research communications
Synthesis,
Hirshfeld surface analysis and DFT study of the 1,1′-(buta-1,3-diyne-1,4-diyl)bis(cyclohexan-1-ol)aChirchik State Pedagogical University, 111700, A. Temur Str. 104, Chirchik, Uzbekistan, and bInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, 100125, M. Ulugbek Str 83, Tashkent, Uzbekistan
*Correspondence e-mail: atom.uz@mail.ru
The title compound, C16H22O2, was synthesized in order to obtain its guest-free form because `wheel-and-axle'-shaped molecules tend to crystallize from solutions as solvates or host–guest molecules. It crystallizes in the monoclinic P2/c with two crystallographically non-equivalent molecules, one situated on an inversion center and the other on a twofold axis. The rod-like 1,3-diyne fragments have the usual linear geometry. In the crystal, O—H ⋯ O bonds form eight-membered rings of the R44(8) type, linking molecules into layers. The Hirshfeld surface analysis indicates that the largest contributions are from intermolecular H⋯H (ca 71%) and H⋯C/C⋯H (ca 19%) contacts. The energies of the frontier molecular orbitals were determined by DFT calculations at the B3LYP/def2-TZVP level of theory.
Keywords: synthesis; 1,1′-(buta-1,3-diyne-1,4-diyl)bis(cyclohexan-1-ol); crystal structure; hydrogen bond; Hirshfeld surface analysis; DFT study..
CCDC reference: 2189423
1. Chemical context
The presence of two triple C≡C bonds and two hydroxy groups in the molecules of diacetylene diols R1R2(OH)C—C≡C—C≡C—C(OH)R3R4, as well as substituents with different structures and functional groups containing heteroatoms, increases the possibilities of synthesis and the production of valuable, chemically stable and biologically active compounds based on such compounds (Cadierno, 2022). In particular, as the hydrogen atom adjacent to the strong C≡C bond is labile (Brücner, 2010), terminal easily undergo nucleophilic addition reactions to the carbonyl group and terminal (Hosseini et al., 2020; Sum et al., 2013) or internal acetylene (Tanaka et al., 2011; Motoki et al., 2007) and diols (Ardila-Fierro et al., 2019) with various substituents. Diacetylene diols and polyacetylene diols (Shi Shun et al., 2006) can also be synthesized by performing dimerization processes. Many reactions, such as (Zhang et al., 2010) or substitution (Kuang et al., 2018), based on the hydroxy group (–OH) or its hydrogen atom in an acetylene alcohol, give opportunities to synthesize new biologically active substances. Hexa-2,4-diene-1,6-diol and its derivatives have been found to have anticancer chemotherapeutic properties (Lee et al., 2015). Moreover, some diacetylene diols and their derivatives have antibacterial (Ankisetty et al., 2012), antiviral (Geng et al., 2015) and neuritogenic (Wang et al., 2011) activities.
Moreover, the above indicated substances behave as versatile host compounds accommodating many guest species (Weber et al., 1991) because the shape of their molecules is inefficient for close packing in crystals. Therefore, the preparation of such compounds in their pure form, i.e. a guest-free state, is of interest. This paper describes the preparation (Fig. 1), molecular and as well Hirshfeld surface analysis of the guest-free crystal of the title compound, (I).
