Supramolecular synthons in crystal engineering—a new organic synthesis

A crystal of an organic compound is the ultimate supermolecule, and its assembly, governed by chemical and geometrical factors, from individual molecules is the perfect example of solid-state molecular recognition. Implicit in the supramolecular description of a crystal structure is the fact that molecules in a crystal are held together by noncovalent interactions. The need for rational approaches towards solid-state structures of fundamental and practical importance has led to the emergence of crystal engineering, which seeks to understand intermolecular interactions and recognition phenomena in the context of crystal packing. The aim of crystal engineering is to establish reliable connections between molecular and supramolecular structure on the basis of intermolecular interactions. Ideally one would like to identify substructural units in a target supermolecule that can be assembled from logically chosen precursor molecules. Indeed, crystal engineering is a new organic synthesis, and the aim of this article is to show that rather than being only nominally relevant to organic chemistry, this subject is well within the mainstream, being surprisingly similar to traditional organic synthesis in concept. The details vary because one is dealing here with intermolecular interactions rather than with covalent bonds; so this article is divided into two parts. The first is concerned with strategy, highlighting the conceptual relationship between crystal engineering and organic synthesis and introduces the term supramolecular synthon. The second part emphasizes methodology, that is, the chemical and geometrical properties of specific intermolecular interactions