Synthesis, non-spherical structure refinement and Hirshfeld surface analysis of racemic 2,2′-diisobut­oxy-1,1′-bi­naphthalene

Coulibaly, P.M.-A.; Ziki, E.; Bisseyou, Y.B.M.; Camara, T.E.; Coulibaly, S.; Sissouma, D.

doi:10.1107/S2056989024009101

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ISSN: 2056-9890

Volume 80| Part 10| October 2024| Pages 1044-1048

https://doi.org/10.1107/S2056989024009101

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Synthesis, non-spherical structure refinement and Hirshfeld surface analysis of racemic 2,2′-diisobutoxy-1,1′-binaphthalene

Pénayori Marie-Aimée Coulibaly,^a Eric Ziki,^b ^* Yvon Bibila Mayaya Bisseyou,^b Tchambaga Etienne Camara,^a Souleymane Coulibaly ^a and Drissa Sissouma ^a

^aLaboratoire de Constitution et de Réaction de la Matière, Equipe Synthèse Organique, UFR de Sciences des Structures de la Matière et Technologie, Université, Félix Houphouët Boigny, 22 BP 582 Abidjan 22, Côte d'Ivoire, and ^bLaboratoire des Sciences de la Matière,de l'Environnement et de l'Energie Solaire, Equipe de Recherche de Cristallographie et Physique Moléculaire, Université Félix Houphouët-Boigny, 08 BP 582, Abidjan 22, Côte d'Ivoire
^*Correspondence e-mail: eric.ziki@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 24 July 2024; accepted 17 September 2024; online 24 September 2024)

In the racemic title compound, C₂₈H₃₀O₂, the naphthyl ring systems subtend a dihedral angle of 68.59 (1)° and the molecular conformation is consolidated by a pair of intramolecular C—H⋯π contacts. The crystal packing features a weak C—H⋯π contact and van der Waals forces. A Hirshfeld surface analysis of the crystal structure reveals that the most significant contributions are from H⋯H (73.2%) and C⋯H/H⋯C (21.2%) contacts.

Keywords: 1–1′-binaphthyl derivative; non-spherical refinement; Hirshfeld surface analysis; crystal structure.

CCDC reference: 2384706

1. Chemical context

1-1′-Binaphthyl-based systems play an important role as ligands in the design of optically active materials (Tkachenko & Scheiner, 2019 ). They are also used for molecular recognition and asymmetric catalysis (Pu, 1998 , 2024 ). The non-coplanar conformation of both naphthyl moieties coupled to their restricted rotation around the transannular covalent bond are the basis of their optical activity (chirality). Furthermore, it has been shown that, when substitutions are carried out at the 2,2′-positions of the 1-1′-binaphthyl system, the chiral conformation of the resulting derivative is very stable (Hall & Turner, 1955 ; Dixon et al., 1971 ). Among these, 1-1′-bi-2-naphthol, C₂₀H₁₄O₂, known as BINOL, with local C₂ symmetry, has been used extensively in the production of chiral catalysts, dendrimers, molecular probes, metal–organic frameworks, covalent organic frameworks, etc. In addition, its hydroxyl functions can be functionalized to generate a wide range of 1-1′-binaphthyl derivatives. Many synthesis procedures of racemic BINOL have been developed using oxidizing agents such as Fe³⁺, Cu²⁺, Mn³⁺, Ti²⁺, Co³⁺, Ag²⁺ or Mo⁵⁺ (Waldvogel, 2002 ; Doussot et al., 2000 ; McKillop et al., 1980 ; Budniak et al., 2017 ) and pure enantiomers can be obtained from the their racemates via diastereoisomer derivatives and their resolution can be achieved by the formation of inclusion crystals with chiral host molecules (Hara et al., 2002 ). Another strategy involves the deracemization of racemates with copper complexes of chiral amines (Bringmann et al., 1990 ; Smrcina et al., 1992 ) or by enzymatic hydrolysis of esters (Miyamo et al., 1987 ; Kazlauskas et al., 1989 ). Optically pure enantiomers can also be synthesized directly and several methods have been reported for this purpose (Chow et al., 1996 ; Kawashima & Hirata, 1993 ; Wang et al., 1995 ).

The racemic title compound, C₂₈H₃₀O₂ (I), is a 1-1′-binaphthyl derivative obtained by the functionalization of BINOL at the hydroxyl positions. Herein, we report its synthesis, spectroscopic characterization and molecular geometry, determined from single-crystal X-ray diffraction analysis using a non-standard aspherical refinement, which combines quantum mechanical calculations and data from diffraction experiments into a single integrated tool (Jayatilaka & Dittrich, 2008 ; Capelli et al., 2014 ; Kleemiss et al., 2021 ). A Hirshfeld surface analysis (Spackman & Byrom, 1997 ; McKinnon et al., 1998 ; McKinnon et al., 2004 ) of the title compound was also performed.

