Crystal structure and Hirshfeld surface analysis of dieth­yl (3aS,3a1R,4S,5S,6R,6aS,7R,9aS)-3a1,5,6,6a-tetra­hydro-1H,3H,4H,7H-3a,6:7,9a-di­epoxy­benzo[de]isochromene-4,5-di­carboxyl­ate

Sadikhova, N.D.; Atioğlu, Z.; Guliyeva, N.A.; Podrezova, A.G.; Nikitina, E.V.; Akkurt, M.; Bhattarai, A.

doi:10.1107/S2056989023010794

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ISSN: 2056-9890

Volume 80| Part 1| January 2024| Pages 83-87

https://doi.org/10.1107/S2056989023010794

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Crystal structure and Hirshfeld surface analysis of diethyl (3aS,3a1R,4S,5S,6R,6aS,7R,9aS)-3a1,5,6,6a-tetrahydro-1H,3H,4H,7H-3a,6:7,9a-diepoxybenzo[de]isochromene-4,5-dicarboxylate

Nurlana D. Sadikhova,^a Zeliha Atioğlu,^b Narmina A. Guliyeva,^c Alexandra G. Podrezova,^d Eugeniya V. Nikitina,^d Mehmet Akkurt ^e ^* and Ajaya Bhattarai ^f ^*

^aOrganic Chemistry Department, Baku State University, Az 1148 Baku, Azerbaijan, ^bDepartment of Aircraft Electrics and Electronics, School of Applied Sciences, Cappadocia University, Mustafapaşa, 50420 Ürgüp, Nevşehir, Türkiye, ^cDepartment of Organic Substances and Technology of High-Molecular Compounds, SRI "Geotechnological Problems of Oil, Gas and Chemistry", Azerbaijan State Oil and Industry University, Azadlig ave. 20, Az-1010 Baku, Azerbaijan, ^dOrganic Chemistry Department, Faculty of Science, RUDN University, Miklukho-Maklaya St., 6, Moscow 117198, Russian Federation, ^eDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Türkiye, and ^fDepartment of Chemistry, M.M.A.M.C (Tribhuvan University) Biratnagar, Nepal
^*Correspondence e-mail: akkurt@erciyes.edu.tr, ajaya.bhattarai@mmamc.tu.edu.np

Edited by J. Reibenspies, Texas A & M University, USA (Received 11 December 2023; accepted 15 December 2023; online 1 January 2024)

In the title compound, C₁₈H₂₂O₇, two hexane rings and an oxane ring are fused together. The two hexane rings tend toward a distorted boat conformation, while the tetrahydrofuran and dihydrofuran rings adopt envelope conformations. The oxane ring is puckered. The crystal structure features C—H⋯O hydrogen bonds, which link the molecules into a three-dimensional network. According to a Hirshfeld surface study, H⋯H (60.3%) and O⋯H/H⋯O (35.3%) interactions are the most significant contributors to the crystal packing.

Keywords: crystal structure; (1R,4S)-7-oxabicyclo[2.2.1]hept-2-ene; (1S,4S)-7-oxabicyclo[2.2.1]heptane; oxane; weak interactions; Hirshfeld surface analysis.

CCDC reference: 2319519

1. Chemical context

The intermolecular Diels–Alder (DA) reaction of furans is a powerful tool in organic and medicinal chemistry, offering a versatile and efficient approach to the synthesis of complex molecules with valuable applications (for reviews and books on the topic, see: Chen et al., 2018 ; Winkler 1996 ; Parvatkar et al., 2014 ; Shi & Wang, 2020 ; Hopf & Sherburn, 2012 ; Safavora et al., 2019 ). The DA reaction of furans is typically carried out under thermal conditions, but the use of high pressure has emerged as a powerful tool for enhancing the reactivity and selectivity of this reaction. High pressure can significantly lower the activation energy of the DA reaction, leading to faster reaction rates and improved yields (see reviews by Rulev & Zubkov, 2022 ; Schettino & Bini, 2007 ). On the other hand, by the attachment of functional groups, the DA reaction products can participate in various sorts of intermolecular interactions with interesting coordination, supramolecular, catalytic and solvatochromic properties (Gurbanov et al., 2020a ,b ; Khalilov et al., 2021 ; Mahmoudi et al., 2017a ,b ; Mahmudov et al., 2015 ). For example, attachment of carboxylate groups to organic molecules can create coordination sites and interesting supramolecular architectures involving monomeric, oligomeric or polymeric subunits in metal complexes, which affects their catalytic activity (Gurbanov et al., 2022a ,b ; Ma et al., 2017 , 2021 ; Shikhaliyev et al., 2019 ). The present work showcases a facile methodology for the synthesis of compound 1a from a simple furan derivative and diethyl fumarate under high-pressure conditions. It is noteworthy that while several methods for the preparation of similar structures using more reactive dienophiles have been documented in the literature (Borisova et al., 2018a ,b ; Kvyatkovskaya et al., 2021a ,b ), this represents the first instance of such a reaction where thermal activation alone is insufficient to drive the transformation.

