There are two main families of 3D frameworks which can be realized for a wide range of compositions: perovskitoid, based on octahedrally-coordinated metals, and diamondoid, based on tetrahedral metals. In common with other metal thiocyanates, the different chemistries of the N and S termini is key, and means that in both cases, 'double' structures with alternating cationorder predominate. The distinctiveness of each end of the ligand means all reported metal thiocyanate perovskitoid and diamondoid structures are containing alternating MN n and MS n polyhedra. This means most of these materials use two different framework-forming metal ions: a harder metal for the MN n polyhedron, and a softer metal for the MS n polyhedron.