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Communication

Crystal Structure of 3-(Anthracen-2′-yl)-ortho-carborane

by
Kyrill Yu. Suponitsky
,
Akim V. Shmal’ko
,
Sergey A. Anufriev
and
Igor B. Sivaev
*
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., 119991 Moscow, Russia
*
Author to whom correspondence should be addressed.
Molbank 2025, 2025(4), M2071; https://doi.org/10.3390/M2071
Submission received: 19 September 2025 / Revised: 3 October 2025 / Accepted: 7 October 2025 / Published: 10 October 2025
(This article belongs to the Section Structure Determination)
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Abstract

Crystal molecular structure of 3-(anthracen-2′-yl)-ortho-carborane was determined by single crystal X-ray diffraction study at 100 K. The asymmetric cell unit contains two enantiomeric pairs of molecules, in one of which the intramolecular dihydrogen bond CH...HB is formed with the participation of the C(1)H hydrogen of the anthracene substituent, and in the other with the participation of the C(3)H hydrogen. In all molecules, the polycyclic aromatic and carborane fragments are rotated relative to each other in such a way that the C-C bond of the ortho-carborane cage is approximately parallel to the plane of the aromatic substituent. According to quantum chemical calculations, the minimum energy corresponds to the formation of an intramolecular dihydrogen bond C(1)H...HB(4/7), whereas the C(3)H...HB(4/7) bond is formed rather as a result of intermolecular interactions in the crystal lattice.

1. Introduction

ortho-Carborane derivatives with polycyclic aromatic substituents attached to carbon atoms have recently attracted increasing attention from researchers as a promising platform for stimuli-responsive luminescence smart materials due to their aggregation-induced emission [1,2,3]. At the same time, derivatives of ortho-carborane with polycyclic aromatic substituents at boron atoms have been studied to a much lesser extent. At present, there are only a few examples of B-substituted ortho-carborane derivatives with tricyclic (anthracene [4,5,6,7]) or tetracyclic (pyrene [7,8]) aromatic substituents. Moreover, information about the structure of these compounds is even more rare; in the literature, there are data on the crystal structures of three B-substituted derivatives of ortho-carborane with pyrene substituents [7] and only one derivative with an anthracene substituent [6]. In the latter case, this is the structure of 3-(anthracen-9′-yl)-ortho-carborane.
In this communication, we report the crystal structure of isomeric 3-(anthracen-2′-yl)-ortho-carborane, which we recently prepared by Pd-catalyzed cross-coupling reaction of anthracen-2-yl zinc bromide with 3-iodo-ortho-carborane [7].