2. Structural commentary
There are the principles of directed host design formulated by Weber (Weber et al., 1991), according to which bulky and rigid compounds are packed in crystals inefficiently, leaving suitable cavities for the accommodation of guest molecules. Indeed, host compounds with a `wheel-and-axle' shape of the molecule easily include several guests (Weber et al., 2004). However, in the case of compound (I) belonging to this family, only one (with 1,4-diazabicyclo-[2.2.2]octane as the guest) has been structurally characterized (Chandrasekhar et al., 2013). In our experimental conditions we have obtained guest-free crystals of (I). They belong to the monoclinic system with P2/c. There are two crystallographically non-equivalent molecules, both situated on symmetry elements: molecule A is located on an inversion center while molecule B lies on a twofold axis. Thus there are two half-molecules in the asymmetric part of the The rod-like 1,3-diyne fragment has the usual linear geometry and bond lengths (Weber et al., 1991, 2004; Chandrasekhar et al., 2013). The molecular structure of (I) is shown in Fig. 2. The cyclohexane moieties of both independent molecules adopt chair conformations, with atoms C1 and C4 deviating from the plane of the remaining four atoms by 0.655 and −0.657 Å, respectively, in molecule A, by 0.668 and −0.638 Å in B. The disposition of the cyclohexane rings relative to the 1,3-diyne chain is the same in molecules A and B, as shown by the similar distances C7A⋯Cg1 = 2.331 Å and C7B⋯Cg2 = 2.329 Å where Cg1 and Cg2 are the ring centroids. However, the orientation of the rings relative to each other is different (Fig. 2, inserts): trans in molecule A, gauche in B, both different from the nearly eclipsed disposition in the one known molecular complex of (I).
3. Supramolecular features
The molecule of (I) has two OH groups. Each group realises its proton-donor and proton-acceptor possibilities, forming intermolecular hydrogen bonds (Table 1) O1A—H1A⋯O1B and O1B—H1B⋯O1A with O⋯O distances of 2.748 (1) and 2.771 (1) Å, respectively. As shown in Fig. 3, each molecule participates in two (8) rings of hydrogen bonds (Grell et al., 1999), each ring involving two molecules of type A and two of B. These bonds give rise to a two-dimensional supramolecular layer parallel to the ac plane. The layers are incorporated into a three-dimensional network by van der Waals interactions (Fig. 3).
4. Hirshfeld surface analysis
Hirshfeld surfaces were calculated and two-dimensional fingerprints generated using CrystalExplorer21 (Spackman et al., 2021). Hirshfeld surfaces were obtained using a standard (high) surface resolution with the three-dimensional dnorm surfaces mapped over a fixed color scale of −0.5154 (red) to 1.9215 (blue) (Fig. 4). The only red spots on the surface (revealing strong interactions) correspond to the O—H⋯O hydrogen bonds, the rest representing standard (white) or longer than standard (blue) van der Waals contacts. This agrees with the calculated electrostatic potential of the molecule (Fig. 5) where the only negative potential (acceptor) areas are around the O atoms. The two-dimensional fingerprint plots (in de vs di coordinates) (Fig. 6) show that molecules A and B have very similar environments, the major contributions being from contacts H⋯H (70.6 for A, 71.1% for B), H⋯C/C⋯H (18.4 and 18.7%) and H⋯O/O⋯H (11.0 and 10.2%).
5. The analysis of DFT calculations
The co-presence of trans and gauche conformations of (I) in the crystal was mentioned above. In order to determine the intramolecular of a cyclohexan-1-ol fragment around the diyne rod (i.e. the Csp3—Csp bond), the relaxed scan calculation has been carried out in a vacuum by B3LYP/def2-TZVP method using the ORCA program package (Neese, 2022). The initial geometry of (I) was taken from the (CIF file) and the input files were prepared using Avogadro program package (Hanwell et al., 2012). The O1—C1⋯C1′—O1′ torsion angle (ω) was varied from 0 to 180° in 3° steps with full optimization of the molecular geometry at each step. Then single-point calculations were performed using the B3LYP-D3BJ/def2-TZVP basis set for the geometries obtained at each step, by