Bilayer formation in metal carboxylate structures: Results from the Cambridge Structural Database

The crystal structures of 272 metal carboxylates were surveyed with regard to the prevalence of bilayer formation. Bilayers affect the chemical and physical properties of solids. In particular, solid-state reactivity may be greatly enhanced by the presence of 2-dimensional metal coordination polymers in a bilayer motif. Bilayer formation is common (≈60% of 2-D coordination polymers) for aliphatic 3-carbon acidate salts and complexes, and is dominant (92%) for salts and complexes of ≥4-carbon aliphatic acids. For aromatic unsubstituted acids, the percentage is remarkably low (32% of all structures in the class - most are 1-D coordination polymers), while addition of a spacer group between the carboxyl group and the aromatic portion leads to >90% bilayer/2-D coordination polymer formation. The above points and other subtle features are illustrated in this contribution, and strategies for planning the production of possible bilayer materials are proposed. © 2000 Elsevier Science Ltd. All rights reserved.