Efficient Synthesis and Properties of Single‐Crystalline [SnTe 4 ] 4− Salts

Single‐crystalline K + , Rb + , and Cs + salts of the ortho ‐tellurostannate anion have been prepared by a very efficient fusing/extraction/evaporation method. The resulting compounds with the general composition [A 4 (H 2 O) n ][SnTe 4 ] can be transferred into mixed H 2 O/ en solvates by solving the hydrates in 1,2‐diaminoethane ( en ) and ensuing layering by toluene. A mixed Rb + /Ba 2+ salt results from a partial cation exchange of the Rb + hydrate phase in solution. All hydrates react to polytellurides when exposed to air and represent useful starting materials for the synthesis of transition metal complexes with [SnTe 4 ] 4− groups as binary main group elemental ligands. [K 4 (H 2 O) 0.5 ][SnTe 4 ] ( 1 ), [Rb 4 (H 2 O) 2 ][SnTe 4 ] ( 2 ), [Cs 4 (H 2 O) 2 ][SnTe 4 ] ( 3 ), [K 4 (H 2 O)( en )][SnTe 4 ] ( 4 ), [Rb 4 (H 2 O) 0.67 ( en ) 0.33 ][SnTe 4 ] ( 5 ), [Cs 4 (H 2 O) 0.5 ( en ) 0.5 ][SnTe 4 ] ( 6 ), and [Rb 2 Ba(H 2 O) 11 ][SnTe 4 ] ( 7 ) were characterized by means of X‐ray diffractometry and optical absorption spectroscopy.