_iso(H) = 1.2U_eq(C) for CH hydrogens or 1.5U_eq(C) for methyl H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₂₀O₄
M_r	288.33
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	6.7641 (3), 6.9254 (3), 31.4538 (14)
V (Å³)	1473.42 (11)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 )
No. of measured, independent and observed [I > 2σ(I)] reflections	12659, 2576, 1857
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.117, 1.05
No. of reflections	2576
No. of parameters	193
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.21
Absolute structure	Flack x determined using 574 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.10 (8)
Computer programs: SMART and SAINT (Bruker, 2002 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2169817

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989022004625/zn2018sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022004625/zn2018Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989022004625/zn2018Isup3.cml

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SMART (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

(4aR,5S,5aR,6aS,6bR)-5-(Acetoxymethyl)-4a,5,5a,6,6a,6b-hexahydro-3,6b-dimethylcyclopropa[2,3]indeno[5,6-b]furan-2(4H)-one top

Crystal data top

C₁₇H₂₀O₄	D_x = 1.300 Mg m⁻³
M_r = 288.33	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 3545 reflections
a = 6.7641 (3) Å	θ = 2.6–20.7°
b = 6.9254 (3) Å	µ = 0.09 mm⁻¹
c = 31.4538 (14) Å	T = 296 K
V = 1473.42 (11) Å³	Block, colorless
Z = 4	0.20 × 0.20 × 0.20 mm
F(000) = 616

Data collection top

Bruker SMART CCD diffractometer	1857 reflections with I > 2σ(I)
phi and ω scans	R_int = 0.057
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θ_max = 25.0°, θ_min = 2.6°
	h = −7→8
12659 measured reflections	k = −8→6
2576 independent reflections	l = −32→37

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.051	w = 1/[σ²(F_o²) + (0.0466P)² + 0.380P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.117	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.30 e Å⁻³
2576 reflections	Δρ_min = −0.21 e Å⁻³
193 parameters	Absolute structure: Flack x determined using 574 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.10 (8)