2. Structural commentary

In the title compound, (Fig. 1), the (1R,4S)-7-oxabicyclo[2.2.1]hept-2-ene (O11/C3B/C6A/C7–C9/C9A), (1S,4S)-7-oxabicyclo[2.2.1]heptane (O10/C3A/C3B/C4–C6/C6A) and and oxane (C1/O2/C3/C3A/C3B/C9A) rings are fused together. The hexane ring (C3B/C6A/C7–C9/C9A) tends towards a distorted boat conformation [the puckering parameters (Cremer & Pople, 1975 ) are Q_T = 1.0005 (15) Å, θ = 89.65 (9)° and φ = 300.58 (8)°], while the tetrahydrofuran (C3B/C6A/C7/O11/C9A) and dihydrofuran (C7–C9/C9A/O11) rings adopt envelope conformations, with puckering parameters Q(2) = 0.5625 (13) Å, φ(2) = 1.70 (14)° and Q(2) = 0.5143 (13) Å, φ(2) = 179.57 (17)°, respectively. The hexane ring (C3A/C3B/C4–C6/C6A) tends towards a distorted boat conformation [puckering parameters Q_T = 0.9758 (14) Å, θ = 91.04 (8)° and φ = 2.99 (8)°], while the tetrahydrofuran rings (C3A/C4–C6/O10 and C6/C6A/C3B/C3A/O10) adopt envelope conformations, with puckering parameters Q(2) = 0.5784 (13) Å, φ(2) = 185.10 (14)° and Q(2) = 0.5235 (13) Å, φ(2) = 357.36 (15)°, respectively. The oxane ring (C3A/C3B/C9A/C1/O2/C3) is puckered with puckering parameters Q_T = 0.5125 (14) Å, θ = 7.89 (15)° and φ = 3.1 (12)°. The C3A—C4—C12—O12, C3A—C4—C12—O13, C4—C12—O13—C13, C6—C5—C15—O15, C6—C5—C15—O16 and C5—C15—O16—C16 torsion angles are 107.12 (15), −72.14 (13), −177.31 (11), 120.28 (15), −60.17 (14) and 178.70 (11)°, respectively. The geometric parameters of the title compound are normal and comparable to those of related compounds listed in the Database survey section.

Figure 1
The molecular structure of the title complex with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level.

3. Supramolecular features and Hirshfeld surface analysis

The crystal structure of the title compound is stabilized by C—H⋯O hydrogen bonds, forming a three-dimensional network (Table 1; Figs. 2, 3 and 4). C—H⋯π and π–π interactions are not observed in the structure.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O13	0.99	2.58	3.1604 (17)	118
C9—H9A⋯O13ⁱ	0.95	2.47	3.1692 (17)	131
C13—H13A⋯O2ⁱⁱ	0.99	2.58	3.1905 (17)	120
C13—H13B⋯O10ⁱⁱ	0.99	2.41	3.2193 (17)	139
C14—H14C⋯O15ⁱ	0.98	2.64	3.5669 (19)	158
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
A packing diagram of the title complex, showing the C—H⋯O interactions along the a axis as dashed lines.

Figure 3
View of the crystal structure of the title complex, along the b axis; the same interactions are as in Fig. 2

Figure 4
View of the crystal structure of the title complex, along the c axis; the same interactions are as in Fig. 2

Crystal Explorer 17.5 (Spackman et al., 2021 ) was used to generate Hirshfeld surfaces and two-dimensional fingerprint plots in order to quantify the intermolecular interactions in the crystal. The Hirshfeld surfaces were mapped over d_norm (Fig. 5). The interactions listed in Table 2 play a key role in the molecular packing of the title compound. The most important interatomic contact is H⋯H as it makes the highest contribution to the crystal packing (60.2%, Fig. 6b). The other major contributor is the O⋯H/H⋯O (35.4%, Fig. 6c) interaction. Other, smaller contributions are made by C⋯H/H⋯C (3.9%), O⋯O (0.3%), C⋯C (0.2%) and O⋯C/C⋯O (0.1%) interactions.