2. Structural commentary

Compound (I) crystallizes in space group P2₁/c as a racemate (Fig. 1). The molecular structure comprises two β-naphthyl isobutyl ether moieties linked by a C1—C1′ covalent bond whose length [1.4867 (3) Å] is in good agreement with the values reported for the same type of bond in related compounds (Allen & Bruno, 2010 ). Both ether units adopt extended conformations [C2—O1—C11—C12 = −175.59 (2)°; C2′—O1′—C11′—C12′ = −175.12 (2)°] and the C₁₄H₁₅O β-naphthyl isobutyl ether moieties exhibit very similar structural parameters with an alignment r.m.s.d. value of 0.023 Å (Fig. 2). The aromatic C—C bonds of the naphthyl ring systems have values in the same range as those obtained by Rivera et al. (2017 ). The planes of the naphthyl ring systems C1–C10 and C1′–C10′ (r.m.s deviations of 0.013 Å and 0.037 Å, respectively) form a twist angle of 68.59 (1)° compared to 68.52 (5)° in BINOL (ref, date). The C_ar—O and C_alkyl—O ether bond lengths in (I) have comparable values to those found in related structures (Allen & Bruno, 2010). The molecular conformation of (I) is consolidated (Table 1) by intramolecular C13′—H13E⋯Cg1 and C13—H13A⋯Cg2 contacts, where Cg1 and Cg2 are the centroids of the C5–C10 and C5′–C10′ rings, respectively (Fig. 3, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C5–C10 and C5′–C10′ rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯Cg2	1.091 (4)	2.998 (5)	4.0338 (4)	158.7 (3)
C13′—H13E⋯Cg1	1.091 (5)	2.877 (5)	3.8615 (4)	150.1 (3)
C13—H13C⋯Cg2ⁱ	1.083 (5)	2.987 (5)	3.6455 (4)	119.6 (3)
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of (I)

with displacement ellipsoids for all atoms including H drawn at the 50% probability level.

Figure 2
An overlay diagram of the β-naphthyl isobutyl ether moieties of (I)

Figure 3
The intramolecular C—H⋯π interactions in (I)

, shown as double dotted lines with centroids as green spheres.

3. Supramolecular features

Although the molecule has two potential hydrogen-bond acceptor sites (atoms O1 and O2), no hydrogen bonding was found in this crystal structure. Indeed, the minimization of steric effects within the molecule gives rise to a structural geometry whose intrinsic molecular and environmental parameters in the crystal would prevent the formation of hydrogen bonding. However, analysis using PLATON (Spek, 2020 ) reveals a C13—H13C⋯Cg2(x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z) (Table 1). In addition, the packing displays several C—H⋯H—C intermolecular contacts ranging from 2.33 to 2.53 Å. Matta (2006 ) reported that these closed-shell intermolecular interactions exhibit energetic stability, potentials typical of bound systems and stable equilibrium geometries.

4. Database survey

A search of the Cambridge Structural Database (CSD version 5.45; Groom et al., 2016 ) for compounds containing the 1-1′-binaphthyl system with an ether moiety linked at the 2,2′ positions gave two hits [CSD refcodes PONTAO (Thoss et al., 2009 ) and PONTAO01 (Maria et al., 2017 )], in which the asymmetric units contain two molecules.

5. Hirshfeld surface analysis

In order to quantify intermolecular interactions revealed by the PLATON analysis, Hirshfeld surface (HS) analysis was performed using CrystalExplorer21.5 (Spackman et al., 2021 ). Fig. 4 shows the three-dimensional HS of (I) mapped over d_norm on a scale ranging from −0.025 to 1.51 a.u. where the colour highlights the different intermolecular contacts: blue, white and red regions indicate contacts whose distances are almost equal, longer and shorter, respectively, than the sum of van der Waals radii. Fig. 5 displays the two-dimensional fingerprint plots of (d_i, d_e) points from all contacts contributing to the HS for all atoms. The H⋯H contacts are the most significant intermolecular interactions and contribute 73.2% whilst C⋯H/H⋯C contacts, which correspond to H⋯π stacking interactions, contribute 21.2%. As expected, the H⋯O contacts make a very weak contribution to the crystal packing at 3.6% and the other contacts C⋯C (1.9%) and C⋯O/O⋯C (0.1%) have a negligible contribution.

Figure 4
The three-dimensional Hirshfeld surface representation of (I)

plotted over d_norm.

Figure 5
The two-dimensional fingerprint plots of (I)

showing (a) the overall interactions and (b)–(f) those delineated into H⋯H, C⋯H/H⋯C, O⋯H/H⋯O, C⋯C and O⋯C/C⋯O contacts, respectively.

6. Synthesis and crystallization

BINOL was produced according to the method described by McKillop et al. (1980). In a 50 ml flask equipped with a magnetic stirrer, 1 eq. (0.70 mmol, 0.20 g) of BINOL was dissolved in 10 ml of ethanol and 10 eq of sodium hydroxide were added. The mixture was refluxed for 1 h and 21 eq. (14.70 mmol, 1.58 ml) of 1-bromo-2-methylpropane were added, then heating was maintained for 24 h. Following CCM, at the end of the reaction, several extractions with ethyl acetate were performed and the organic phase was dried with NaSO₄, then concentrated under reduced pressure. The crude product was purified on a chromatographic silica gel column using hexane/ethyl acetate 90/10 as eluent. A chick yellow powder (60 mg, 21%) was obtained. Single crystals of (I) suitable for X-ray diffraction analysis were grown by slow evaporation from the mixed solvents of hexane and ethyl acetate at room temperature.