including dispersion corrections (Grimme et al., 2011). Thus we observed energy minima at ω = 9, 30, 61, 85, 109, 146 and 180° (Fig. 7), the deepest one being at 61° by DFT/def2-TZVP calculations (or 64° by DFT-D3BJ/def2-TZVP); however, the rotation barrier was low, 0.7 or 0.9 kJ mol−11, respectively. Thus, an easy transition between conformations can occur in solution and, apparently, the intermolecular (packing) interactions played a decisive role in the implementation of the gauche (ω = 85°) and trans (ω = 180°) conformations in the crystal. To study the influence of ω variation on the electronic parameters, we analyzed the changes of HOMO and LUMO energies, and the energy gap upon varying ω from 0 to 180°. The energy and electron density at these orbitals are important in defining the molecule's chemistry (Fukui, 1982; Hoffmann et al., 1965), the HOMO correlating with the and representing the electron-donating ability of a molecule, while the LUMO correlates with the of a molecule and represents its electron-accepting ability. The energy difference (energy gap) between HOMO and LUMO is known to represent the stability or reactivity of a molecule in a series of related compounds (Pearson, 1988; Jahnke et al., 2010). For (I), the HOMO and LUMO energies and the energy gap change slightly with ω, the former varying from −6.63 to −6.72 eV and the latter from −0.69 to −0.84 eV, while the energy gap varies from 5.79 to 5.99 eV (Fig. 8). The widest energy gap (5.99 eV) was found at energetically optimal conformation with ω = 61 or 64° (vide supra). Molecule (I) has a low-lying HOMO and a high-lying LUMO and consequently a wide HOMO–LUMO gap, which indicates the high thermodynamic stability and low reactivity of the molecule. Despite this, the highly unsaturated carbon chains could also exhibit various reaction properties (photoisomerization, nucleophilic addition of and to the triple bond) under special conditions (Shi et al., 2014). The reactivity of (I) toward nucleophiles can be inferred from the electron density on LUMO, which is predominantly the π* orbital of diacetylene C atoms (Fig. 9). The HOMO is a π-type MO and is mainly delocalized along the diacetylene fragment (Fig. 9). However, these atoms are unlikely to have an electron-donating ability to reagents because of the low-lying HOMO.
Thus, theoretical calculations showed that the rotation of hexanol-1 fragment around the Csp3—Csp bond can pass through several conformational minima that differ in ω. However, all these conformations make a negligible difference to the total energies and the between them. The conformations observed in the crystal packing arose as a result of the action of intermolecular interaction forces.
6. Database survey
A survey of the Cambridge Structural Database (CONQUEST version 2021 3.0; Groom et al., 2016) revealed 198 structures in which an OH group and any other substituents are attached to each end of a hexa-2,4-diyne rod. However, the only compound involving compound (I) is its complex with 1,4-diazabicyclo [2.2.2]octane (MIRJEE; Chandrasekhar et al., 2013). The existence of this could be expected from the propensity of `wheel-and-axle'-shaped molecules to form host–guest structures.
7. Synthesis and crystallization
The dimerization process of 1-ethynylcyclohexanol was conducted at 298 K for 48 h, based on a catalytic system with a copper(I) chloride catalyst, tetrachloromethane, N1,N1,N2,N2-tetramethylethylenediamine as a ligand and ethanol as the solvent, following the general routine used by Tirkasheva et al. (2022) to prepare 8,13-dimethylcosa-9,11-diyne-8,13-diol. This yielded 1,1′-(buta-1,3-diyne-1,4-diyl)bis(cyclohexan-1-ol) (I) as a brown liquid. 25 mg (0.1 mmol) of (I) were dissolved in 2 ml of chloroform in a 50 ml round-bottom flask and the solvent was removed under vacuum. After the chloroform was completely removed, 2 ml of CH2Cl2 and 1 ml of methanol were added to the flask. Brown single crystals of the title compound suitable for X-ray were grown over three days by slow evaporation of the solvent, yield 76%, m.p. 448 K. Elemental analysis for C16H22O2 (246.33): calculated C 78.01; H 9.00%; found C 77.95; H 8.94%. FTIR (ATR), cm−1: 3326 (OH).