2. Results and Discussion

It was found that the luminescent properties of C-substituted polycyclic aryl-ortho-carboranes are largely determined by the mutual orientation of the planar organic substituent and the carborane cage [9,10,11]. In most of the aryl-substituted ortho-carboranes, when the carborane C-C bond is coplanar with the aryl π-plane, there is virtually no electronic interaction between them. Therefore, the emission band in this conformation is associated with the transition from the locally excited (LE) state of the aryl substituent. In contrast, when the C-C bond in ortho-carborane is perpendicular to the π-plane of the aryl group, the carborane cage can serve as an electron acceptor. As a result, in such conformers, photoexcitation will lead to intramolecular charge transfer (ICT) and subsequent generation of a significant emission band with an ICT character.
The simplest example of a C-aryl derivative of ortho-carborane is 1-phenyl-ortho-carborane. In an isolated molecule, the structure of which was determined by gas-phase electron diffraction, the torsion angle Ccarb-Ccarb-Car-Car θ is 25° [12]. This is close to the values characterized by the minimum energy, which were found using HF (θ = 25° [12]) and DFT (θ = 30.2° [13]) quantum chemical calculations [13]. In the crystalline state, 1-phenyl-ortho-carborane can exist in the form of two polymorphic modifications (α- and β-forms), the molecules of which differ in the orientation of the phenyl ring with θ values equal to 22.2° and 18.3° in the α- and β-forms, respectively [12,14,15]. A notable contribution to the stabilization of the most preferred conformation is made by the presence of intramolecular H...H interactions between the carborane cage and the phenyl ring [15]. At the same time, since the rotational barrier of the phenyl ring is very small, in solution there is an equilibrium between the different rotational conformers, which is confirmed by 1H NMR spectroscopy data [16]. It is worth noting that in the structure of polymorph β, in contrast to polymorph α, in addition to the intramolecular H...H contacts, there are numerous intermolecular H...H contacts [15]. An increase in the size of the substituent leads to a predominance of the role of intermolecular contacts, as a result of which they can have a determining effect on the conformational structure of the molecule in the solid state. Moreover, different polymorphs of the same compound may demonstrate various luminescent behaviors [17].
As for B(3)-substituted aryl derivatives of ortho-carborane, in which the substituent is attached to the boron atom adjacent to carbon atoms rather than to one carbon atom, little is known about their geometry and its potential effect on luminescent properties. Although the synthesis of 3-aryl-ortho-carborane derivatives was first described more than 50 years ago [18], only limited information is available on their crystal structure. At the same time, it should be noted that in most structures of 3-phenyl-ortho-carboranes, intramolecular CH...HB contacts are observed, rather than CH...HC contacts characteristic of C-aryl derivatives of ortho-carborane [4,19,20]. However, in the crystal structure of 3-(pyren-1′-yl)-ortho-carborane, it is the CH...HC contact, together with the additional CH...HB contact involving the fused ring, that “directs” the pyrene moiety almost perpendicular to the C-C bond of the carborane [7]. On the other hand, in the structure of 3-(anthracen-9′-yl)-ortho-carborane, the substituent adopts an intermediate orientation between perpendicular and parallel to the C-C bond of the carborane cage in the presence of shorter CH...HC and longer CH...HB intramolecular contacts involving the fused rings of the substituent [6].
3-(Anthracen-2′-yl)-ortho-carborane was prepared by Pd-catalyzed cross-coupling reaction of anthracen-2-yl zinc bromide with 3-iodo-ortho-carborane, as earlier described (Scheme 1) [7].
3-(Anthracen-2′-yl)-ortho-carborane crystallizes in chiral space group P21, and its asymmetric unit cell contains four molecules, which is a relatively rare case. The molecule is chiral. It is seen that in each pair of molecules (A,D (Figure 1 top) and B,C (Figure 1 bottom)), the molecules are almost related to each other by the mirror plane.
We tried to solve and refine the structure of 3-(anthracen-2′-yl)-ortho-carborane in the centrosymmetric space group P21/n. It led to significant disorder in one carborane cage and unstable refinement. Based on that, we believe that correct space group is P21 with four independent molecules.
Two slightly different conformations, with respect to the orientation of the anthracene substituent relative to the carborane cage, are observed (Figure 2, molecules A (left) and B (right)).
In molecule A, a shortened C(4A)-H(4AA)…H(4A)-B(4A) contact is observed (2.37 Å in molecule A and 2.34 Å in molecule D), while in molecule B, the anthracene substituent is slightly rotated around the C(3)-B(3) bond to form a shortened C(16B)-H(16B)…H(7B)-B(7B) contact (2.39 Å in molecules B and C).
To gain a deeper insight into the structure and intramolecular interactions in 3-(anthracen-2′-yl)-ortho-carborane, quantum chemical calculations were carried out. The PBE0 functional with the triplet-zeta basis set was used, the reliability of which for molecular geometry, non-covalent interactions and conformational analysis has been confirmed by our recent studies [21,22,23]. As initial geometries for optimization, both experimentally observed conformations (molecules A and B) were used. However, only one of them (conformation B Figure 2 (right)) corresponds to the true minimum. The theoretically obtained electron density of the optimized geometry of 3-(anthracen-2′-yl)-ortho-carborane was processed using the topological theory by R. Bader [24,25] to search for bond critical points (BCP) between noncovalently bonded atoms. Indeed, BCP between H16B and H7B atoms was localized. To estimate the energy of the H…H contact, we used LMS correlation between the energy and the potential energy density at BCP [26] which is often used to estimate the energy of non-covalent interactions [27,28,29,30]. The energy of the H16…H7 contact is equal to −1.4 kcal/mol, which stabilizes conformation B. However, such energy is comparable to energies of intermolecular interactions, and conformation A is the result of intermolecular interactions in the crystal.
The presence of the planar aromatic fragment in such a dipolar molecule (the calculated dipole moment of 3-(anthracen-2′-yl)-ortho-carborane is 2D) may imply the formation of π…π stacking interactions. However, no such interactions are observed. Instead, the crystal packing is stabilized by close H…π and B-H…H-C contacts.
We have considered the immediate molecular environment of all four independent molecules and calculated the interaction energies of the central molecule with each of its nearest neighbors (pairwise interaction energies). Each molecule in the crystal has eleven neighbors. Of these, four interactions occur between molecules of the same symmetry (A…A, B…B, C…C, D…D), and one interaction occurs between pseudo-centrosymmetric molecules (A…D and B…C). The remaining six interactions are formed between symmetrically independent molecules. The results are presented in Table S1. As a result of all these interactions, the molecules form a complex three-dimensional structure. However, Table S1 shows that each molecule has its strongest interaction with two neighboring molecules. Based on the energies given in Table S1, the crystal packing of 3-(anthracen-2′-yl)-ortho-carborane can be viewed as built up of columns along the b axis, in which the molecules are linked by the strongest H…π interactions, while the intercolumn bonds are provided by weaker H…π and H…H interactions (Figure 3).

