Energies and Geometries of Isographic Hydrogen-Bonded Networks. 1. The (8) Graph Set

Abstract

The bidentate hydrogen-bonding patterns frequently formed by the side chains of the amino acids arginine, asparagine, and glutamine can be described, using graph-set notation, as (8) (ring pattern of eight atoms with two donor and two acceptor hydrogen bonds). It is shown that this hydrogen-bonding pattern is present in approximately 34% of the high-resolution crystal structures in the Cambridge Structural Database (CSD) that have the potential to form this particular pattern. Most of these crystal structures involve an interaction between two amide groups, but a significant number involve an interaction between an amidinium cation and a carboxylate anion. The mean H···O bond distances and the N−H···O bond angles found for these two types of interaction are nearly the same. Ab initio molecular orbital calculations are used to investigate the structure, charge distribution, and decomposition enthalpies of several gas phase hydrogen-bonded complexes which have these types of (8) interactions. Calculated H··...