8. Refinement
Crystal data, data collection and structure . All H atoms were positioned geometrically, C—H 0.97 Å (methylene), O—H 0.82 Å (hydroxyl group) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O).
details are summarized in Table 2Supporting information
CCDC reference: 2189423
https://doi.org/10.1107/S2056989023004772/zv2024sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023004772/zv2024Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989023004772/zv2024Isup3.cml
Data collection: CrysAlis PRO 1.171.40.84a (Rigaku OD, 2020); cell
CrysAlis PRO 1.171.40.84a (Rigaku OD, 2020); data reduction: CrysAlis PRO 1.171.40.84a (Rigaku OD, 2020); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019/2 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).C16H22O2 | F(000) = 536 |
Mr = 246.33 | Dx = 1.109 Mg m−3 |
Monoclinic, P2/c | Cu Kα radiation, λ = 1.54184 Å |
a = 10.4134 (2) Å | Cell parameters from 4018 reflections |
b = 6.9167 (2) Å | θ = 4.2–70.2° |
c = 20.4801 (5) Å | µ = 0.56 mm−1 |
β = 90.308 (2)° | T = 293 K |
V = 1475.09 (6) Å3 | Block, colorless |
Z = 4 | 0.30 × 0.24 × 0.15 mm |
XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer | 2866 independent reflections |
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source | 2161 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.038 |
Detector resolution: 10.0000 pixels mm-1 | θmax = 71.5°, θmin = 4.3° |
ω scans | h = −12→12 |
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020) | k = −8→8 |
Tmin = 0.960, Tmax = 1.000 | l = −25→25 |
13939 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.044 | w = 1/[σ2(Fo2) + (0.0565P)2 + 0.2398P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.129 | (Δ/σ)max = 0.001 |
S = 1.07 | Δρmax = 0.12 e Å−3 |
2866 reflections | Δρmin = −0.16 e Å−3 |
166 parameters | Extinction correction: SHELXL2019/2 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0018 (4) |
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. |
x | y | z | Uiso*/Ueq | ||
O1A | 0.61299 (10) | 0.28504 (18) | 0.67530 (5) | 0.0500 (3) | |
H1A | 0.534651 | 0.297081 | 0.675485 | 0.075* | |
O1B | 0.35098 (10) | 0.28922 (18) | 0.69056 (5) | 0.0514 (3) | |
H1B | 0.352776 | 0.275754 | 0.730331 | 0.077* | |
C8B | 0.05502 (14) | 0.1260 (2) | 0.73133 (7) | 0.0436 (4) | |
C7B | 0.15086 (14) | 0.1312 (2) | 0.69953 (7) | 0.0428 (4) | |
C7A | 0.59587 (14) | 0.4643 (3) | 0.57736 (7) | 0.0438 (4) | |