3. Materials and Methods

3.1. General Methods

3-Iodo-ortho-carborane [31], and bis(triphenylphosphine)palladium dichloride [(Ph3P)2PdCl2] [32] were prepared according to the literature procedures. Anhydrous cobalt dibromide was prepared from cobalt bromide hexahydrate by heating at 160 °C under vacuum for 3 h and stored under an argon atmosphere. Acetonitrile was dried using standard procedure [33]. The reaction progress was monitored by thin-layer chromatography (Merck F254 silica gel on aluminum plates (Merck KGaA, Darmstadt, Germany)) and visualized using 0.5% PdCl2 in 1% HCl in aq. MeOH (1:10). Acros Organics silica gel (0.060–0.200 mm) was used for column chromatography. The NMR spectra at 400.1 MHz (1H), 128.3 MHz (11B), and 100.0 MHz (13C) were recorded with a Varian Inova-400 spectrometer (see Figures S1–S15 in Supplementary Materials). The signals in the 1H and 13C NMR spectra were referenced to Me4Si, whereas the signals in the 11B NMR spectra were referenced to BF3·Et2O. High resolution mass spectra were recorded on an LCMS-9030 device (Shimadzu, Japan) using electrospray ionization mass spectrometry (ESI-MS). Molecular ions in the spectra were analyzed and matched with the appropriately calculated m/z and isotopic profiles in the LabSolutions v.5.114 program.