Chick yellow powder, yield = 47%, m.p = 387–389 K. ¹H NMR (500 MHz, CDCl₃) δ (ppm) 7.88 (d, J = 9.0 Hz, 2H, HAr), 7.81 (dt, J = 8.2, 1.1 Hz, 2H, HAr), 7.36 (d, J = 9.0 Hz, 2H, HAr), 7.26 (ddd, J = 8.1, 5.8, 2.1 Hz, 2H, HAr), 7.21–7.13 (m, 4H, HAr), 3.67 (qd, J = 8.8, 6.4 Hz, 4H, –CH₂–), 1.67 [dh, J = 13.2, 6.7 Hz, 2H, –CH–(CH₃)₂], 0.56 [d, J = 6.7 Hz, 6H, (CH₃) –CH–], 0.54 [d, J = 6.7 Hz, 6H, (CH₃)–CH–]. ¹³C NMR (126 MHz, CDCl₃) δ (ppm) 154.66, 134.44, 129.30, 129.09, 127.85, 126.10, 125.65, 123.42, 120.71, 115.62, 76.06, 28.45, 18.98.

7. Refinement details

The crystal structure of (I) was refined using SHELXL (Sheldrick, 2015b ) with the standard independent atom model (IAM). Subsequently, this structural model was used as a starting point in a non-spherical refinement procedure. The computational wavefunctions were determined with the ORCA program (Neese et al., 2020 ) using the DFT method at the PBE0/def2-TZVP level of theory. The non-spherical atomic form factors were calculated using NoSpherA2 (Kleemiss et al., 2021). Final refinements were performed with OLEX2.refine (Bourhis et al., 2015 ). All atoms including H atoms were refined anisotropically. Crystal data, data collection and structure refinement details for the last least-squares refinement are summarized in Table 2. This process leads to improved precision of the geometrical parameters and more physically realistic C—H separations. For example, the refined C2—O1 bond length obtained here with the non-spherical model is 1.3622 (3) Å compared to 1.3652 (5) Å with IAM and the refined C2—O1—C11 bond angles are 118.315 (17)° (non-spherical) and 118.13 (3)° (IAM). For the background to non-spherical refinement, see Sanjuan-Szklarz et al. (2020 ) and Jha et al. (2023 ).

Table 2
Experimental details

Crystal data
Chemical formula	C₂₈H₃₀O₂
M_r	398.55
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	11.3889 (8), 15.6537 (11), 12.5193 (9)
β (°)	99.920 (2)
V (Å³)	2198.6 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.07
Crystal size (mm)	0.48 × 0.31 × 0.23

Data collection
Diffractometer	Bruker D8 Venture
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.000, 0.000
No. of measured, independent and observed [I ≥ 2u(I)] reflections	215936, 17714, 14265
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.989

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.050, 1.08
No. of reflections	17714
No. of parameters	541
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.17
Computer programs: APEX4 and SAINT (Bruker, 2019 ), SHELXT2018/2 (Sheldrick, 2015a ), OLEX2.refine (Bourhis et al., 2015) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2384706

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989024009101/hb8104sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024009101/hb8104Isup2.hkl

checkCIF report

Computing details top

2,2'-Diisobutoxy-1,1'-binaphthalene top

Crystal data top

C₂₈H₃₀O₂	D_x = 1.204 Mg m⁻³
M_r = 398.55	Melting point: 389 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.3889 (8) Å	Cell parameters from 17714 reflections
b = 15.6537 (11) Å	θ = 3.0–44.7°
c = 12.5193 (9) Å	µ = 0.07 mm⁻¹
β = 99.920 (2)°	T = 100 K
V = 2198.6 (3) Å³	Prism, colourless
Z = 4	0.48 × 0.31 × 0.23 mm
F(000) = 856.478

Data collection top

Bruker D8 Venture diffractometer	17714 independent reflections
Radiation source: fine-focus sealed tube	14265 reflections with I ≥ 2u(I)
Mirror monochromator	R_int = 0.038
φ and ω scan	θ_max = 44.7°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −22→22
T_min = 0.000, T_max = 0.000	k = −30→30
215936 measured reflections	l = −24→24

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.023	Hydrogen site location: difference Fourier map
wR(F²) = 0.050	All H-atom parameters refined
S = 1.08	w = 1/[σ²(F_o²) + (0.0137P)² + 0.0711P] where P = (F_o² + 2F_c²)/3
17714 reflections	(Δ/σ)_max = 0.002
541 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³
0 constraints