C1A | 0.66899 (13) | 0.4401 (2) | 0.63846 (7) | 0.0396 (4) | |
C1B | 0.27132 (13) | 0.1416 (2) | 0.66200 (7) | 0.0393 (4) | |
C8A | 0.53529 (14) | 0.4875 (2) | 0.52842 (7) | 0.0454 (4) | |
C6B | 0.24442 (16) | 0.2025 (3) | 0.59194 (7) | 0.0515 (4) | |
H6BA | 0.325069 | 0.226105 | 0.569837 | 0.062* | |
H6BB | 0.195840 | 0.322206 | 0.591871 | 0.062* | |
C2A | 0.80687 (15) | 0.3812 (3) | 0.62439 (9) | 0.0572 (5) | |
H2AA | 0.806869 | 0.268548 | 0.596191 | 0.069* | |
H2AB | 0.849339 | 0.346281 | 0.664971 | 0.069* | |
C6A | 0.66516 (19) | 0.6273 (3) | 0.67772 (8) | 0.0578 (5) | |
H6AA | 0.576503 | 0.666216 | 0.683656 | 0.069* | |
H6AB | 0.702445 | 0.604832 | 0.720557 | 0.069* | |
C2B | 0.33965 (16) | −0.0527 (3) | 0.66322 (10) | 0.0581 (5) | |
H2BA | 0.423514 | −0.038974 | 0.643367 | 0.070* | |
H2BB | 0.352351 | −0.092677 | 0.708192 | 0.070* | |
C5B | 0.1692 (2) | 0.0480 (4) | 0.55515 (9) | 0.0738 (6) | |
H5BA | 0.084237 | 0.036283 | 0.573930 | 0.089* | |
H5BB | 0.159152 | 0.086946 | 0.509906 | 0.089* | |
C3B | 0.2648 (2) | −0.2066 (3) | 0.62734 (12) | 0.0791 (7) | |
H3BA | 0.184876 | −0.230967 | 0.650026 | 0.095* | |
H3BB | 0.313885 | −0.325736 | 0.627015 | 0.095* | |
C3A | 0.88123 (18) | 0.5442 (4) | 0.59165 (11) | 0.0813 (7) | |
H3AA | 0.845971 | 0.567268 | 0.548409 | 0.098* | |
H3AB | 0.970324 | 0.506143 | 0.586823 | 0.098* | |
C5A | 0.7378 (2) | 0.7890 (3) | 0.64418 (11) | 0.0819 (7) | |
H5AA | 0.695858 | 0.820426 | 0.603132 | 0.098* | |
H5AB | 0.736769 | 0.903581 | 0.671491 | 0.098* | |
C4A | 0.8742 (3) | 0.7302 (4) | 0.63159 (13) | 0.0994 (9) | |
H4AA | 0.918322 | 0.711258 | 0.672939 | 0.119* | |
H4AB | 0.917728 | 0.833008 | 0.608294 | 0.119* | |
C4B | 0.2359 (3) | −0.1460 (4) | 0.55798 (13) | 0.0955 (9) | |
H4BA | 0.181703 | −0.242772 | 0.537411 | 0.115* | |
H4BB | 0.315449 | −0.139078 | 0.533687 | 0.115* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0444 (6) | 0.0596 (7) | 0.0460 (6) | −0.0077 (5) | −0.0005 (5) | 0.0128 (5) |
O1B | 0.0458 (6) | 0.0646 (8) | 0.0439 (6) | −0.0126 (5) | 0.0007 (5) | −0.0067 (6) |
C8B | 0.0370 (7) | 0.0557 (10) | 0.0381 (8) | −0.0001 (7) | 0.0016 (6) | −0.0007 (7) |
C7B | 0.0391 (8) | 0.0511 (9) | 0.0382 (8) | −0.0013 (7) | 0.0020 (6) | −0.0006 (7) |
C7A | 0.0400 (8) | 0.0532 (10) | 0.0381 (8) | −0.0031 (7) | −0.0021 (6) | 0.0029 (7) |
C1A | 0.0371 (7) | 0.0488 (9) | 0.0327 (7) | −0.0037 (6) | −0.0029 (6) | 0.0055 (6) |
