Hydrogen-Bonding Motifs in Adducts of Allylamine with the 10 Simplest n-Alcohols: Single-Crystal X-ray Diffraction Studies and Computational Analysis.

Abstract

In this paper, we analyzed the homologous series of 10 allylamine adducts with n-alcohols from methanol to decanol. These are the first adduct structures containing aliphatic n-alcohols and an aliphatic amine as co-formers. While all of the ingredients are liquids under ambient conditions, the phases were synthesized with the use of the in situ crystallization technique assisted by IR laser-focused radiation at atmospheric pressure. The structures were characterized by single-crystal X-ray diffraction. All of the phases contain the amine and alcohol in a 1:1 ratio. The architecture of the structures, based on hydrogen-bonding interactions between NH2 and OH moieties, depends on the size of the alcohol and changes in a systematic way. The three smallest alcohol adducts contain centrosymmetric layers of molecules of the L4(4)8(8) type. The next four alcohol adducts have the T4(2) topology. The structures with the biggest alcohols contain non-centrosymmetric L6(6) layers. The structural investigations were supported by periodic DFT calculations at the B3LYP/pobTZVP level. The cohesive and adhesive energies made up of layer (E lbe) and ribbon (E rbe) binding energies were used to predict which type of architecture can be formed. The thermal stabilities of the adducts correlate with the melting points of the co-forming alcohols, with no evident relation to the adduct architecture.