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

	x	y	z	U_iso*/U_eq
O1'	0.776199 (14)	0.498356 (11)	0.341745 (13)	0.01666 (3)
O1	0.734447 (14)	0.575536 (12)	0.638617 (13)	0.01737 (3)
C13'	0.59639 (2)	0.44710 (2)	0.15859 (2)	0.02417 (4)
C12'	0.70148 (2)	0.391771 (15)	0.210094 (18)	0.01879 (4)
C11'	0.80870 (2)	0.444976 (15)	0.259094 (18)	0.01713 (3)
C2'	0.857985 (17)	0.555997 (14)	0.390229 (16)	0.01385 (3)
C1'	0.816020 (16)	0.618843 (13)	0.452436 (15)	0.01271 (3)
C1	0.686874 (16)	0.621349 (13)	0.458654 (16)	0.01309 (3)
C2	0.648288 (17)	0.598891 (14)	0.554230 (17)	0.01449 (3)
C11	0.70253 (2)	0.567336 (16)	0.743665 (18)	0.01806 (4)
C12	0.81506 (2)	0.547883 (16)	0.824239 (18)	0.01962 (4)
C13	0.90482 (2)	0.62078 (2)	0.83150 (2)	0.02380 (4)
C14	0.78109 (3)	0.52831 (2)	0.93444 (2)	0.03137 (6)
C3	0.525397 (19)	0.598393 (16)	0.56113 (2)	0.01904 (4)
C4	0.442362 (19)	0.617508 (17)	0.47119 (2)	0.02111 (4)
C10	0.477288 (18)	0.639919 (15)	0.37163 (2)	0.01831 (4)
C9	0.601102 (18)	0.643888 (14)	0.366043 (17)	0.01499 (3)
C14'	0.74018 (3)	0.331031 (18)	0.12705 (2)	0.02435 (5)
C3'	0.980012 (19)	0.551723 (16)	0.380747 (18)	0.01786 (3)
C4'	1.059045 (19)	0.609785 (17)	0.43474 (2)	0.01970 (4)
C10'	1.020820 (18)	0.674390 (15)	0.500151 (18)	0.01737 (4)
C5'	1.10225 (2)	0.733859 (18)	0.55771 (2)	0.02357 (5)
C6'	1.06387 (3)	0.796215 (18)	0.62076 (2)	0.02631 (5)
C7'	0.94151 (3)	0.801770 (17)	0.62857 (2)	0.02385 (5)
C8'	0.86073 (2)	0.744848 (15)	0.574119 (19)	0.01854 (4)
C9'	0.897770 (17)	0.679042 (14)	0.508850 (16)	0.01448 (3)
C8	0.63491 (2)	0.670193 (16)	0.266644 (19)	0.01898 (4)
C7	0.55041 (2)	0.688558 (18)	0.17723 (2)	0.02395 (5)
C6	0.42742 (2)	0.681410 (19)	0.18200 (2)	0.02650 (5)
C5	0.39219 (2)	0.658060 (18)	0.27738 (2)	0.02444 (5)
H13D	0.6189 (4)	0.4843 (3)	0.0920 (4)	0.0446 (13)
H13E	0.5691 (4)	0.4921 (3)	0.2162 (4)	0.0384 (12)
H13F	0.5196 (4)	0.4074 (4)	0.1267 (4)	0.0510 (15)
H12'	0.6746 (4)	0.3538 (3)	0.2761 (3)	0.0326 (11)
H11C	0.8815 (4)	0.4033 (3)	0.2933 (4)	0.0337 (11)
H11D	0.8373 (4)	0.4850 (3)	0.1965 (3)	0.0306 (10)
H11A	0.6380 (4)	0.5162 (3)	0.7433 (4)	0.0360 (11)
H11B	0.6621 (4)	0.6265 (3)	0.7650 (3)	0.0355 (11)
H12	0.8545 (4)	0.4902 (3)	0.7947 (4)	0.0343 (11)
H13A	0.9295 (4)	0.6347 (3)	0.7529 (4)	0.0387 (12)
H13B	0.9853 (5)	0.6062 (4)	0.8885 (4)	0.0524 (15)
H13C	0.8669 (5)	0.6788 (3)	0.8581 (4)	0.0472 (14)
H14A	0.7414 (5)	0.5840 (4)	0.9646 (4)	0.0519 (15)
H14B	0.8591 (5)	0.5115 (4)	0.9937 (4)	0.0610 (17)
H14C	0.7172 (5)	0.4763 (4)	0.9293 (4)	0.0532 (15)
H3	0.4960 (4)	0.5800 (3)	0.6352 (4)	0.0368 (12)
