Treatment of the heterocycle 5-thioxo-4,5-dihydro-3,4-dimethyl-1,2,4-triazole (thioxotriazole) with sodium tetrahydroborate at 210 degreesC provides the new [N-3/S-3] ambidentate tripod ligand hydridotris(thioxotriazolyl)borate (Tt) as its sodium complex salt. Complexes of this ligand with sodium, bismuth(III), tin(IV), and manganese(I) have been synthesized and characterized by X-ray crystallography. The structures of these complexes illustrate the ambidentate character of the ligand with the softer metals bismuth and tin exhibiting sulfur coordination, while sodium and manganese(I) bond via the ligand nitrogen donors. In the [S-3] coordination mode the li-and creates eight-membered chelate rings with the metal with the consequence that the metal ligand unit adopts a propeller-type conformation with C-3-symmetry. However, in the [N-3] mode six-membered chelate rings are formed analogous to the familiar hydrotris(pyrazolyl)borate (Tp) ligand.