The perovskitoid structures comprise corner-sharing octahedra linked by a single µ 1,1 coordinated thiocyanate potentially with cations contained with the pseudocubic cavity (Fig. ). Like the non-molecular perovskitoid analogues, these metal thiocyanates are an extremely diverse family. I have also included here some perovskitoids of more complex stoichiometry, to situate the chemistry of these materials within the broader family and highlight some of the unique structural features. The limited range of softer metals means currently known NCS-perovskitoids can be classified into three families by the identity of the MS 6 cation: A x M[Bi(SCN 6 ) y ], AxM[Pt(SCN) 6 ] 19? and AxM[Cd(SCN) 6 ] 153,156,157 . The occupancy of A site cation varies from x = 0, (i.e. an ReO 3 or Prussian Blue type structure ), to x = 2, the standard perovskite stoichiometry.