Dalton Transactions

Dalton Transactions View Article Online PAPER View Journal | View Issue Dihydrogen intermolecular contacts in group 13 compounds: H⋯HorE⋯H (E = B, Al, Ga) Cite this: Dalton Trans., 2017, 46, 2844 interactions?† Jorge Echeverría,* Gabriel Aullón and Santiago Alvarez A systematic theoretical analysis of homopolar dihydrogen interactions in group 13 compounds is presented here. Ab initio calculations and structural analysis allow us to demonstrate that interactions involving B–H⋯H–B contacts are comparable in strength to the previously studied C–H⋯H–C ones, yet attractive and important for the stabilization of dimers of large molecules. We have also shown that a polyhedral skeleton enhances the B–H⋯H–B interaction strength with respect to non-polyhedral compounds, and it has also been proven that Al–H⋯H–Al and Ga–H⋯H–Ga interactions can be attractive in Received 19th July 2016, some cases. If H⋯E (B, Al and Ga) short contacts are present, the interaction is significantly strengthened, Accepted 26th January 2017 especially for Al and Ga. In general, H⋯H interactions combined with associated H⋯E (B, Al and Ga) short Creative Commons Attribution 3.0 Unported Licence. DOI: 10.1039/c6dt02854c contacts are responsible for the stability of a large number of dimers of group 13 compounds and may rsc.li/dalton play an important role in the packing of their crystal structures. Introduction an increase in the number of publications on the subject. For example, the surprising strength of some C–H⋯H–C contacts During the last few decades, it has been observed that weak was for the first time evaluated via a theoretical analysis,17,18 This article is licensed under a intermolecular interactions play an important role in deter- and confirmed experimentally by the stabilization of alkanes mining the structure and reactivity of several families of with very long C–C bonds.19 On the other hand, in group – compounds.1 5 Dihydrogen contacts are a type of inter- 13 compounds, B–H⋯H–B interactions have been observed in 20 Open Access Article. Published on 09 February 2017. Downloaded 8/13/2019 9:06:03 AM. molecular interaction that involves two hydrogen atoms with boron hydrides and complex metal hydrides and lyotropic the same (X–H⋯H–X) or different polarities (X–H⋯H–Y).6 lamellar phases of carborane-cage amphiphiles,21 and they Usually, the term dihydrogen bond is reserved for the second seem to play an important role in the design of materials for case whereas the first one is referred to as dihydrogen inter- hydrogen storage.22 Descending down the group 13, Al–H⋯H–Al δ δ− action.7 While X–H +⋯ H–Y dihydrogen bonds have an intramolecular contacts have been found in several polymorphs electrostatic contribution due to the opposite charge of the of the crystal structure of alane,23 whereas short Ga–H⋯H–Ga δ δ two hydrogen atoms, the homopolar X–H +⋯ +H–X dihydrogen contacts can be found only in a handful of structures and, to interactions are generally classified as weak and governed by our knowledge, there is no theoretical work in the literature dispersion. The dihydrogen bonding of heteropolar units devoted to them. However, short heteropolar N–H⋯H–Ga con- such as C–H⋯H–B8 or N–H⋯H–B9,10 has been widely studied tacts have been detected, for example, in the crystal structure of – and many experimental11,12 and theoretical13 16 works can be methylamine-gallane.24 Homopolar dihydrogen contacts have found in the literature. However, homopolar contacts have not been observed in compounds of the two heaviest elements attracted less attention and only in recent years has there been of group 13, In and Tl. From a theoretical point of view, dihydrogen bonding has been approached in several ways. The quantum theory of Departament de Química Inorgànica i Orgànica and Institut de Química Teòrica i atoms in molecules (AIM) has been used by McGrady and Computacional, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Wolstenholme to prove the existence of a bond path typical of Spain. E-mail: [email protected] attractive interactions between two hydrogen atoms of the † Electronic supplementary information (ESI) available: Angular distribution of same polarity.20 The electron localization function (ELF) can B–H⋯H–B intermolecular contacts, distribution of Al⋯H distances, structure of be also employed to find and characterize dihydrogen bonds.25 Al H , Cartesian coordinates of all calculated dimers characterized as true 4 12 18 minima and thermochemical properties of selected dimers. See DOI: 10.1039/ Modern Valence Bond (VB) and, especially, Molecular Orbital c6dt02854c (MO)-based methods have been widely used to investigate the 2844 | Dalton