Controlling multiple orderings in metal thiocyanate molecular perovskites A(x){Ni[Bi(SCN)(6)]}

We report four new A-site vacancy ordered thiocyanate double double perovskites, [Image: see text] , A = K(+), NH(4)(+), CH(3)(NH(3))(+) (MeNH(3)(+)) and C(NH(2))(3)(+) (Gua(+)), including the first examples of thiocyanate perovskites containing organic A-site cations. We show, using a combination of X-ray and neutron diffraction, that the structure of these frameworks depends on the A-site cation, and that these frameworks possess complex vacancy-ordering patterns and cooperative octahedral tilts distinctly different from atomic perovskites. Density functional theory calculations uncover the energetic origin of these complex orders and allow us to propose a simple rule to predict favoured A-site cation orderings for a given tilt sequence. We use these insights, in combination with symmetry mode analyses, to show that these complex orders suggest a new route to non-centrosymmetric perovskites, and mean this family of materials could contain excellent candidates for piezo- and ferroelectric applications.