Table 2
Summary of short interatomic contacts (Å) in the title compound

Contact	Distance	Symmetry operation
H3A⋯H6AA	2.49	1 + x, y, z
O10⋯H13B	2.41	x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z
H16B⋯H16B	2.57	−x, 1 − y, 1 − z
H1A⋯O11	2.73	1 − x, −y, 1 − z
H17A⋯H13B	2.29	−x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
O13⋯H9A	2.47	1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
H7A⋯C8	3.02	−x, −y, 1 − z
H6A⋯H14A	2.50	−1 + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z

Figure 5
(a) Front and (b) back sides of the three-dimensional Hirshfeld surface of the title compound mapped over d_norm, with a fixed colour scale of −0.1982 to +1.2419 a.u.

Figure 6
The two-dimensional fingerprint plots of the title compound, showing (a) all interactions, and delineated into (b) H⋯H and (c) O⋯H/H⋯O interactions. [d_e and d_i represent the distances from a point on the Hirshfeld surface to the nearest atoms outside (external) and inside (internal) the surface, respectively].

4. Database survey

Four related compounds were found in a search of the Cambridge Structural Database (CSD, version 5.42, update of September 2021; Groom et al., 2016 ), viz. N-carbamothioylamino-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (CSD refcode WAFPOK; Li, 2010 ), {3-hydroxymethyl-1-[2-(3-methoxyphenyl)ethyl]-7-oxabicyclo(2.2.1)hept-5-en-2-yl}methanol (SIMPUA; Wang & Peng, 2007 ), (1SR,2SR,4SR)-7-oxabicyclo(2.2.1)hept-5-ene-2-carboxylic acid (ETEYEH; Gartenmann Dickson et al., 2004 ) and (1S*,2R*,5S*,6S*,7R*)-5-hydroxy-4-(4-methoxyphenyl)-10-oxa-4-azatricyclo(5.2.1.02,6)dec-8-en-one (DIWLEB; Gökçe et al., 2008 ).

The compound WAFPOK comprises a racemic mixture of chiral molecules containing four stereogenic centres. The cyclohexane ring tends towards a boat conformation, while the tetrahydrofuran and dihydrofuran rings adopt envelope conformations. The dihedral angle between the thiosemicarbazide fragment and the fused-ring system is 77.20 (10)°. The crystal structure is stabilized by two intermolecular N—H⋯O hydrogen bonds. SIMPUA is an oxabicyclo[2.2.1]hept-5- ene with two exo-oriented hydroxymethyl groups, which are not parallel to each other. The molecules are linked to each other by hydrogen bonds, resulting in a supramolecular network. Intermolecular O—H⋯O hydrogen bonding is observed between the hydroxyl groups. In ETEYEH, the molecules are connected by O—H⋯O hydrogen bonds, forming centrosymmetric dimers. The structure of DIWLEB comprises a racemic mixture of chiral molecules containing five stereogenic centres. The cyclohexane ring tends towards a boat conformation and the two tetrahydrofuran rings adopt envelope conformations. Molecules are linked into sheets parallel to (100) by a combination of O—H⋯O, C—H⋯O and C—H⋯π interactions, leading to a di-periodic supramolecular structure.

5. Synthesis and crystallization

A solution of diethyl fumarate (850 mg, 4.95 mmol, 1.1 equiv) and difurfuryl ether (800 mg, 4.5 mmol) in methanol (21 mL) was placed in a Teflon ampoule. The reaction mixture was then held at 15 kbar and r.t. for two days in a piston-cylinder type steel pressure chamber. The obtained methanol solution was concentrated in vacuo. The resulting light-yellow oil was solidified in hexane and then recrystallized from ethyl acetate to isolate diastereomer 1a exclusively (Fig. 7). The residue was filtered off and dried under reduced pressure in a vacuum desiccator to constant weight, yielding the target product as white crystals. White crystals, 0.32 g, 0.94 mmol, yield is 21%, R_f = 0.7 (`Sorbfil' plates for thin-layer chromatography, CHCl₃); mp: 418.1–419.1 K. A single-crystal of compound 1a was obtained by slow evaporation from ethyl acetate at 298 K.

Figure 7
Reaction mechanism.