3.2. Synthesis of 3-(Anthracen-2′-yl)-ortho-carborane

3-(Anthracen-2′-yl)-ortho-carborane was prepared as described in the literature [7]. Allyl chloride (82 μL, 77 mg, 1.00 mmol) and trifluoroacetic acid (25 μL) were added to a blue mixture of zinc powder (490 mg, 7.50 mmol) and anhydrous CoBr2 (55 mg, 0.25 mmol) in 5 mL of freshly distilled acetonitrile and the resulting dark orange mixture was stirred at room temperature for 15 min. Then 2-anthracenyl bromide (643 mg, 2.50 mmol) was added and the reaction mixture was stirred at room temperature for another 45 min. Then 3-iodo-ortho-carborane (270 mg, 1.00 mmol) and [(Ph3P)2PdCl2] (14 mg, 0.02 mmol) were added, and the reaction mixture was stirred at room temperature overnight. Then the mixture was filtered, and the residue was washed with hot acetone (until traces of carborane-containing products disappeared on TLC). The organic phases were combined, concentrated under reduced pressure with the addition of silica, and subjected to column chromatography on silica using a mixture of n-hexane: ethyl acetate (9:1.5, v/v) as eluent to obtain 3-(anthracen-2′-yl)-ortho-carborane as a pale green crystalline solid (265 mg, yield 83%). 1H{11B} NMR (400 MHz, acetone-d6): δ 8.55 (1H, s, CHAr), 8.50 (2H, s, CHAr), 8.07 (3H, m, CHAr), 7.77 (1H, d, J = 8.6 Hz, CHAr), 7.51 (2H, m, CHAr), 4.87 (2H, br s, CHCarb), 2.58 (2H, br s, BHCarb), 2.51 (2H, br s, BHCarb), 2.44 (2H, br s, BHCarb), 2.29 (2H, br s, BHCarb), 2.20 (1H, br s, BHCarb) ppm. 13C{1H} NMR (100 MHz, acetone-d6): δ CAr-B not observed, 135.5 (CHAr), 133.2 (CAr), 132.9 (CAr), 132.5 (CAr), 132.0 (CAr), 129.7 (CHAr), 129.1 (CHAr), 129.0 (CHAr), 128.4 (CHAr), 127.5 (CHAr), 126.8 (CHAr), 126.7 (CHAr), 126.5 (CHAr), 58.9 (CHCarb) ppm. 11B NMR (128 MHz, acetone-d6): δ −3.0 (2B, d, J = 148 Hz, B(9,12)), −4.5 (1B, s, B(3)-C), −8.8 (1B, d, J = 149 Hz, B(8)), −12.5 (3B, d, J = 154 Hz, B(4,7,6/10)), −13.3 (3B, d, J = 164 Hz, B(5,6/10,11)) ppm. 1H{11B} NMR (400 MHz, CDCl3): δ 8.44 (1H, s, CHAr), 8.43 (1H, s, CHAr), 8.28 (1H, s, CHAr), 8.02 (3H, m, CHAr), 7.61 (1H, d, J = 8.6 Hz, CHAr), 7.51 (2H, m, CHAr), 3.85 (2H, br s, CHCarb), 2.54 (4H, br s, BHCarb), 2.46 (2H, br s, BHCarb), 2.27 (2H, br s, BHCarb), 2.22 (1H, br s, BHCarb) ppm. 11B NMR (128 MHz, CDCl3): δ −2.3 (2B, d, J = 149 Hz, B(9,12)), −4.9 (1B, s, B(3)-C), −8.4 (1B, d, J = 152 Hz, B(8)), −12.8 (3B, d, J = 156 Hz, B(4,7,6/10)), −13.5 (3B, d, J = 161 Hz, B(5,6/10,11)) ppm. HRMS-ESI (m/z): obsd. 320.2569 [M]+, calcd. for C16H20B10: 320.2571 [M]+.

3.3. Single Crystal X-Ray Diffraction Study

Single crystals suitable for X-ray diffraction study were prepared by slow evaporation of a solution of 3-(anthracen-2′-yl)-ortho-carborane in acetone. Single crystal X-ray diffraction experiment was carried out using SMART APEX2 CCD diffractometer (Bruker Scientific LLC, Billerica, MA, USA) (λ(Mo-Kα) = 0.71073 Å, graphite monochromator, ω-scans) at 100 K. Collected data were processed by the SAINT and SADABS programs incorporated into the APEX2 program package [34]. The structure was solved by the direct methods and refined by the full-matrix least-squares procedure against F2 in anisotropic approximation. The positions of hydrogen atoms of the anthracene substituents were calculated and included in the refinement within isotropic approximation using the riding model. H atoms of the carborane cages were found in the difference Fourier maps and refined isotropically. The refinement was carried out with the SHELXTL program [35]. The CCDC number 2489838 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif.
Crystallographic data for 3-(anthracen-2′-yl)-ortho-carborane: C16H20B10 are monoclinic, space group P21: a = 16.1771(11) Å, b = 13.6919(9) Å, c = 16.4224(11) Å, β = 95.155(2)°, V = 3622.8(4) Å3, Z = 8, M = 320.42, dcryst = 1.175 g·cm−3. wR2 = 0.1084 calculated on F2hkl for all 15853 independent reflections with 2θ < 54.1°, (GOOF = 1.030, R = 0.0475 calculated on Fhkl for 13099 reflections with I > 2σ(I)).