H4	0.3491 (4)	0.6135 (3)	0.4759 (4)	0.0402 (12)
H14D	0.6658 (4)	0.2919 (3)	0.0891 (4)	0.0437 (13)
H14E	0.8111 (5)	0.2894 (3)	0.1636 (4)	0.0430 (13)
H14F	0.7714 (5)	0.3666 (3)	0.0630 (4)	0.0430 (13)
H3'	1.0126 (4)	0.5020 (3)	0.3349 (4)	0.0362 (11)
H4'	1.1523 (4)	0.6049 (3)	0.4296 (4)	0.0378 (12)
H5'	1.1953 (4)	0.7284 (3)	0.5514 (4)	0.0402 (12)
H6'	1.1258 (4)	0.8434 (3)	0.6632 (4)	0.0470 (14)
H7'	0.9117 (4)	0.8505 (3)	0.6778 (4)	0.0439 (13)
H8'	0.7674 (4)	0.7488 (3)	0.5805 (4)	0.0316 (11)
H8	0.7285 (4)	0.6756 (3)	0.2629 (3)	0.0335 (11)
H7	0.5776 (4)	0.7082 (3)	0.1026 (4)	0.0428 (13)
H6	0.3615 (4)	0.6941 (3)	0.1094 (4)	0.0448 (13)
H5	0.2992 (4)	0.6533 (3)	0.2823 (4)	0.0424 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1'	0.01473 (6)	0.01960 (7)	0.01643 (6)	−0.00056 (5)	0.00487 (5)	−0.00336 (5)
O1	0.01438 (6)	0.02456 (8)	0.01393 (6)	0.00018 (5)	0.00453 (4)	0.00063 (5)
C13'	0.02086 (10)	0.03031 (12)	0.02154 (10)	−0.00184 (9)	0.00422 (8)	−0.00185 (9)
C12'	0.02491 (9)	0.01793 (9)	0.01485 (7)	−0.00341 (7)	0.00716 (7)	−0.00102 (6)
C11'	0.01920 (8)	0.01764 (8)	0.01564 (7)	0.00106 (7)	0.00607 (6)	−0.00095 (6)
C2'	0.01112 (6)	0.01761 (8)	0.01319 (6)	0.00082 (5)	0.00311 (5)	0.00077 (6)
C1'	0.01002 (6)	0.01598 (7)	0.01205 (6)	−0.00073 (5)	0.00165 (5)	0.00026 (5)
C1	0.00996 (6)	0.01569 (7)	0.01349 (6)	−0.00009 (5)	0.00166 (5)	−0.00110 (5)
C2	0.01134 (6)	0.01750 (8)	0.01524 (7)	−0.00087 (6)	0.00397 (5)	−0.00182 (6)
C11	0.01926 (8)	0.02077 (9)	0.01563 (7)	−0.00217 (7)	0.00720 (6)	0.00007 (6)
C12	0.02480 (10)	0.02033 (9)	0.01447 (7)	−0.00012 (7)	0.00543 (7)	0.00196 (7)
C13	0.02319 (10)	0.02987 (12)	0.01826 (9)	−0.00493 (9)	0.00332 (8)	0.00032 (8)
C14	0.04086 (16)	0.03786 (16)	0.01659 (9)	−0.00750 (13)	0.00833 (10)	0.00571 (10)
C3	0.01227 (7)	0.02384 (10)	0.02220 (9)	−0.00155 (6)	0.00635 (6)	−0.00351 (7)
C4	0.01030 (7)	0.02574 (10)	0.02732 (10)	−0.00002 (7)	0.00334 (7)	−0.00593 (8)
C10	0.01116 (7)	0.01935 (9)	0.02290 (9)	0.00211 (6)	−0.00134 (6)	−0.00484 (7)
C9	0.01172 (6)	0.01579 (8)	0.01639 (7)	0.00122 (5)	−0.00054 (5)	−0.00140 (6)
C14'	0.03660 (13)	0.01943 (10)	0.01878 (9)	−0.00291 (9)	0.00972 (9)	−0.00368 (8)
C3'	0.01218 (7)	0.02384 (10)	0.01839 (8)	0.00213 (6)	0.00501 (6)	0.00207 (7)
C4'	0.01049 (7)	0.02758 (11)	0.02121 (9)	−0.00055 (7)	0.00324 (6)	0.00521 (8)
C10'	0.01166 (7)	0.02219 (9)	0.01729 (8)	−0.00383 (6)	−0.00025 (6)	0.00516 (7)
C5'	0.01586 (8)	0.02704 (11)	0.02524 (10)	−0.00856 (8)	−0.00369 (7)	0.00664 (8)
C6'	0.02446 (11)	0.02484 (11)	0.02592 (11)	−0.01121 (9)	−0.00610 (8)	0.00256 (9)