C1B | 0.0336 (7) | 0.0472 (9) | 0.0372 (8) | −0.0037 (6) | 0.0038 (6) | −0.0016 (6) |
C8A | 0.0410 (8) | 0.0567 (10) | 0.0382 (8) | −0.0043 (7) | −0.0039 (6) | 0.0053 (7) |
C6B | 0.0540 (9) | 0.0611 (11) | 0.0394 (8) | −0.0133 (8) | 0.0027 (7) | 0.0063 (8) |
C2A | 0.0415 (8) | 0.0768 (13) | 0.0533 (10) | 0.0059 (8) | 0.0012 (7) | 0.0159 (9) |
C6A | 0.0735 (12) | 0.0561 (11) | 0.0438 (9) | −0.0029 (9) | −0.0048 (8) | −0.0029 (8) |
C2B | 0.0479 (9) | 0.0556 (11) | 0.0708 (12) | 0.0078 (8) | 0.0113 (8) | 0.0058 (9) |
C5B | 0.0848 (14) | 0.0970 (17) | 0.0396 (9) | −0.0355 (13) | −0.0045 (9) | 0.0000 (10) |
C3B | 0.0827 (14) | 0.0484 (11) | 0.1065 (19) | −0.0005 (10) | 0.0212 (13) | −0.0140 (12) |
C3A | 0.0423 (10) | 0.120 (2) | 0.0817 (14) | −0.0086 (11) | 0.0073 (9) | 0.0352 (15) |
C5A | 0.121 (2) | 0.0562 (13) | 0.0686 (13) | −0.0264 (13) | −0.0130 (13) | −0.0001 (10) |
C4A | 0.0975 (19) | 0.114 (2) | 0.0869 (17) | −0.0640 (17) | −0.0204 (14) | 0.0256 (16) |
C4B | 0.112 (2) | 0.0905 (19) | 0.0837 (17) | −0.0338 (16) | 0.0247 (14) | −0.0436 (15) |
O1A—H1A | 0.8200 | C6A—H6AB | 0.9700 |
O1A—C1A | 1.4365 (18) | C6A—C5A | 1.517 (3) |
O1B—H1B | 0.8200 | C2B—H2BA | 0.9700 |
O1B—C1B | 1.4379 (18) | C2B—H2BB | 0.9700 |
C8B—C8Bi | 1.381 (3) | C2B—C3B | 1.508 (3) |
C8B—C7B | 1.195 (2) | C5B—H5BA | 0.9700 |
C7B—C1B | 1.4764 (19) | C5B—H5BB | 0.9700 |
C7A—C1A | 1.4709 (19) | C5B—C4B | 1.512 (4) |
C7A—C8A | 1.192 (2) | C3B—H3BA | 0.9700 |
C1A—C2A | 1.521 (2) | C3B—H3BB | 0.9700 |
C1A—C6A | 1.525 (2) | C3B—C4B | 1.510 (4) |
C1B—C6B | 1.520 (2) | C3A—H3AA | 0.9700 |
C1B—C2B | 1.521 (2) | C3A—H3AB | 0.9700 |
C8A—C8Aii | 1.384 (3) | C3A—C4A | 1.526 (4) |
C6B—H6BA | 0.9700 | C5A—H5AA | 0.9700 |
C6B—H6BB | 0.9700 | C5A—H5AB | 0.9700 |
C6B—C5B | 1.522 (3) | C5A—C4A | 1.501 (4) |
C2A—H2AA | 0.9700 | C4A—H4AA | 0.9700 |
C2A—H2AB | 0.9700 | C4A—H4AB | 0.9700 |
C2A—C3A | 1.525 (3) | C4B—H4BA | 0.9700 |
C6A—H6AA | 0.9700 | C4B—H4BB | 0.9700 |
C1A—O1A—H1A | 109.5 | C3B—C2B—C1B | 112.03 (15) |
C1B—O1B—H1B | 109.5 | C3B—C2B—H2BA | 109.2 |
C7B—C8B—C8Bi | 178.17 (13) | C3B—C2B—H2BB | 109.2 |
C8B—C7B—C1B | 178.07 (17) | C6B—C5B—H5BA | 109.3 |
C8A—C7A—C1A | 178.52 (18) | C6B—C5B—H5BB | 109.3 |
O1A—C1A—C7A | 108.79 (12) | H5BA—C5B—H5BB | 107.9 |
O1A—C1A—C2A | 106.62 (13) | C4B—C5B—C6B | 111.67 (18) |
O1A—C1A—C6A | 110.19 (12) | C4B—C5B—H5BA | 109.3 |