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
O1	0.1658 (5)	0.5144 (4)	0.54793 (8)	0.0745 (9)
O2	0.1329 (4)	0.5303 (4)	0.47683 (7)	0.0537 (7)
O3	0.9151 (4)	0.1520 (4)	0.31668 (8)	0.0566 (8)
O4	0.9315 (6)	−0.1600 (5)	0.32844 (14)	0.1261 (18)
C1	0.2446 (6)	0.5140 (6)	0.51366 (12)	0.0536 (10)
C2	0.4539 (6)	0.4960 (5)	0.50214 (10)	0.0480 (9)
C3	0.4648 (5)	0.4991 (5)	0.45952 (10)	0.0418 (8)
C4	0.2650 (5)	0.5215 (5)	0.44282 (11)	0.0442 (9)
C5	0.2143 (5)	0.5386 (5)	0.40250 (11)	0.0447 (10)
H5	0.0829	0.5495	0.3942	0.054*
C6	0.3810 (5)	0.5396 (5)	0.37059 (10)	0.0389 (9)
C7	0.5465 (5)	0.4057 (5)	0.38746 (10)	0.0387 (9)
H7	0.4802	0.2839	0.3944	0.046*
C8	0.6345 (5)	0.4765 (6)	0.42937 (10)	0.0426 (9)
H8A	0.7290	0.3836	0.4403	0.051*
H8B	0.7014	0.5991	0.4253	0.051*
C9	0.6749 (5)	0.3603 (5)	0.34836 (10)	0.0414 (9)
H9	0.7586	0.4713	0.3414	0.050*
C10	0.5169 (6)	0.3322 (6)	0.31409 (11)	0.0503 (10)
H10	0.4988	0.2025	0.3023	0.060*
C11	0.3340 (6)	0.4435 (6)	0.32784 (11)	0.0506 (11)
H11	0.2047	0.3818	0.3243	0.061*
C12	0.4461 (6)	0.5003 (7)	0.28864 (10)	0.0613 (11)
H12A	0.3853	0.4739	0.2613	0.074*
H12B	0.5235	0.6181	0.2897	0.074*
C13	0.4477 (6)	0.7496 (5)	0.36559 (12)	0.0523 (11)
H13A	0.3469	0.8217	0.3511	0.078*
H13B	0.5679	0.7539	0.3494	0.078*
H13C	0.4701	0.8050	0.3932	0.078*
C14	0.6127 (7)	0.4764 (6)	0.53450 (12)	0.0650 (12)
H14A	0.6047	0.3512	0.5475	0.098*
H14B	0.5968	0.5743	0.5558	0.098*
H14C	0.7393	0.4911	0.5211	0.098*
C15	0.8003 (6)	0.1832 (5)	0.35511 (11)	0.0488 (10)
H15A	0.8877	0.2019	0.3792	0.059*
H15B	0.7171	0.0720	0.3608	0.059*
C16	0.9745 (5)	−0.0230 (6)	0.30723 (13)	0.0550 (10)
C17	1.1017 (6)	−0.0305 (7)	0.26893 (12)	0.0660 (12)
H17A	1.2179	0.0462	0.2735	0.099*
H17B	1.0301	0.0192	0.2450	0.099*
H17C	1.1394	−0.1619	0.2635	0.099*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.106 (2)	0.074 (2)	0.0437 (16)	0.017 (2)	0.0283 (16)	−0.0019 (15)
O2	0.0592 (16)	0.0591 (17)	0.0427 (15)	0.0035 (15)	0.0182 (13)	−0.0021 (13)
O3	0.076 (2)	0.0422 (16)	0.0520 (16)	0.0031 (15)	0.0267 (16)	−0.0038 (13)
O4	0.137 (4)	0.058 (2)	0.184 (4)	0.013 (2)	0.101 (3)	0.014 (3)
C1	0.080 (3)	0.040 (2)	0.040 (2)	0.013 (2)	0.014 (2)	−0.001 (2)
C2	0.069 (3)	0.036 (2)	0.039 (2)	0.002 (2)	0.0037 (19)	−0.0026 (18)
C3	0.054 (2)	0.0344 (19)	0.0366 (19)	0.000 (2)	0.0037 (17)	−0.0007 (17)
C4	0.049 (2)	0.043 (2)	0.040 (2)	0.000 (2)	0.0113 (18)	−0.0030 (19)
C5	0.038 (2)	0.052 (2)	0.044 (2)	−0.003 (2)	0.0027 (17)	−0.0035 (19)
C6	0.0395 (19)	0.045 (2)	0.0324 (18)	−0.0053 (18)	0.0005 (16)	−0.0023 (16)
C7	0.042 (2)	0.040 (2)	0.0340 (19)	−0.0054 (18)	0.0046 (17)	−0.0033 (15)
C8	0.044 (2)	0.047 (2)	0.0366 (18)	−0.003 (2)	−0.0007 (16)	−0.0045 (17)
C9	0.045 (2)	0.041 (2)	0.039 (2)	−0.0055 (18)	0.0052 (18)	−0.0040 (16)
C10	0.054 (2)	0.058 (3)	0.039 (2)	−0.005 (2)	0.005 (2)	−0.0120 (19)
C11	0.044 (2)	0.068 (3)	0.040 (2)	−0.011 (2)	0.0019 (18)	−0.0067 (18)
C12	0.061 (2)	0.091 (3)	0.0322 (19)	−0.002 (3)	−0.0002 (18)	0.002 (2)
C13	0.057 (3)	0.048 (2)	0.052 (2)	−0.006 (2)	0.000 (2)	0.0053 (18)
C14	0.093 (3)	0.058 (3)	0.044 (2)	0.004 (3)	−0.006 (2)	−0.003 (2)
C15	0.062 (2)	0.046 (2)	0.039 (2)	−0.001 (2)	0.015 (2)	−0.0029 (18)
C16	0.047 (2)	0.048 (3)	0.070 (3)	−0.006 (2)	0.013 (2)	−0.007 (2)
C17	0.063 (3)	0.071 (3)	0.064 (3)	0.006 (3)	0.014 (2)	−0.017 (2)

