The very first known perovskitoids were M[Pt(SCN) 6 ], M = Fe, Cu, Co, reported by Buckton in 1856, though the stated stoichiometry was wrong due to the incorrectly determined masses of N and S at the time, and the lack of structural characterization techniques available at the time precluded an understanding of its perovskitoid structure. Recent work has determined the structures of not only these, but also M = Mn and Ni, . Although Buckton's initial report was understandably lacking in diffraction-based characterization, it did include an unlikely to be replicated thorough gustatory characterization, highlighting the "exceedingly nauseous taste" of soluble [Pt(SCN) 6 ] 4 -compounds. In addition to the perovskitoid structured compounds, Buckton also reported K 2 [Pt(SCN) 6 ] (Buckton's salt), now partially structurally determined (Section 3.6), and otherwise unknown compounds of [Pt(SCN) 6 ] 4 -with Hg, Ag, Pb and Au. Other platinum-based perovskitoids are very likely feasible. The first metal thiocyanate perovskitoid to have its structure The use of Cr[Bi(SCN) 6 ] to quantitatively analyse the presence of bismuth in solution date from the 1930s, 161 but its structure was determined only recently, together with the isostructural Sc[Bi(SCN) 6 ] and Fe[Bi(SCN) 6 ]. Other bismuthbased perovskitoids containing divalent transition metals and A site cations are now known, including both A{Ni[Bi(SCN) 6 ]}, A = K, NH 4 and CH 3 NH 3 , and more complex stoichiometries: As perovskitoids, multiple orderings lowering the symmetry from the Pm3m naturally arise. Rocksalt 'M' site order is strongly enforced in all known NCS perovskitoids, due to the preference for MS 6 and MN 6 octahedra. The fact that the S-terminus binds in a bent fashion imposes large cooperative tilts, meaning that NCS perovskitoids have tilts along every axis, which combined with the presence of the rocksalt order means only six simple tilt-sequences are possible, in the Glazer notation a + a + a + , Of these, the M[Pt(SCN) 6 ] perovskitoids adopt the a -b -c -sequence and most M[Bi(SCN) 6 ] and M[Cd(SCN) 6 ] compounds adopt the a + b -b - sequence. As the sulfur bond angle guarantees a tilted structure, larger cations (e.g. molecular cations) induce complex tilts, e.g. CH 3 NH 3 {Ni[Bi(SCN) 6 ]} adopts the a + b ++-++-c +-+-tilt, or cation vacancies, e.g. C(NH 2 ) 3 {Ni[Bi(SCN) 6 ] 5/6 } to accommodate them. The greater coordinative flexibility of perovskites with Cd(NCS) 6 or Mn(NCS) 6 octahedra, allows for unconventionial tilts and columnar shifts (a degree of freedom impossible in non-molecular perovskites), particular in the presence of larger cations, whether molecular or Cs + . 153,157 (CH 3 ) 3 S) + is the largest ' A' site cation reported in a thiocyanate perovskitoid, and when even larger cations are used which cannot be included within the cages non-perovskite phases start to form, most typically a 1D face-sharing chain CsNiCl 3 -analogue structure type. There are also potential orderings associated with the A-site. In general, molecular A-site cations are orientationally ordered due to the low-symmetry of the frameworks 154 , but an order-disorder phase transition has been found in (NH 4 ) 2 {Ni[Cd(SCN) 6 ]}, 156 and A-sites are often disordered in frameworks containing B-site vacancies. In perovskites with partial occupancy of the A site, the tilts strongly couple to the A-site order, producing complex orders not found in non-molecular perovskites, which have the potential to produce electrical polarity. 154