Crystal Engineering: A Holistic View

TLDR

Crystal engineering designs functional solid‑state structures by exploiting intermolecular interactions such as hydrogen and coordination bonds, integrating concepts from supramolecular chemistry, crystallography, materials science, and solid‑state chemistry into a distinct, interdisciplinary discipline. This review aims to highlight current challenges in the rapidly evolving field of crystal engineering. The review discusses the nature of intermolecular interactions in crystal design, contrasts geometrical and chemical models, relates them to polymorphism, explores computational prediction of crystal structures, and maps crystallization pathways.

Abstract

Crystal engineering, the design of molecular solids, is the synthesis of functional solid-state structures from neutral or ionic building blocks, using intermolecular interactions in the design strategy. Hydrogen bonds, coordination bonds, and other less directed interactions define substructural patterns, referred to in the literature as supramolecular synthons and secondary building units. Crystal engineering has considerable overlap with supramolecular chemistry, X-ray crystallography, materials science, and solid-state chemistry and yet it is a distinct discipline in itself. The subject goes beyond the traditional divisions of organic, inorganic, and physical chemistry, and this makes for a very eclectic blend of ideas and techniques. The purpose of this Review is to highlight some current challenges in this rapidly evolving subject. Among the topics discussed are the nature of intermolecular interactions and their role in crystal design, the sometimes diverging perceptions of the geometrical and chemical models for a molecular crystal, the relationship of these models to polymorphism, knowledge-based computational prediction of crystal structures, and efforts at mapping the pathway of the crystallization reaction.