We report the structures of six new divalent transition metal hexathiocyanatobismuthate frameworks with the generic formula , M = Mn, Co, Ni and Zn. These frameworks are defective analogues of the perovskite-derived trivalent transition metal hexathiocyanatobismuthates MIII[Bi(SCN)6]. The defects in these new thiocyanate frameworks order and produce complex superstructures due to the low symmetry of the parent structure, in contrast to the related and more well-studied cyanide Prussian Blue analogues. Despite the close similarities in the chemistries of these four transition metal cations, we find that each framework contains a different mechanism for accommodating the lowered transition metal charge, making use of some combination of Bi(SCN)6 3- vacancies, MBi antisite defects, water substitution for thiocyanate, adventitious extra-framework cations and reduced metal coordination number. These materials provide an unusually clear view of defects in molecular framework materials and their variety suggests that similar richness may be waiting to be uncovered in other hybrid perovskite frameworks
