Room‐Temperature Synthesis of Three Compounds Featuring the [Ge 4 S 10 ] 4– Anion from a Water‐Soluble Thiogermanate Precursor

Applying a new synthetic approach in which transition metal complexes and a thiogermanate source are in different liquid phases resulted in crystallization of three new compounds with the adamantane‐like [Ge 4 S 10 ] 4– anion at room temperature. In the crystal structure of [Ni(cyclam)] 3 [Ni(cyclam)(H 2 O) 2 ][Ge 4 S 10 ] 2 · 21H 2 O ( I , cyclam = 1,4,8,11‐tetraazacyclotetradecane), the two different Ni 2+ ‐centered complexes and two unique [Ge 4 S 10 ] 4– anions are joined by H‐bonding interactions with a water cluster composed of condensed pentameric and hexameric rings. The compound {[Mn(2,2′‐bipy) 2 (H 2 O)] 2 Ge 4 S 10 } · 3H 2 O ( II , bipy = bipyridine) also contains the [Ge 4 S 10 ] 4– anion, which is expanded by two Mn 2+ ‐centered complexes through Mn–S–Ge bonds. The aqua ligand of the Mn 2+ ‐centered complex is involved in O–H ··· S H‐bonding to a terminal S atom of the anion with formation of a chain of {[Mn(2,2′‐bipy) 2 (H 2 O)] 2 Ge 4 S 10 } molecules. In the structure of [Fe(2,2′‐bipy) 3 ] 2 [Ge 4 S 10 ] · 10H 2 O ( III ), the [Fe(2,2′‐bipy) 3 ] 2+ complexes are arranged to form channels that host the thiogermanate anions. Between the 2,2′‐bipy ligands of the complexes π–π interactions are observed. The water molecules of crystallization form two different types of water clusters.