Bi(NCS) 3 can be synthesized as a orange-yellow crystals through the slow evaporation of aqueous H 3 [Bi(SCN) 6 ] solutions obtained by the acid-base reaction between ethereal HSCN and Bi 2 O 2 (CO 3 ). Like Sn(NCS) 2 , it also has stereochemically active metal ions, crystallising in P1, however it is the most structurally complex of all the reported metal thiocyanate binaries, with two distinct metal ions and six distinct NCS -ions. Both bismuth sites are very distorted, Bi1 has four short bonds, BiN 2 S 2 , but including longer bonds can be considered to be seven coordinate, BiN 4 S 3 ; Bi2 considering short bonds is a very distorted octahedron,BiN 2 S 4 , but has an additional short contact to third N atom to make a seven coordinate {BiN_3S_4} coordination. These larger (seven vertex) polyhedra directly edge-share through one nitrogen and one sulfur, and are connected into a 3D framework through the length of the thiocyanates. Sb(NCS) 3 can be obtained as colourless crystals by removing THF from the relevant solvate, itself synthesized from the reaction of SbF 3 and trimethylsilyl isothiocyanate. It crystallizes in the high-symmetry yet polar I4 1 cd space group, with a very significant stereochemically active lone pair. Considering only the shortest bonds it can be thought of as comprising solely of molecular Sb(NCS) 3 units. If slightly longer (3.1 Å) Sb-S bonds are considered, the Sb(III) cation has distorted octahedral coordination, SbN 3S3 . These octahedra edge-share (through the length of the thiocyanate) to form infinite chains. These chains corner-share (though only on alternate layers) to form a 3D network. For these main-group and d 10 transition metal elements, the lack of crystalfield stabilization energy appears to permit a much wider variety of structure types, and indeed the presence of significant stereochemically active lone-pairs in Sn(II), Sb(III) and Bi(III) produces the most complex reported binary metal thiocyanate structures.