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Acta Crystallographica Section E: Crystallographic Communications logoLink to Acta Crystallographica Section E: Crystallographic Communications
. 2023 Jun 2;79(Pt 7):605–609. doi: 10.1107/S2056989023004772

Synthesis, crystal structure, Hirshfeld surface analysis and DFT study of the 1,1′-(buta-1,3-diyne-1,4-di­yl)bis­(cyclo­hexan-1-ol)

Sarvinoz I Tirkasheva a, Odiljon E Ziyadullaev a, Alisher G Eshimbetov b, Bakhtiyar T Ibragimov b, Jamshid M Ashurov b,*
Editor: A S Batsanovc
PMCID: PMC10439439  PMID: 37601586

The two crystallographically non-equivalent mol­ecules in the title compound have C 2 and Ci symmetries. The crystal structure features strong inter­mol­ecular O—H⋯O hydrogen bonds, which form eight-membered rings with Inline graphic (8) graph-set motifs, linking the mol­ecules into layers.

Keywords: synthesis; 1,1′-(buta-1,3-diyne-1,4-di­yl)bis­(cyclo­hexan-1-ol); crystal structure; hydrogen bond; Hirshfeld surface analysis; DFT study.

Abstract

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 space group 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 R 4 4(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.

1. Chemical context

The presence of two triple C≡C bonds and two hy­droxy groups in the mol­ecules of di­acetyl­ene diols R 1 R 2(OH)C—C≡C—C≡C—C(OH)R 3 R 4, 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 alkynes easily undergo nucleophilic addition reactions to the carbonyl group and terminal (Hosseini et al., 2020 ▸; Sum et al., 2013 ▸) or inter­nal acetyl­ene alcohols (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 cyclization (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 crystal structure, as well Hirshfeld surface analysis of the guest-free crystal of the title compound, (I). 1.

Figure 1.

Figure 1

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Synthesis of 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 inclusion compound (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 space group 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 unit cell. 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).

Figure 2.

Figure 2

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The mol­ecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level, hydrogen bonds are shown as dotted lines. Symmetrically independent atoms are labelled, the rest are generated by the symmetry operations 1 − x, 1 − y, 1 − z (for A) and −x, y, Inline graphic  − z (for B).

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 Inline graphic (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 ▸).

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O1B—H1B⋯O1A i 0.82 1.96 2.7709 (15) 168
O1A—H1A⋯O1B 0.82 1.94 2.7481 (15) 168
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Symmetry code: (i) Inline graphic .

Figure 3.

Figure 3

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Packing diagram of (I). Dotted lines indicate hydrogen bonds. Symmetry operation for primed atoms: 1 − x, y, Inline graphic  − z.

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 d norm 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 d e vs d i 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%).

Figure 4.

Figure 4

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Three-dimensional Hirshfeld surfaces of mol­ecules A and B of (I) plotted over d norm in the range −0.5154 to 1.9215 a.u.

Figure 5.

Figure 5

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Hirshfeld surfaces of mol­ecules A and B plotted over electrostatic potential in the range −0.05 to 0.05 a.u. using the B3LYP/6–311 G(d,p) basis set at the Hartree–Fock level of theory. Blue and red regions indicate positive and negative potentials, respectively.

Figure 6.

Figure 6

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Complete two-dimensional fingerprint plots for mol­ecules A (a) and B (b) of (I) with relative contributions of individual contacts. Note the ‘spikes’ indicating strong hydrogen bonds.

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 rotational barrier of a cyclo­hexan-1-ol fragment around the diyne rod (i.e. the Csp 3—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 crystal structure (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 ionization potential and representing the electron-donating ability of a mol­ecule, while the LUMO correlates with the electron affinity 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 alcohols, thiols and amines 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 electrophile reagents because of the low-lying HOMO.

Figure 7.

Figure 7

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Potential energy curve for mol­ecule (I) as a function of the dihedral angle ω.

Figure 8.

Figure 8

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The HOMO–LUMO energy gap of mol­ecule (I) as a function of ω.

Figure 9.

Figure 9

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(a) Optimized conformation (ω = 61°) of (I) and (b) electron densities on its frontier MOs by the DFT/def2-TZVP method.

Thus, theoretical calculations showed that the rotation of hexa­nol-1 fragment around the Csp 3—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 rotational barrier 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 co-crystal 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, N 1,N 1,N 2,N 2-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 diffraction analysis 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 refinement details are summarized in Table 2 ▸. All H atoms were positioned geometrically, C—H 0.97 Å (methyl­ene), O—H 0.82 Å (hydroxyl group) and refined as riding with U iso(H) = 1.2U eq(C) or 1.5U eq(O).

Table 2. Experimental details.

Crystal data
Chemical formula C16H22O2
M r 246.33
Crystal system, space group Monoclinic, P2/c
Temperature (K) 293
a, b, c (Å) 10.4134 (2), 6.9167 (2), 20.4801 (5)
β (°) 90.308 (2)
V (Å3) 1475.09 (6)
Z 4
Radiation type Cu Kα
μ (mm−1) 0.56
Crystal size (mm) 0.30 × 0.24 × 0.15
 
Data collection
Diffractometer XtaLAB Synergy, Single source at home/near, HyPix3000
Absorption correction Multi-scan (CrysAlis PRO; Rigaku OD, 2020 ▸)
T min, T max 0.960, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 13939, 2866, 2161
R int 0.038
(sin θ/λ)max (Å−1) 0.615
 
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S 0.044, 0.129, 1.07
No. of reflections 2866
No. of parameters 166
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.12, −0.16
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Computer programs: CrysAlis PRO (Rigaku OD, 2020 ▸), SHELXT2018/2 (Sheldrick, 2015a ▸), SHELXL2019/2 (Sheldrick, 2015b ▸), Mercury (Macrae et al., 2020 ▸) and publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023004772/zv2024sup1.cif

e-79-00605-sup1.cif (442.2KB, cif)

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989023004772/zv2024Isup2.hkl

e-79-00605-Isup2.hkl (229.2KB, hkl)
Click here for additional data file. (5.5KB, cml)

Supporting information file. DOI: 10.1107/S2056989023004772/zv2024Isup3.cml

CCDC reference: 2189423

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Crystal data

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
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Data collection

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
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Refinement

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)
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Special details

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

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*
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Atomic displacement parameters (Å2)

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)
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Geometric parameters (Å, º)

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

Hydrogen-bond geometry (Å, º)

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
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Symmetry code: (iii) −x+1, y, −z+3/2.

References

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023004772/zv2024sup1.cif

e-79-00605-sup1.cif (442.2KB, cif)

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989023004772/zv2024Isup2.hkl

e-79-00605-Isup2.hkl (229.2KB, hkl)
Click here for additional data file. (5.5KB, cml)

Supporting information file. DOI: 10.1107/S2056989023004772/zv2024Isup3.cml

CCDC reference: 2189423

Additional supporting information: crystallographic information; 3D view; checkCIF report

Articles from Acta Crystallographica Section E: Crystallographic Communications are provided here courtesy of International Union of Crystallography

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