¹H NMR (700 MHz, CDCl₃, 298 K) δ 6.40 (d, J = 5.7 Hz, 1H, CH=CH), 6.20 (d, J = 5.7 Hz, 1H, CH=CH), 5.02 (s, 1H, CH), 4.83 (s, 1H, CH), 4.38 (d, J = 12.8 Hz, 1H, from CH₂), 4.27 (d, J = 12.9 Hz, 1H, from CH₂), 4.23–4.13 (m, 4H, 2OCH₂CH₃), 4.02 (d, J = 12.9 Hz, 1H, from CH₂), 3.89 (d, J = 12.8 Hz, 1H, from CH₂), 3.19 (d, J = 5.2 Hz, 1H, CH), 3.12 (d, J = 5.2 Hz, 1H, CH), 2.13 (d, J = 6.4 Hz, 1H, CH), 1.75 (d, J = 6.3 Hz, 1H, CH), 1.36–1.14 (m, 6H, 2OCH₂CH₃) . ¹³C NMR (175 MHz, CDCl₃, 298 K) δ 171.69, 170.50, 138.05, 136.58, 84.04, 82.64, 82.26, 81.65, 66.67, 66.29, 61.52 (2C), 53.12, 52.70, 49.90, 43.15, 14.34, 14.25. IR ν_max/cm⁻¹ (tablet KBr): 3440, 2982, 2950, 2910, 2859, 1728, 1473, 1311, 1211, 1174, 1093, 1029, 973, 912, 856, 697. HRMS (ESI-TOF): calculated for C₁₈H₂₃O₇ [M + H]⁺ 351.1443; found 351.1440.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. C-bound H atoms were included in the refinement using the riding-model approximation with C—H distances of 0.95–1.00 Å, and with U_iso(H) = 1.2 or 1.5U_eq(C). Two reflections (0 1 1 and 1 1 0), affected by the incident beam-stop, were omitted in the final cycles of refinement.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₈H₂₂O₇
M_r	350.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.1566 (4), 14.1907 (9), 16.2737 (10)
β (°)	91.329 (2)
V (Å³)	1652.27 (17)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.40 × 0.36 × 0.34

Data collection
Diffractometer	Bruker Kappa APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 ).
T_min, T_max	0.941, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	28552, 4921, 3615
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.709

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.119, 1.03
No. of reflections	4921
No. of parameters	226
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.30
Computer programs: APEX3 and SAINT (Bruker, 2018 ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2319519

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023010794/jy2042sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023010794/jy2042Isup2.hkl

checkCIF report

Computing details top

Diethyl (3aS,3a1R,4S,5S,6R,6aS,7R,9aS)-3a1,5,6,6a-tetrahydro-1H,3H,4H,7H-3a,6:7,9a-diepoxybenzo[de]isochromene-4,5-dicarboxylate top

Crystal data top

C₁₈H₂₂O₇	F(000) = 744
M_r = 350.35	D_x = 1.408 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.1566 (4) Å	Cell parameters from 5852 reflections
b = 14.1907 (9) Å	θ = 2.5–29.9°
c = 16.2737 (10) Å	µ = 0.11 mm⁻¹
β = 91.329 (2)°	T = 100 K
V = 1652.27 (17) Å³	Bulk, colourless
Z = 4	0.40 × 0.36 × 0.34 mm

Data collection top

Bruker KAPPA APEXII area-detector diffractometer	3615 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.051
Absorption correction: multi-scan (SADABS; Krause et al., 2015).	θ_max = 30.3°, θ_min = 2.9°
T_min = 0.941, T_max = 1.000	h = −10→10
28552 measured reflections	k = −20→18
4921 independent reflections	l = −23→22

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0541P)² + 0.5731P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
4921 reflections	Δρ_max = 0.35 e Å⁻³
226 parameters	Δρ_min = −0.30 e Å⁻³

