Out of the metals which preferentially coordinate to S-terminus of NCS -Bi 3+ is perhaps the most attractive option, as it is a non-toxic and inexpensive. Previous work has established that the homoleptic octahedral [Bi(SCN) 6 ] 3 -anion can be used to form framework structures, in the alkali metal double hexagonal perovskite Cs 2 Na[Bi(SCN) 6 ] and the nickel arsenide structured Ln[Bi(SCN) 6 ] • xH 2 O, x = 3 -5, Ln = La-Dy. In addition, [Bi(SCN) 6 ] 3 -has been reported to form an insoluble compound suitable for a quantitative chemical analysis with chromium(III) solutions. A further interesting feature of these bismuth thiocyanate frameworks are their yellow and orange colours, also found in bismuth thiocyanate hemihydrate Bi(SCN) 3 • 1 2 H 2 O. 20 There are, however, no reported structures or physical properties of either cubic perovskite derived structures or transition metal based bismuth thiocyanate frameworks.