Graph-set analysis of hydrogen-bond patterns: some mathematical concepts

Abstract

To provide a foundation for further theoretical and software development of the application of graph sets to patterns of hydrogen bonding and other intermolecular interactions a number of mathematical concepts and tools are defined, developed and demonstrated. Following a review of the basic definitions and uses of graph sets, the directional properties of hydrogen bonds are now included in the treatment. The concepts of a constructor graph and covalent distance matrix have been developed to aid in the generation of a qualitative descriptor for the straightforward, consistent and ultimately automatic (with appropriate software) definition of patterns. An additional mathematical tool, the arrowed T-labeling, has been developed to deal with situations in which pattern-forming moieties are located on crystallographic special positions. To demonstrate the utility and various features of these concepts they are applied in detail to two particular structures, polymorphic iminodiacetic acid [N-(carboxymethyl)glycine] and trans-tetraamminedinitrocobalt(III) acetate. To facilitate the application and use of graph sets many of these developments have already been incorporated into the software of the Cambridge Structural Database, as described in the accompanying paper.