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
O2	0.65003 (13)	0.14690 (7)	0.39784 (6)	0.0185 (2)
O10	0.32231 (13)	0.27216 (6)	0.41424 (6)	0.01429 (19)
O11	0.28123 (13)	0.08569 (7)	0.44881 (6)	0.0166 (2)
O12	0.20009 (15)	0.28745 (9)	0.14509 (7)	0.0289 (3)
O13	0.51089 (13)	0.30191 (7)	0.16601 (6)	0.0202 (2)
O15	0.20749 (15)	0.50604 (7)	0.32809 (7)	0.0275 (3)
O16	−0.06545 (14)	0.45134 (7)	0.37426 (6)	0.0203 (2)
C1	0.56703 (19)	0.05898 (10)	0.37326 (9)	0.0190 (3)
H1A	0.604785	0.009304	0.412996	0.023*
H1B	0.613288	0.040808	0.318629	0.023*
C3B	0.28585 (17)	0.15148 (9)	0.31737 (8)	0.0127 (2)
H3BA	0.276226	0.137729	0.257158	0.015*
C3A	0.39716 (17)	0.24133 (9)	0.33732 (8)	0.0129 (2)
C3	0.60532 (18)	0.22335 (10)	0.34389 (8)	0.0167 (3)
H3A	0.652818	0.209205	0.288583	0.020*
H3B	0.668881	0.281058	0.364234	0.020*
C4	0.32813 (18)	0.32304 (9)	0.28048 (8)	0.0132 (2)
H4A	0.406592	0.379971	0.292317	0.016*
C5	0.13032 (18)	0.34034 (9)	0.31390 (8)	0.0139 (2)
H5A	0.033387	0.321017	0.271973	0.017*
C6	0.12801 (18)	0.27188 (9)	0.38872 (8)	0.0144 (3)
H6A	0.040849	0.291342	0.432769	0.017*
C6A	0.09390 (18)	0.17152 (9)	0.35618 (8)	0.0141 (2)
H6AA	−0.012435	0.168001	0.315333	0.017*
C7	0.08827 (19)	0.09147 (9)	0.42186 (9)	0.0173 (3)
H7A	−0.003793	0.100706	0.466452	0.021*
C8	0.0674 (2)	0.00021 (10)	0.37333 (10)	0.0224 (3)
H8A	−0.041834	−0.037460	0.367396	0.027*
C9A	0.35656 (18)	0.06594 (9)	0.36921 (8)	0.0155 (3)
C9	0.2335 (2)	−0.01604 (9)	0.34091 (9)	0.0210 (3)
H9A	0.267854	−0.067681	0.307329	0.025*
C12	0.33375 (18)	0.30231 (9)	0.18944 (8)	0.0136 (2)
C13	0.5500 (2)	0.28738 (11)	0.07909 (8)	0.0200 (3)
H13A	0.568211	0.348732	0.051437	0.024*
H13B	0.444317	0.254289	0.051389	0.024*
C14	0.7242 (2)	0.22918 (11)	0.07489 (10)	0.0259 (3)
H14A	0.754364	0.218155	0.017244	0.039*
H14B	0.827848	0.262688	0.102366	0.039*
H14C	0.704464	0.168635	0.102318	0.039*
C15	0.10027 (19)	0.44187 (9)	0.33870 (8)	0.0159 (3)
C16	−0.1128 (2)	0.54538 (10)	0.40327 (9)	0.0216 (3)
H16A	−0.109745	0.591211	0.357452	0.026*
H16B	−0.022582	0.565926	0.446699	0.026*
C17	−0.3058 (2)	0.53933 (13)	0.43679 (13)	0.0369 (4)
H17A	−0.343372	0.601375	0.457067	0.055*
H17B	−0.393486	0.518921	0.393188	0.055*
H17C	−0.306732	0.493754	0.482017	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0118 (4)	0.0270 (5)	0.0167 (5)	0.0022 (4)	−0.0019 (4)	0.0041 (4)
O10	0.0130 (4)	0.0189 (4)	0.0110 (4)	0.0006 (3)	0.0019 (3)	−0.0018 (3)
O11	0.0142 (4)	0.0204 (5)	0.0150 (5)	0.0032 (4)	0.0017 (4)	0.0033 (4)
O12	0.0162 (5)	0.0536 (7)	0.0168 (5)	0.0001 (5)	−0.0023 (4)	−0.0039 (5)
O13	0.0136 (5)	0.0351 (6)	0.0121 (5)	−0.0026 (4)	0.0021 (4)	−0.0042 (4)
O15	0.0267 (6)	0.0169 (5)	0.0394 (7)	−0.0021 (4)	0.0097 (5)	−0.0038 (4)
O16	0.0207 (5)	0.0145 (4)	0.0260 (6)	0.0047 (4)	0.0069 (4)	−0.0019 (4)
C1	0.0142 (6)	0.0225 (7)	0.0204 (7)	0.0070 (5)	0.0014 (5)	0.0027 (5)
C3B	0.0105 (5)	0.0150 (6)	0.0126 (6)	0.0016 (4)	0.0000 (5)	−0.0006 (4)
C3A	0.0113 (6)	0.0171 (6)	0.0102 (6)	0.0008 (4)	0.0015 (5)	−0.0012 (4)
C3	0.0108 (6)	0.0244 (7)	0.0148 (6)	0.0006 (5)	0.0006 (5)	0.0034 (5)
C4	0.0129 (6)	0.0148 (6)	0.0120 (6)	−0.0005 (4)	0.0017 (5)	−0.0005 (4)
C5	0.0125 (6)	0.0143 (6)	0.0149 (6)	0.0014 (5)	0.0019 (5)	−0.0010 (5)
C6	0.0115 (6)	0.0164 (6)	0.0153 (6)	0.0024 (5)	0.0028 (5)	0.0006 (5)
C6A	0.0103 (6)	0.0147 (6)	0.0175 (6)	0.0011 (4)	0.0016 (5)	0.0027 (5)
C7	0.0117 (6)	0.0178 (6)	0.0224 (7)	0.0011 (5)	0.0023 (5)	0.0043 (5)
C8	0.0204 (7)	0.0155 (6)	0.0310 (8)	−0.0027 (5)	−0.0031 (6)	0.0049 (6)
C9A	0.0143 (6)	0.0164 (6)	0.0158 (6)	0.0037 (5)	0.0005 (5)	0.0003 (5)
C9	0.0245 (7)	0.0132 (6)	0.0251 (7)	0.0030 (5)	−0.0033 (6)	0.0009 (5)
C12	0.0146 (6)	0.0126 (6)	0.0134 (6)	0.0008 (4)	0.0007 (5)	0.0022 (4)
C13	0.0203 (7)	0.0295 (7)	0.0103 (6)	0.0035 (6)	0.0025 (5)	−0.0019 (5)
C14	0.0276 (8)	0.0308 (8)	0.0194 (7)	0.0090 (6)	0.0048 (6)	−0.0007 (6)
C15	0.0180 (6)	0.0166 (6)	0.0132 (6)	0.0035 (5)	0.0008 (5)	0.0006 (5)
C16	0.0267 (7)	0.0154 (6)	0.0226 (7)	0.0093 (5)	0.0013 (6)	−0.0026 (5)
C17	0.0280 (9)	0.0320 (9)	0.0512 (12)	0.0115 (7)	0.0102 (8)	−0.0112 (8)