Supplementary Materials

Figures S1–S13: NMR spectra of 3-(anthracen-2′-yl)-ortho-carborane; Figures S14 and S15: HRMS spectra of 3-(anthracen-2′-yl)-ortho-carborane; Table S1: Types of intermolecular interactions and pair interaction energies (kcal/mol) of the molecules with their closest environment in the crystal of 3-(anthracen-2′-yl)-ortho-carborane.

Author Contributions

Synthesis and purification, A.V.S.; synthesis and NMR study, S.A.A.; single crystal X-ray diffraction, quantum chemical calculations, and manuscript preparation, K.Y.S.; supervision, manuscript concept, and preparation, I.B.S. All authors have read and agreed to the published version of the manuscript.

Funding

This research was supported by the Russian Science Foundation (25-43-00072).

Data Availability Statement

Crystallographic data for the structure of 3-(anthracen-2′-yl-ortho-carborane) was deposited in the Cambridge Crystallographic Data Centre as supplementary publication CCDC 2489838.

Acknowledgments

The single crystal diffraction data and NMR spectra were obtained using equipment from the Center for Molecular Structure Studies at the A.N. Nesmeyanov Institute of Organoelement Compounds, operating with financial support from the Ministry of Science and Higher Education of the Russian Federation.

Conflicts of Interest

The authors declare no conflicts of interest. The funders had no role in the design of the study; the collection, analyses, or interpretation of data; the writing of the manuscript; or in the decision to publish the results.

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Molbank 2025 m2071 sch001
Scheme 1. Synthesis of 3-anthracen-2′-yl-ortho-carborane.
Scheme 1. Synthesis of 3-anthracen-2′-yl-ortho-carborane.
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Figure 1. General view of four independent molecules of 3-(anthracen-2′-yl)-ortho-carborane showing atomic labeling scheme. Thermal ellipsoids are given at 50% probability level.
Figure 1. General view of four independent molecules of 3-(anthracen-2′-yl)-ortho-carborane showing atomic labeling scheme. Thermal ellipsoids are given at 50% probability level.
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Figure 2. Projection of the anthracene substituent plane onto the C1-C2-B4-B8-B7 face of ortho-carborane.
Figure 2. Projection of the anthracene substituent plane onto the C1-C2-B4-B8-B7 face of ortho-carborane.
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Figure 3. Crystal-packing fragment of 3-(anthracen-2′-yl)-ortho-carborane. Projection onto ac plane. Columns are perpendicular to the plane of figure and are shown by ovals. Blue-columns from molecules A; green-columns from molecules B; orange-columns from molecules C; and red-columns from molecules D.
Figure 3. Crystal-packing fragment of 3-(anthracen-2′-yl)-ortho-carborane. Projection onto ac plane. Columns are perpendicular to the plane of figure and are shown by ovals. Blue-columns from molecules A; green-columns from molecules B; orange-columns from molecules C; and red-columns from molecules D.
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MDPI and ACS Style

Suponitsky, K.Y.; Shmal’ko, A.V.; Anufriev, S.A.; Sivaev, I.B. Crystal Structure of 3-(Anthracen-2′-yl)-ortho-carborane. Molbank 2025, 2025, M2071. https://doi.org/10.3390/M2071

AMA Style

Suponitsky KY, Shmal’ko AV, Anufriev SA, Sivaev IB. Crystal Structure of 3-(Anthracen-2′-yl)-ortho-carborane. Molbank. 2025; 2025(4):M2071. https://doi.org/10.3390/M2071

Chicago/Turabian Style

Suponitsky, Kyrill Yu., Akim V. Shmal’ko, Sergey A. Anufriev, and Igor B. Sivaev. 2025. "Crystal Structure of 3-(Anthracen-2′-yl)-ortho-carborane" Molbank 2025, no. 4: M2071. https://doi.org/10.3390/M2071

APA Style

Suponitsky, K. Y., Shmal’ko, A. V., Anufriev, S. A., & Sivaev, I. B. (2025). Crystal Structure of 3-(Anthracen-2′-yl)-ortho-carborane. Molbank, 2025(4), M2071. https://doi.org/10.3390/M2071

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