C7'	0.02753 (11)	0.02049 (10)	0.02134 (9)	−0.00791 (8)	−0.00194 (8)	−0.00221 (8)
C8'	0.01907 (8)	0.01821 (9)	0.01760 (8)	−0.00435 (7)	0.00107 (6)	−0.00208 (6)
C9'	0.01218 (6)	0.01710 (8)	0.01350 (7)	−0.00279 (6)	0.00037 (5)	0.00179 (6)
C8	0.01749 (8)	0.02077 (9)	0.01702 (8)	0.00143 (7)	−0.00166 (6)	0.00284 (7)
C7	0.02476 (10)	0.02396 (10)	0.01983 (9)	0.00367 (8)	−0.00547 (8)	0.00346 (8)
C6	0.02236 (10)	0.02659 (11)	0.02585 (11)	0.00696 (8)	−0.00914 (8)	−0.00190 (9)
C5	0.01440 (8)	0.02673 (11)	0.02878 (11)	0.00514 (7)	−0.00592 (8)	−0.00621 (9)
H13D	0.043 (3)	0.049 (3)	0.044 (3)	0.013 (3)	0.012 (2)	0.014 (3)
H13E	0.035 (3)	0.044 (3)	0.038 (3)	0.003 (2)	0.009 (2)	−0.004 (2)
H13F	0.035 (3)	0.061 (4)	0.055 (4)	−0.010 (3)	0.000 (3)	−0.014 (3)
H12'	0.046 (3)	0.031 (3)	0.023 (2)	−0.009 (2)	0.012 (2)	−0.0006 (19)
H11C	0.033 (3)	0.035 (3)	0.034 (3)	0.006 (2)	0.006 (2)	−0.005 (2)
H11D	0.034 (3)	0.033 (2)	0.028 (2)	−0.008 (2)	0.012 (2)	−0.003 (2)
H11A	0.038 (3)	0.042 (3)	0.030 (3)	−0.012 (2)	0.011 (2)	0.000 (2)
H11B	0.040 (3)	0.041 (3)	0.027 (2)	0.008 (2)	0.010 (2)	−0.002 (2)
H12	0.046 (3)	0.029 (3)	0.028 (3)	0.006 (2)	0.006 (2)	0.001 (2)
H13A	0.039 (3)	0.049 (3)	0.030 (3)	−0.009 (2)	0.011 (2)	0.003 (2)
H13B	0.041 (3)	0.072 (4)	0.039 (3)	−0.012 (3)	−0.008 (2)	0.012 (3)
H13C	0.047 (3)	0.042 (3)	0.054 (3)	−0.012 (3)	0.014 (3)	−0.011 (3)
H14A	0.063 (4)	0.065 (4)	0.032 (3)	−0.008 (3)	0.021 (3)	−0.002 (3)
H14B	0.061 (4)	0.093 (5)	0.025 (3)	−0.006 (4)	−0.001 (3)	0.018 (3)
H14C	0.069 (4)	0.060 (4)	0.034 (3)	−0.025 (3)	0.016 (3)	0.011 (3)
H3	0.023 (2)	0.053 (3)	0.037 (3)	−0.002 (2)	0.011 (2)	−0.001 (2)
H4	0.022 (2)	0.056 (3)	0.044 (3)	0.004 (2)	0.007 (2)	−0.006 (3)
H14D	0.051 (3)	0.046 (3)	0.037 (3)	−0.014 (3)	0.017 (2)	−0.019 (2)
H14E	0.060 (3)	0.034 (3)	0.037 (3)	0.007 (3)	0.014 (3)	−0.004 (2)
H14F	0.061 (4)	0.041 (3)	0.032 (3)	−0.005 (3)	0.023 (3)	−0.004 (2)
H3'	0.026 (2)	0.040 (3)	0.045 (3)	0.003 (2)	0.014 (2)	−0.002 (2)
H4'	0.023 (2)	0.047 (3)	0.043 (3)	0.000 (2)	0.006 (2)	0.002 (2)
H5'	0.024 (2)	0.042 (3)	0.052 (3)	−0.013 (2)	0.001 (2)	0.003 (3)
H6'	0.033 (3)	0.057 (3)	0.045 (3)	−0.016 (3)	−0.008 (2)	−0.012 (3)
H7'	0.039 (3)	0.043 (3)	0.048 (3)	−0.013 (2)	0.003 (2)	−0.009 (3)
H8'	0.032 (2)	0.027 (2)	0.036 (3)	−0.002 (2)	0.005 (2)	−0.012 (2)
H8	0.031 (2)	0.045 (3)	0.024 (2)	0.004 (2)	0.0031 (19)	0.013 (2)
H7	0.045 (3)	0.048 (3)	0.030 (3)	0.006 (3)	−0.007 (2)	0.011 (2)
H6	0.032 (3)	0.050 (3)	0.046 (3)	0.011 (2)	−0.011 (2)	0.008 (3)
H5	0.026 (3)	0.056 (3)	0.041 (3)	0.003 (2)	−0.005 (2)	−0.006 (3)