Geometric parameters (Å, º) top

O2—C3	1.4274 (16)	C5—C15	1.5130 (18)
O2—C1	1.4347 (17)	C5—C6	1.5580 (18)
O10—C3A	1.4410 (15)	C5—H5A	1.0000
O10—C6	1.4420 (15)	C6—C6A	1.5370 (18)
O11—C7	1.4414 (16)	C6—H6A	1.0000
O11—C9A	1.4420 (16)	C6A—C7	1.5609 (18)
O12—C12	1.2035 (16)	C6A—H6AA	1.0000
O13—C12	1.3323 (16)	C7—C8	1.522 (2)
O13—C13	1.4630 (16)	C7—H7A	1.0000
O15—C15	1.2058 (17)	C8—C9	1.332 (2)
O16—C15	1.3384 (16)	C8—H8A	0.9500
O16—C16	1.4581 (16)	C9A—C9	1.5241 (19)
C1—C9A	1.5094 (18)	C9—H9A	0.9500
C1—H1A	0.9900	C13—C14	1.498 (2)
C1—H1B	0.9900	C13—H13A	0.9900
C3B—C3A	1.5341 (18)	C13—H13B	0.9900
C3B—C6A	1.5515 (17)	C14—H14A	0.9800
C3B—C9A	1.5561 (18)	C14—H14B	0.9800
C3B—H3BA	1.0000	C14—H14C	0.9800
C3A—C3	1.5127 (17)	C16—C17	1.499 (2)
C3A—C4	1.5565 (18)	C16—H16A	0.9900
C3—H3A	0.9900	C16—H16B	0.9900
C3—H3B	0.9900	C17—H17A	0.9800
C4—C12	1.5120 (18)	C17—H17B	0.9800
C4—C5	1.5478 (18)	C17—H17C	0.9800
C4—H4A	1.0000

