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The nature of hydrogen bonding in R22(8) crystal motifs – a computational exploration

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journal contribution
posted on 07.12.2014 by P. Deepa, R. Vijay Solomon, S. Angeline Vedha, P. Kolandaivel, P. Venuvanalingam

R22(8), a commonly occurring motif in organic crystals, has been examined here through ab initio and density functional theory (DFT) methods. The 11 R22(8) motifs reported by Allen et al. have been classified into five types; their structural features, hydrogen-bonding patterns and the kind of interactions stabilising these motifs have been studied. Results reveal that the electronegativity of donor atoms plays a major role in directing the hydrogen bonds, whereas their positions in the motif have been found to be less important. Quantum theory of atoms in molecules (QTAIM) and reduced density gradient-based non-covalent-interaction analyses have been used to understand the weak interactions between monomers. Homonuclear interactions within the motifs have been found to be stronger with higher covalent character at the bond critical points than heteronuclear interactions. In addition, a localised molecular orbital energy decomposition analysis (LMOEDA) has been accomplished to provide useful insight into various long- and short-range interactions that contribute to the total stabilisation energies. The stabilising n → σ* interactions have been explained using natural bond orbital (NBO) analysis. Overall, this study provides the essential criteria for an organic crystal to be in an R22(8) motif and further discusses the different combinations of hydrogen-bonding features within the R22(8) motifs.