Geometric parameters (Å, º) top

O1'—C11'	1.4276 (3)	C3—C4	1.3729 (4)
O1'—C2'	1.3621 (3)	C3—H3	1.077 (4)
O1—C2	1.3622 (3)	C4—C10	1.4162 (4)
O1—C11	1.4293 (3)	C4—H4	1.075 (4)
C13'—C12'	1.5272 (4)	C10—C9	1.4252 (3)
C13'—H13D	1.083 (5)	C10—C5	1.4206 (3)
C13'—H13E	1.091 (5)	C9—C8	1.4253 (3)
C13'—H13F	1.091 (5)	C14'—H14D	1.086 (5)
C12'—C11'	1.5176 (3)	C14'—H14E	1.076 (5)
C12'—C14'	1.5287 (4)	C14'—H14F	1.086 (5)
C12'—H12'	1.103 (4)	C3'—C4'	1.3724 (4)
C11'—H11C	1.084 (4)	C3'—H3'	1.071 (4)
C11'—H11D	1.096 (4)	C4'—C10'	1.4162 (4)
C2'—C1'	1.3896 (3)	C4'—H4'	1.078 (4)
C2'—C3'	1.4166 (3)	C10'—C5'	1.4197 (3)
C1'—C1	1.4867 (3)	C10'—C9'	1.4261 (3)
C1'—C9'	1.4238 (3)	C5'—C6'	1.3733 (5)
C1—C2	1.3891 (3)	C5'—H5'	1.080 (4)
C1—C9	1.4258 (3)	C6'—C7'	1.4163 (4)
C2—C3	1.4170 (3)	C6'—H6'	1.093 (4)
C11—C12	1.5190 (4)	C7'—C8'	1.3744 (3)
C11—H11A	1.086 (4)	C7'—H7'	1.073 (5)
C11—H11B	1.088 (4)	C8'—C9'	1.4232 (3)
C12—C13	1.5243 (4)	C8'—H8'	1.081 (4)
C12—C14	1.5268 (4)	C8—C7	1.3750 (3)
C12—H12	1.101 (4)	C8—H8	1.078 (4)
C13—H13A	1.091 (4)	C7—C6	1.4167 (4)
C13—H13B	1.085 (5)	C7—H7	1.078 (5)
C13—H13C	1.083 (5)	C6—C5	1.3732 (5)
C14—H14A	1.079 (6)	C6—H6	1.093 (4)
C14—H14B	1.088 (5)	C5—H5	1.074 (5)
C14—H14C	1.086 (5)

C2'—O1'—C11'	117.900 (17)	H14C—C14—H14B	108.6 (4)
C11—O1—C2	118.315 (17)	C4—C3—C2	119.79 (2)
H13D—C13'—C12'	110.9 (3)	H3—C3—C2	120.7 (2)
H13E—C13'—C12'	112.2 (3)	H3—C3—C4	119.4 (2)
H13E—C13'—H13D	107.1 (4)	C10—C4—C3	121.17 (2)
H13F—C13'—C12'	110.6 (3)	H4—C4—C3	119.3 (3)
H13F—C13'—H13D	107.8 (4)	H4—C4—C10	119.5 (3)
H13F—C13'—H13E	107.9 (4)	C9—C10—C4	118.97 (2)
C11'—C12'—C13'	112.14 (2)	C5—C10—C4	121.71 (2)
C14'—C12'—C13'	111.25 (2)	C5—C10—C9	119.32 (2)
C14'—C12'—C11'	108.06 (2)	C10—C9—C1	119.63 (2)
H12'—C12'—C13'	108.9 (2)	C8—C9—C1	122.086 (19)
H12'—C12'—C11'	107.5 (2)	C8—C9—C10	118.285 (19)
H12'—C12'—C14'	108.9 (2)	H14D—C14'—C12'	110.7 (3)
C12'—C11'—O1'	108.854 (18)	H14E—C14'—C12'	111.7 (2)
H11C—C11'—O1'	110.1 (2)	H14E—C14'—H14D	108.4 (4)
H11C—C11'—C12'	109.6 (2)	H14F—C14'—C12'	110.7 (3)
H11D—C11'—O1'	109.3 (2)	H14F—C14'—H14D	107.2 (4)
H11D—C11'—C12'	110.0 (2)	H14F—C14'—H14E	107.9 (4)
H11D—C11'—H11C	109.0 (3)	C4'—C3'—C2'	119.81 (2)
C1'—C2'—O1'	116.352 (17)	H3'—C3'—C2'	121.0 (2)
C3'—C2'—O1'	122.466 (19)	H3'—C3'—C4'	119.2 (2)
C3'—C2'—C1'	121.164 (19)	C10'—C4'—C3'	121.12 (2)
C1—C1'—C2'	119.137 (17)	H4'—C4'—C3'	119.5 (3)
C9'—C1'—C2'	119.204 (18)	H4'—C4'—C10'	119.3 (3)
C9'—C1'—C1	121.659 (18)	C5'—C10'—C4'	121.51 (2)
C2—C1—C1'	120.070 (17)	C9'—C10'—C4'	118.988 (19)
C9—C1—C1'	120.620 (18)	C9'—C10'—C5'	119.50 (2)
C9—C1—C2	119.275 (18)	C6'—C5'—C10'	120.86 (2)
C1—C2—O1	116.325 (17)	H5'—C5'—C10'	118.3 (3)
C3—C2—O1	122.572 (19)	H5'—C5'—C6'	120.8 (3)
C3—C2—C1	121.080 (19)	C7'—C6'—C5'	119.85 (2)
C12—C11—O1	108.047 (18)	H6'—C6'—C5'	121.1 (3)
H11A—C11—O1	110.0 (2)	H6'—C6'—C7'	119.0 (3)
H11A—C11—C12	110.3 (2)	C8'—C7'—C6'	120.57 (3)
H11B—C11—O1	109.6 (2)	H7'—C7'—C6'	119.8 (2)
H11B—C11—C12	110.6 (2)	H7'—C7'—C8'	119.7 (3)
H11B—C11—H11A	108.3 (3)	C9'—C8'—C7'	120.97 (2)
C13—C12—C11	111.71 (2)	H8'—C8'—C7'	120.6 (2)
C14—C12—C11	108.91 (2)	H8'—C8'—C9'	118.4 (2)
C14—C12—C13	111.60 (2)	C10'—C9'—C1'	119.71 (2)
H12—C12—C11	106.7 (2)	C8'—C9'—C1'	122.050 (19)
H12—C12—C13	109.0 (2)	C8'—C9'—C10'	118.242 (19)
H12—C12—C14	108.7 (2)	C7—C8—C9	120.98 (2)
H13A—C13—C12	111.7 (3)	H8—C8—C9	118.6 (2)
H13B—C13—C12	111.3 (3)	H8—C8—C7	120.4 (2)
H13B—C13—H13A	108.4 (4)	C6—C7—C8	120.51 (3)
H13C—C13—C12	110.4 (3)	H7—C7—C8	120.0 (2)
H13C—C13—H13A	106.7 (4)	H7—C7—C6	119.5 (2)
H13C—C13—H13B	108.1 (4)	C5—C6—C7	119.79 (2)
H14A—C14—C12	109.9 (3)	H6—C6—C7	119.6 (3)
H14B—C14—C12	111.1 (3)	H6—C6—C5	120.6 (3)
H14B—C14—H14A	107.3 (4)	C6—C5—C10	121.04 (2)
H14C—C14—C12	111.6 (3)	H5—C5—C10	118.5 (3)
H14C—C14—H14A	108.0 (4)	H5—C5—C6	120.5 (3)