Geometric parameters (Å, º) top

O1—C1	1.202 (4)	C9—C15	1.507 (5)
O2—C1	1.388 (4)	C9—C10	1.530 (5)
O2—C4	1.396 (4)	C9—H9	0.9800
O3—C16	1.311 (5)	C10—C12	1.492 (6)
O3—C15	1.453 (4)	C10—C11	1.520 (5)
O4—C16	1.196 (5)	C10—H10	0.9800
C1—C2	1.467 (6)	C11—C12	1.500 (5)
C2—C3	1.343 (4)	C11—H11	0.9800
C2—C14	1.486 (5)	C12—H12A	0.9700
C3—C4	1.458 (5)	C12—H12B	0.9700
C3—C8	1.497 (5)	C13—H13A	0.9600
C4—C5	1.319 (5)	C13—H13B	0.9600
C5—C6	1.509 (5)	C13—H13C	0.9600
C5—H5	0.9300	C14—H14A	0.9600
C6—C13	1.531 (5)	C14—H14B	0.9600
C6—C11	1.534 (5)	C14—H14C	0.9600
C6—C7	1.548 (5)	C15—H15A	0.9700
C7—C8	1.528 (4)	C15—H15B	0.9700
C7—C9	1.538 (5)	C16—C17	1.481 (5)
C7—H7	0.9800	C17—H17A	0.9600
C8—H8A	0.9700	C17—H17B	0.9600
C8—H8B	0.9700	C17—H17C	0.9600

C1—O2—C4	106.7 (3)	C11—C10—C9	107.7 (3)
C16—O3—C15	119.3 (3)	C12—C10—H10	118.1
O1—C1—O2	120.4 (4)	C11—C10—H10	118.1
O1—C1—C2	130.5 (4)	C9—C10—H10	118.1
O2—C1—C2	109.0 (3)	C12—C11—C10	59.2 (3)
C3—C2—C1	107.4 (3)	C12—C11—C6	120.1 (3)
C3—C2—C14	130.2 (4)	C10—C11—C6	107.5 (3)
C1—C2—C14	122.4 (3)	C12—C11—H11	118.2
C2—C3—C4	108.1 (3)	C10—C11—H11	118.2
C2—C3—C8	132.3 (3)	C6—C11—H11	118.2
C4—C3—C8	119.6 (3)	C10—C12—C11	61.1 (3)
C5—C4—O2	124.5 (3)	C10—C12—H12A	117.7
C5—C4—C3	126.6 (3)	C11—C12—H12A	117.7
O2—C4—C3	108.8 (3)	C10—C12—H12B	117.7
C4—C5—C6	116.5 (3)	C11—C12—H12B	117.7
C4—C5—H5	121.8	H12A—C12—H12B	114.8
C6—C5—H5	121.8	C6—C13—H13A	109.5
C5—C6—C13	107.0 (3)	C6—C13—H13B	109.5
C5—C6—C11	115.2 (3)	H13A—C13—H13B	109.5
C13—C6—C11	112.5 (3)	C6—C13—H13C	109.5
C5—C6—C7	108.0 (3)	H13A—C13—H13C	109.5
C13—C6—C7	113.1 (3)	H13B—C13—H13C	109.5
C11—C6—C7	101.0 (3)	C2—C14—H14A	109.5
C8—C7—C9	122.4 (3)	C2—C14—H14B	109.5
C8—C7—C6	112.7 (3)	H14A—C14—H14B	109.5
C9—C7—C6	104.9 (3)	C2—C14—H14C	109.5
C8—C7—H7	105.2	H14A—C14—H14C	109.5
C9—C7—H7	105.2	H14B—C14—H14C	109.5
C6—C7—H7	105.2	O3—C15—C9	107.7 (3)
C3—C8—C7	106.3 (3)	O3—C15—H15A	110.2
C3—C8—H8A	110.5	C9—C15—H15A	110.2
C7—C8—H8A	110.5	O3—C15—H15B	110.2
C3—C8—H8B	110.5	C9—C15—H15B	110.2
C7—C8—H8B	110.5	H15A—C15—H15B	108.5
H8A—C8—H8B	108.7	O4—C16—O3	122.2 (4)
C15—C9—C10	112.9 (3)	O4—C16—C17	124.5 (4)
C15—C9—C7	111.8 (3)	O3—C16—C17	113.3 (4)
C10—C9—C7	101.2 (3)	C16—C17—H17A	109.5
C15—C9—H9	110.2	C16—C17—H17B	109.5
C10—C9—H9	110.2	H17A—C17—H17B	109.5
C7—C9—H9	110.2	C16—C17—H17C	109.5
C12—C10—C11	59.7 (3)	H17A—C17—H17C	109.5
C12—C10—C9	120.2 (4)	H17B—C17—H17C	109.5