C3—O2—C1	113.82 (10)	C3B—C6A—H6AA	112.8
C3A—O10—C6	97.15 (9)	C7—C6A—H6AA	112.8
C7—O11—C9A	96.51 (10)	O11—C7—C8	101.02 (10)
C12—O13—C13	118.82 (11)	O11—C7—C6A	102.12 (10)
C15—O16—C16	116.54 (11)	C8—C7—C6A	105.52 (11)
O2—C1—C9A	111.20 (10)	O11—C7—H7A	115.4
O2—C1—H1A	109.4	C8—C7—H7A	115.4
C9A—C1—H1A	109.4	C6A—C7—H7A	115.4
O2—C1—H1B	109.4	C9—C8—C7	105.96 (12)
C9A—C1—H1B	109.4	C9—C8—H8A	127.0
H1A—C1—H1B	108.0	C7—C8—H8A	127.0
C3A—C3B—C6A	102.82 (10)	O11—C9A—C1	111.53 (11)
C3A—C3B—C9A	111.90 (10)	O11—C9A—C9	101.20 (11)
C6A—C3B—C9A	101.66 (10)	C1—C9A—C9	122.17 (11)
C3A—C3B—H3BA	113.2	O11—C9A—C3B	102.22 (10)
C6A—C3B—H3BA	113.1	C1—C9A—C3B	112.73 (11)
C9A—C3B—H3BA	113.1	C9—C9A—C3B	104.67 (11)
O10—C3A—C3	112.03 (10)	C8—C9—C9A	105.25 (12)
O10—C3A—C3B	103.56 (10)	C8—C9—H9A	127.4
C3—C3A—C3B	112.36 (10)	C9A—C9—H9A	127.4
O10—C3A—C4	99.83 (9)	O12—C12—O13	125.17 (12)
C3—C3A—C4	117.78 (11)	O12—C12—C4	125.66 (12)
C3B—C3A—C4	109.72 (10)	O13—C12—C4	109.17 (11)
O2—C3—C3A	112.21 (11)	O13—C13—C14	107.45 (12)
O2—C3—H3A	109.2	O13—C13—H13A	110.2
C3A—C3—H3A	109.2	C14—C13—H13A	110.2
O2—C3—H3B	109.2	O13—C13—H13B	110.2
C3A—C3—H3B	109.2	C14—C13—H13B	110.2
H3A—C3—H3B	107.9	H13A—C13—H13B	108.5
C12—C4—C5	114.86 (11)	C13—C14—H14A	109.5
C12—C4—C3A	114.96 (10)	C13—C14—H14B	109.5
C5—C4—C3A	100.93 (10)	H14A—C14—H14B	109.5
C12—C4—H4A	108.6	C13—C14—H14C	109.5
C5—C4—H4A	108.6	H14A—C14—H14C	109.5
C3A—C4—H4A	108.6	H14B—C14—H14C	109.5
C15—C5—C4	112.43 (11)	O15—C15—O16	124.01 (12)
C15—C5—C6	112.40 (11)	O15—C15—C5	125.88 (12)
C4—C5—C6	101.66 (10)	O16—C15—C5	110.11 (11)
C15—C5—H5A	110.0	O16—C16—C17	106.76 (12)
C4—C5—H5A	110.0	O16—C16—H16A	110.4
C6—C5—H5A	110.0	C17—C16—H16A	110.4
O10—C6—C6A	104.25 (10)	O16—C16—H16B	110.4
O10—C6—C5	101.29 (10)	C17—C16—H16B	110.4
C6A—C6—C5	108.24 (11)	H16A—C16—H16B	108.6
O10—C6—H6A	114.0	C16—C17—H17A	109.5
C6A—C6—H6A	114.0	C16—C17—H17B	109.5
C5—C6—H6A	114.0	H17A—C17—H17B	109.5
C6—C6A—C3B	100.08 (10)	C16—C17—H17C	109.5
C6—C6A—C7	116.41 (11)	H17A—C17—H17C	109.5
C3B—C6A—C7	100.52 (10)	H17B—C17—H17C	109.5
C6—C6A—H6AA	112.8