Trans.,2017,46,2844–2854 This journal is © The Royal Society of Chemistry 2017 View Article Online Dalton Transactions Paper nature of C–H⋯H–C interactions (see section 2.1 in ref. 1 for a for B–H⋯H angles range from 80° to 180° and show a clear comprehensive account of theoretical methods that take into maximum at around 115° (Fig. 1b). This is similar to what was account dispersion forces). found for R3C–H⋯H–CR3 contacts, where the C–H⋯H angle In this work, we undertake a combined structural and sys- presents a peak at 125°.18 tematic ab initio analysis of intermolecular E–H⋯H–E contacts As for the quality of the analysed data, it is important to in group 13 compounds, focusing on those with a homopolar assess how the positions of the H atoms have been determined character. E⋯H (B, Al and Ga) short contacts will also be evalu- in the corresponding crystal structures. We have only found ated since they are often associated with dihydrogen contacts. three examples of neutron diffraction structures, containing Since Hartree–Fock theory completely neglects dispersion, we 37 short B–H⋯H–B contacts (CSD refcodes FUYYIH02,30 have employed second-order Møller–Plesset (MP2) pertur- KOMZAN,31 SOHZIZ32), which exclude the possibility of a bation theory combined with a large basis set to capture the meaningful statistical analysis. However, X-ray structures can non-covalent nature of the interaction. This theoretical also be useful, especially when the H positions have been approach has been extensively tested and compared to high refined. On the other hand, structures where the H atoms have level calculations such as CCSD(T)/CBS, giving very good been artificially placed at fixed distances (1.1 and 1.12 Å in the results for the study of H⋯H contacts in alkanes17 and other case of B–H) can introduce relatively large errors in the aver- families of compounds.26 We have studied small boranes, as aged H⋯H distances. In Fig. 1a, we compare the H⋯H dis- well as larger arachno, nido and closo polyhedral boranes, and tances obtained with and without the inclusion of this set of also Al and Ga hydrides. The heaviest elements of group 13, In structures with fixed hydrogens, obtaining similar results. In and Tl, have been excluded in the present study, because these both cases, the van der Waals peak can be adjusted to a atoms are affected by relativistic effects27 and, thus, their Gaussian function centred at 2.91 Å ± 0.02. This can be due to hydrides behave differently from those of the lighter elements the fact that the geometrical parameters associated with the of the group (B, Al and Ga). interaction topologies, with B–H⋯H angles around 115°, com- Creative Commons Attribution 3.0 Unported Licence. pensate in part the error introduced by the fixed bond lengths. Only in the case of linear topologies (B–H⋯H angles close to Structural evidence 180°) would the error in the H⋯H distance be added. An 84% of all the B–H⋯H–B short contacts was found to Boron hydrides correspond to the crystal structures of polyhedral boranes. We have searched the Cambridge Structural Database (CSD)28 This is evidenced by the data analysis shown in Fig. 1a, where for E–H⋯H–E (E = B, Al, Ga, In and Tl) contacts shorter than the B–H⋯H–B contacts shorter than 5 Å are presented. The twice the van der Waals radius of hydrogen29 plus 25%, i.e. blue bars represent the frequency of all B–H⋯H–B contacts, 3 Å, in order to have a global picture of the occurrence of these while the grey bars represent the subset of contacts in which This article is licensed under a interactions. B–H⋯H–B contacts were the most numerous both B atoms involved in the interaction are hexacoordinated, ones with 3542 hits (Fig. 1a). We have also analyzed the B– which is the most common coordination number for the B H⋯H angles associated with those contacts. Since angles atom in polyhedral boranes. Within the remaining 16%, Open Access Article. Published on 09 February 2017. Downloaded 8/13/2019 9:06:03 AM. smaller than 80° are unlikely due to steric hindrance, values borane adducts with Lewis bases like amines and phosphines Fig. 1 (a) Distribution of B–H⋯H–B distances shorter than 5 Å as found in the CSD. The blue bars represent all B–H⋯H–B contacts, the transparent bars with grey outline represent only the contacts involving two hexacoordinate B atoms, and the solid grey bars correspond to all the crystal structures excluding artificially fixed B–H bond lengths and R < 5%. (b) Distribution of the B–H⋯H angles for the H⋯H contacts (a) within the van der Waals peak (i.e., shorter than 3.5 Å) in blue, and the same distribution for the two distinct angles α and β (Fig.

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