Syntheses, Structures and Reactivity of Novel Hydrates of ortho ‐Sulfidostannte Salts

By the synthesis of single‐crystalline K + , Rb + , Cs + and Ba 2+ salts of the ortho ‐sulfidostannate anion, using an efficient, three‐step fusing/extraction/evaporation method, all of the “missing links” in the table of ortho ‐sulfidostannates that can be prepared by this method, were added. The resulting hydrate compounds have the general composition [A n (H 2 O) m ][SnS 4 ] and represent useful starting materials for the synthesis of transition metal complexes with [SnS 4 ] 4− groups as binary main group elemental ligands. A quaternary salt [Cs 10 (H 2 O) 18 ][Mn 4 ( μ 4 ‐S)(SnS 4 ) 4 ] results from a reaction of the ternary Cs + salt with MnCl 2 ·4H 2 O. [K 4 (H 2 O) 4 ][SnS 4 ] ( 1 ), [Rb 4 (H 2 O) 4 ][SnS 4 ] ( 2 ), [Cs 4 (H 2 O) 3 ][SnS 4 ] ( 3 ), [Ba 2 (H 2 O) 11 ][SnS 4 ] ( 4 ), and [Cs 10 (H 2 O) 18 ][Mn 4 ( μ 4 ‐S)(SnS 4 ) 4 ] ( 5 ) were characterized by means of X‐ray diffractometry and optical absorption spectroscopy.