Aside from 6, all structures retain strong similarities to the parent Fe[Bi(SCN) 6 ] structure, despite the stark differences in composition. If one normalises the cell volume by the number of Bi atoms, this normalised volume is within a few percent of Fe[Bi(SCN) 6 ] for every compound, with the biggest discrepancy (5.5%) found for compound 6. This suggests that the high vacancy concentration does not produce significantly contracted frameworks, which is likely due to the fact that potential voids are filled by water clusters and molecular complexes. For the compounds containing octahedrally coordinated transition metal ions, 1-4, the pattern of tilts observed in the parent structure is retained [ESI Videos 1-3]. † In addition, the (large) magnitude of the octahedral tilting is not significantly perturbed, as the primary source of tilts is the shape of the frontier orbitals of NCS -and the resultant bent Bi-S-C bond angle. The retention of tilt-cooperativity in each of 1-4 is more surprising and is probably due in part to the presence of three dimensional connectivity of octahedra combined with the fact that no framework node has lower than four-fold coordination. These factors suggest that this Fe[Bi(SCN) 6 ] structure type is robust and likely to be found in other members of this family, and is suggestive that porous analogues may well be possible.