Hydrogen-bonded frameworks in molecular metal-organic crystals: the network approach

Supramolecular architectures in molecular metal-organic crystals with three-dimensional networks of hydrogen bonds have been studied from the topological point of view. 636 hydrogen-bonded frameworks have been classified into 78 types of three-dimensional nets. It is shown that the resulting type of a framework is predetermined by prevailing octahedral coordination of metals in complexes that leads to the preference of 6-and 8-coordinated net topologies and those framework types compatible with the inversion symmetry of a complex. The study of molecular packings in rnetal-organic crystals with three-dimensional hydrogen-bonded frameworks and in those without hydrogen bonding has confirmed the trend to form close-packed motifs, irrespective of the presence of hydrogen bonds. Finally, a comparative analysis of organic and rnetal-organic hydrogen-bonded molecular frameworks as well as valence-bonded metal-organic frameworks is presented.