3 ) and quadrupoles (e.g Gua + ). The orientational order of organic A-site cations can thus generate electrical polarisation, either directly through ferrodipolar order, as in the formate perovskites, or indirectly through coupling of ferroquadrupolar order to other order parameters, for example (Gua){Cu(HCO 2 ) 3 }. We did not find polar orientational order in these new perovskites, and complete orientational order was only present in 1, as 3 shows partial disorder and 4 complete disorder. Our variable temperature diffraction studies found no evidence of any phase transitions below 260 K, implying that the observed A-site disorder is static, which for compound 4 is likely related to the presence of M-site vacancies. Our DFT calculations suggest that orientational order in 3 is moderately favourable as ∆E CN,av = 16 kJmol -1 (0.17 eV ≈ 6kT at room temperature). Careful structural examination revealed that hydrogen bonding is an important factor in the structures of these materials, as in other molecular perovskites, and indeed, ∆E CN,av is comparable to the H-bonding energies found in formate perovskites. This suggests that temperature-induced phase transitions might be uncovered with careful comprehensive variable temperature structural and calorimetric studies, as in (NH 4 ) 2 {Ni[Cd(SCN) 6 ]}, which undergoes an order-disorder transition associated with the NH + 4 cation at around 120 K. Optimisation of the orientational order of A-site cations towards ferroic order might be possible through crystal-engineering, by tuning the hydrogen-bonding or introducing halogen-bonding moieties, and by deepening our understanding of the role of framework entropy in NCS-perovskites.