O1'—C11'—C12'—C13'	60.63 (2)	C1—C2—C3—C4	2.26 (3)
O1'—C11'—C12'—C14'	−176.40 (2)	C1—C9—C10—C4	3.02 (2)
O1'—C2'—C1'—C1	−2.31 (2)	C1—C9—C10—C5	−176.67 (2)
O1'—C2'—C1'—C9'	177.507 (17)	C1—C9—C8—C7	177.56 (2)
O1'—C2'—C3'—C4'	−177.60 (2)	C2—C3—C4—C10	−1.58 (3)
O1—C2—C1—C1'	0.17 (2)	C3—C4—C10—C9	−1.05 (3)
O1—C2—C1—C9	178.054 (19)	C3—C4—C10—C5	178.64 (2)
O1—C2—C3—C4	−175.95 (2)	C4—C10—C9—C8	−177.27 (2)
O1—C11—C12—C13	62.99 (2)	C4—C10—C5—C6	178.65 (3)
O1—C11—C12—C14	−173.29 (2)	C10—C9—C8—C7	−2.14 (3)
C2'—C1'—C1—C2	109.31 (2)	C10—C5—C6—C7	−0.70 (3)
C2'—C1'—C1—C9	−68.54 (2)	C9—C8—C7—C6	−0.21 (3)
C2'—C1'—C9'—C10'	0.44 (2)	C3'—C4'—C10'—C5'	178.96 (2)
C2'—C1'—C9'—C8'	−179.856 (19)	C3'—C4'—C10'—C9'	−0.49 (3)
C2'—C3'—C4'—C10'	−0.05 (3)	C4'—C10'—C5'—C6'	179.95 (2)
C1'—C1—C2—C3	−178.14 (2)	C4'—C10'—C9'—C8'	−179.43 (2)
C1'—C1—C9—C10	175.502 (19)	C10'—C5'—C6'—C7'	−0.19 (3)
C1'—C1—C9—C8	−4.19 (2)	C10'—C9'—C8'—C7'	−0.86 (2)
C1'—C9'—C10'—C4'	0.29 (2)	C5'—C6'—C7'—C8'	0.46 (3)
C1'—C9'—C10'—C5'	−179.17 (2)	C6'—C7'—C8'—C9'	0.08 (3)
C1'—C9'—C8'—C7'	179.43 (2)	C8—C7—C6—C5	1.66 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C5–C10 and C5'–C10' rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···Cg2	1.091 (4)	2.998 (5)	4.0338 (4)	158.7 (3)
C13′—H13E···Cg1	1.091 (5)	2.877 (5)	3.8615 (4)	150.1 (3)
C13—H13C···Cg2ⁱ	1.083 (5)	2.987 (5)	3.6455 (4)	119.6 (3)

Symmetry code: (i) x, −y+3/2, z+1/2.

Acknowledgements

The authors thank the PMD2X X-ray diffraction facility (https://crm2.univ-lorraine.fr/lab/fr/services/pmd2x) of the Institut Jean Barriol, Université de Lorraine, for X-ray diffraction measurements and the AFRAMED project. CCDC is also thanked for providing access to the Cambridge Structural Database through the FAIRE program. The authors are very grateful to UNESCO, CNRS and the IUCr for their support to the AFRAMED project. The authors also thank PASRES for funding Coulibaly's thesis project. The authors pay a fitting tribute to Professor Ané Adjou of the Félix Houphouët-Boigny University, Supervisor of Coulibaly's PhD, who passed away in October 2023 before the thesis defence.

Funding information

Funding for this research was provided by: PASRES, a strategic support program for scientific research in Ivory Coast (studentship No. 235/1st session of 2020 to Pénayori Marie-Aimée Coulibaly).

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