Abundance and Strength of M–H···H–C (M = Al, Ga, In) Dihydrogen Bonds

Dihydrogen bonds involving carbon and metals of group 13, M–H···H–C (M = Al, Ga, In), were analyzed theoretically. A structural survey of the Cambridge Structural Database revealed the surprising abundance of these interactions in the solid state, where they are often accompanied by weaker C–H···H–C...

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Bibliographic Details
Published in:Crystal growth & design 2017-04, Vol.17 (4), p.2097-2103
Main Author: Echeverría, Jorge
Format: Article
Language:English
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Summary:Dihydrogen bonds involving carbon and metals of group 13, M–H···H–C (M = Al, Ga, In), were analyzed theoretically. A structural survey of the Cambridge Structural Database revealed the surprising abundance of these interactions in the solid state, where they are often accompanied by weaker C–H···H–C homopolar contacts. Furthermore, cooperative effects were observed to reinforce both interactions in the case of bifurcated short contacts. To study the energetics of the interaction, a comprehensive computational benchmarking was first carried out to find the most suitable calculation method. Dispersion corrected functionals (DFT-D) give good results in terms of both intermolecular distance and binding energies. Interaction energies were then calculated for systems involving terminal and bridging hydrogen atoms, obtaining values in the range 1–2.5 kJ/mol. For dimers of Lewis acid–base adducts, binding energies increase up to 10 kJ/mol per H···H contact due to the redistribution of the electron density of the monomers, which eventually leads to an enhancement of the electrostatic character of the interacting unit.
ISSN:1528-7483
1528-7505
DOI:10.1021/acs.cgd.7b00069