C7A—C1A—C2A | 110.74 (13) | C4B—C5B—H5BB | 109.3 |
C7A—C1A—C6A | 109.69 (14) | C2B—C3B—H3BA | 109.4 |
C2A—C1A—C6A | 110.76 (14) | C2B—C3B—H3BB | 109.4 |
O1B—C1B—C7B | 108.22 (12) | C2B—C3B—C4B | 111.26 (19) |
O1B—C1B—C6B | 106.85 (12) | H3BA—C3B—H3BB | 108.0 |
O1B—C1B—C2B | 110.61 (13) | C4B—C3B—H3BA | 109.4 |
C7B—C1B—C6B | 110.61 (12) | C4B—C3B—H3BB | 109.4 |
C7B—C1B—C2B | 110.33 (13) | C2A—C3A—H3AA | 109.4 |
C6B—C1B—C2B | 110.15 (14) | C2A—C3A—H3AB | 109.4 |
C7A—C8A—C8Aii | 179.4 (2) | C2A—C3A—C4A | 111.19 (18) |
C1B—C6B—H6BA | 109.4 | H3AA—C3A—H3AB | 108.0 |
C1B—C6B—H6BB | 109.4 | C4A—C3A—H3AA | 109.4 |
C1B—C6B—C5B | 111.36 (15) | C4A—C3A—H3AB | 109.4 |
H6BA—C6B—H6BB | 108.0 | C6A—C5A—H5AA | 109.5 |
C5B—C6B—H6BA | 109.4 | C6A—C5A—H5AB | 109.5 |
C5B—C6B—H6BB | 109.4 | H5AA—C5A—H5AB | 108.1 |
C1A—C2A—H2AA | 109.3 | C4A—C5A—C6A | 110.6 (2) |
C1A—C2A—H2AB | 109.3 | C4A—C5A—H5AA | 109.5 |
C1A—C2A—C3A | 111.56 (16) | C4A—C5A—H5AB | 109.5 |
H2AA—C2A—H2AB | 108.0 | C3A—C4A—H4AA | 109.3 |
C3A—C2A—H2AA | 109.3 | C3A—C4A—H4AB | 109.3 |
C3A—C2A—H2AB | 109.3 | C5A—C4A—C3A | 111.62 (18) |
C1A—C6A—H6AA | 109.2 | C5A—C4A—H4AA | 109.3 |
C1A—C6A—H6AB | 109.2 | C5A—C4A—H4AB | 109.3 |
H6AA—C6A—H6AB | 107.9 | H4AA—C4A—H4AB | 108.0 |
C5A—C6A—C1A | 111.90 (15) | C5B—C4B—H4BA | 109.3 |
C5A—C6A—H6AA | 109.2 | C5B—C4B—H4BB | 109.3 |
C5A—C6A—H6AB | 109.2 | C3B—C4B—C5B | 111.81 (18) |
C1B—C2B—H2BA | 109.2 | C3B—C4B—H4BA | 109.3 |
C1B—C2B—H2BB | 109.2 | C3B—C4B—H4BB | 109.3 |
H2BA—C2B—H2BB | 107.9 | H4BA—C4B—H4BB | 107.9 |
O1A—C1A—C2A—C3A | −173.86 (15) | C1B—C6B—C5B—C4B | −54.8 (2) |
O1A—C1A—C6A—C5A | 173.01 (15) | C1B—C2B—C3B—C4B | 55.6 (2) |
O1B—C1B—C6B—C5B | 175.44 (15) | C6B—C1B—C2B—C3B | −56.09 (19) |
O1B—C1B—C2B—C3B | −173.98 (14) | C6B—C5B—C4B—C3B | 54.0 (2) |
C7B—C1B—C6B—C5B | −67.0 (2) | C2A—C1A—C6A—C5A | 55.3 (2) |
C7B—C1B—C2B—C3B | 66.31 (19) | C2A—C3A—C4A—C5A | −55.5 (3) |
C7A—C1A—C2A—C3A | 67.9 (2) | C6A—C1A—C2A—C3A | −54.0 (2) |
C7A—C1A—C6A—C5A | −67.3 (2) | C6A—C5A—C4A—C3A | 56.3 (3) |
C1A—C2A—C3A—C4A | 54.2 (2) | C2B—C1B—C6B—C5B | 55.26 (19) |
C1A—C6A—C5A—C4A | −56.5 (2) | C2B—C3B—C4B—C5B | −54.2 (3) |
Symmetry codes: (i) −x, y, −z+3/2; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1B—H1B···O1Aiii | 0.82 | 1.96 | 2.7709 (15) | 168 |
O1A—H1A···O1B | 0.82 | 1.94 | 2.7481 (15) | 168 |
Symmetry code: (iii) −x+1, y, −z+3/2. |
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