C3—O2—C1—C9A	−59.58 (14)	C9A—O11—C7—C8	50.63 (11)
C6—O10—C3A—C3	−173.99 (10)	C9A—O11—C7—C6A	−58.08 (11)
C6—O10—C3A—C3B	−52.67 (11)	C6—C6A—C7—O11	−70.74 (13)
C6—O10—C3A—C4	60.53 (10)	C3B—C6A—C7—O11	36.17 (12)
C6A—C3B—C3A—O10	31.09 (12)	C6—C6A—C7—C8	−175.97 (11)
C9A—C3B—C3A—O10	−77.27 (12)	C3B—C6A—C7—C8	−69.05 (12)
C6A—C3B—C3A—C3	152.18 (11)	O11—C7—C8—C9	−32.10 (14)
C9A—C3B—C3A—C3	43.82 (14)	C6A—C7—C8—C9	73.94 (14)
C6A—C3B—C3A—C4	−74.76 (12)	C7—O11—C9A—C1	177.58 (10)
C9A—C3B—C3A—C4	176.89 (10)	C7—O11—C9A—C9	−51.00 (11)
C1—O2—C3—C3A	59.76 (14)	C7—O11—C9A—C3B	56.88 (11)
O10—C3A—C3—O2	64.99 (14)	O2—C1—C9A—O11	−63.19 (14)
C3B—C3A—C3—O2	−51.11 (15)	O2—C1—C9A—C9	177.15 (12)
C4—C3A—C3—O2	179.91 (11)	O2—C1—C9A—C3B	51.15 (15)
O10—C3A—C4—C12	−163.65 (10)	C3A—C3B—C9A—O11	75.48 (12)
C3—C3A—C4—C12	74.92 (15)	C6A—C3B—C9A—O11	−33.62 (12)
C3B—C3A—C4—C12	−55.30 (14)	C3A—C3B—C9A—C1	−44.38 (15)
O10—C3A—C4—C5	−39.44 (11)	C6A—C3B—C9A—C1	−153.48 (11)
C3—C3A—C4—C5	−160.87 (11)	C3A—C3B—C9A—C9	−179.32 (11)
C3B—C3A—C4—C5	68.91 (12)	C6A—C3B—C9A—C9	71.58 (12)
C12—C4—C5—C15	−110.49 (13)	C7—C8—C9—C9A	−0.35 (15)
C3A—C4—C5—C15	125.24 (11)	O11—C9A—C9—C8	32.70 (14)
C12—C4—C5—C6	129.10 (11)	C1—C9A—C9—C8	157.22 (13)
C3A—C4—C5—C6	4.83 (12)	C3B—C9A—C9—C8	−73.26 (14)
C3A—O10—C6—C6A	54.98 (11)	C13—O13—C12—O12	3.4 (2)
C3A—O10—C6—C5	−57.36 (10)	C13—O13—C12—C4	−177.31 (11)
C15—C5—C6—O10	−89.24 (12)	C5—C4—C12—O12	−9.39 (19)
C4—C5—C6—O10	31.18 (12)	C3A—C4—C12—O12	107.12 (15)
C15—C5—C6—C6A	161.48 (10)	C5—C4—C12—O13	171.36 (10)
C4—C5—C6—C6A	−78.09 (12)	C3A—C4—C12—O13	−72.14 (13)
O10—C6—C6A—C3B	−34.93 (12)	C12—O13—C13—C14	−143.18 (13)
C5—C6—C6A—C3B	72.31 (12)	C16—O16—C15—O15	−1.7 (2)
O10—C6—C6A—C7	72.24 (13)	C16—O16—C15—C5	178.70 (11)
C5—C6—C6A—C7	179.48 (10)	C4—C5—C15—O15	6.3 (2)
C3A—C3B—C6A—C6	2.12 (12)	C6—C5—C15—O15	120.28 (15)
C9A—C3B—C6A—C6	118.07 (10)	C4—C5—C15—O16	−174.16 (11)
C3A—C3B—C6A—C7	−117.38 (11)	C6—C5—C15—O16	−60.17 (14)
C9A—C3B—C6A—C7	−1.44 (12)	C15—O16—C16—C17	177.50 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O13	0.99	2.58	3.1604 (17)	118
C9—H9A···O13ⁱ	0.95	2.47	3.1692 (17)	131
C13—H13A···O2ⁱⁱ	0.99	2.58	3.1905 (17)	120
C13—H13B···O10ⁱⁱ	0.99	2.41	3.2193 (17)	139
C14—H14C···O15ⁱ	0.98	2.64	3.5669 (19)	158

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

Summary of short interatomic contacts (Å) in the title compound top

Contact	Distance	Symmetry operation
H3A···H6AA	2.49	1 + x, y, z
O10···H13B	2.41	x, 1/2 - y, 1/2 + z
H16B···H16B	2.57	-x, 1 - y, 1 - z
H1A···O11	2.73	1 - x, -y, 1 - z
H17A···H13B	2.29	-x, 1/2 + y, 1/2 - z
O13···H9A	2.47	1 - x, 1/2 + y, 1/2 - z
H7A···C8	3.02	-x, -y, 1 - z
H6A···H14A	2.50	-1 + x, 1/2 - y, 1/2 + z

Acknowledgements

NDS and NAG thank Baku State University and Azerbaijan State Oil and Industry University, respectively, for financial support. The author's contributions are as follows. Conceptualization, MA and AB; synthesis, AGP, NAG and EVN; X-ray analysis, NDS and ZA; writing (review and editing of the manuscript) MA and AB; funding acquisition, NDS, NAG, AGP and EVN; supervision, MA and AB.

Funding information

Funding for this research was provided by: the Russian Science Foundation (contract No. 23–23-00577).

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