C4—O2—C1—O1	−178.9 (4)	C4—C3—C8—C7	−21.5 (5)
C4—O2—C1—C2	0.5 (4)	C9—C7—C8—C3	−178.6 (3)
O1—C1—C2—C3	178.5 (4)	C6—C7—C8—C3	55.0 (4)
O2—C1—C2—C3	−0.8 (5)	C8—C7—C9—C15	69.2 (4)
O1—C1—C2—C14	−0.9 (7)	C6—C7—C9—C15	−161.0 (3)
O2—C1—C2—C14	179.8 (3)	C8—C7—C9—C10	−170.4 (3)
C1—C2—C3—C4	0.7 (5)	C6—C7—C9—C10	−40.5 (3)
C14—C2—C3—C4	−179.9 (4)	C15—C9—C10—C12	−151.0 (3)
C1—C2—C3—C8	−176.5 (4)	C7—C9—C10—C12	89.3 (4)
C14—C2—C3—C8	2.9 (7)	C15—C9—C10—C11	144.3 (3)
C1—O2—C4—C5	−177.6 (4)	C7—C9—C10—C11	24.6 (4)
C1—O2—C4—C3	0.0 (4)	C9—C10—C11—C12	115.2 (4)
C2—C3—C4—C5	177.1 (4)	C12—C10—C11—C6	−115.2 (4)
C8—C3—C4—C5	−5.3 (6)	C9—C10—C11—C6	0.0 (4)
C2—C3—C4—O2	−0.4 (4)	C5—C6—C11—C12	155.4 (4)
C8—C3—C4—O2	177.2 (3)	C13—C6—C11—C12	32.3 (5)
O2—C4—C5—C6	175.6 (3)	C7—C6—C11—C12	−88.5 (4)
C3—C4—C5—C6	−1.5 (6)	C5—C6—C11—C10	−140.6 (3)
C4—C5—C6—C13	−88.5 (4)	C13—C6—C11—C10	96.4 (4)
C4—C5—C6—C11	145.6 (4)	C7—C6—C11—C10	−24.5 (4)
C4—C5—C6—C7	33.5 (4)	C9—C10—C12—C11	−93.8 (4)
C5—C6—C7—C8	−62.8 (4)	C6—C11—C12—C10	93.4 (4)
C13—C6—C7—C8	55.4 (4)	C16—O3—C15—C9	−153.7 (3)
C11—C6—C7—C8	175.8 (3)	C10—C9—C15—O3	66.5 (4)
C5—C6—C7—C9	161.8 (3)	C7—C9—C15—O3	179.9 (3)
C13—C6—C7—C9	−80.0 (3)	C15—O3—C16—O4	2.8 (6)
C11—C6—C7—C9	40.5 (3)	C15—O3—C16—C17	−175.9 (3)
C2—C3—C8—C7	155.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1ⁱ	0.97	2.81	3.481 (5)	127
C11—H11···O3ⁱⁱ	0.98	2.54	3.497 (5)	167
C13—H13C···O1ⁱⁱⁱ	0.96	2.60	3.499 (5)	157
C13—H13B···O4^iv	0.96	2.61	3.530 (6)	160
C14—H14A···O2ⁱ	0.96	2.76	3.530 (5)	138
C17—H17C···O3^v	0.96	2.86	3.478 (5)	124

Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x−1, y, z; (iii) x+1/2, −y+3/2, −z+1; (iv) x, y+1, z; (v) −x+2, y−1/2, −z+1/2.

Acknowledgements

The authors thank Hubei Normal University and Nian Zhao for recording the X-ray crystallographic data for the crystals.

Funding information

Funding for this research was provided by: Natural Science Basic Research Program of Shaanxi (grant Nos. 2020JM-708 and 2021JQ-968); Science and Technology Program of Shaanxi Academy of Sciences (grant Nos. 2018nk-01 and 2018k-11); Xi'an Science and Technology Plan Project (grant No. 20NYYF0043).

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