First Example of a Coordination Polymer Based on a Tetrahedral Cluster Cyano Complex of Re, Ag(I), bpy

Single crystals of Na2[{Ag(bpy)2}{Ag(H2O)}{Ag3(bpy)2(μ-CN)}{Re4As2S2(CN)12}]·2.75H2O are prepared by the reaction of the Na6[Re4As2S2(CN)12]·0.75CH3OH·6H2O tetrahedral cluster cyano complex, AgCN, NaCN and bpy (2,2′-bipyridine) in an aqueous solution. The obtained compound is the first example of a coordination polymer based on a tetrahedral cluster anion and Ag(I). In its structure, 3D layers are formed due to numerous bridges of CN groups and As–Ag bonds. The 3D supramolecular networks are additionally stabilized by weak intermolecular interactions, π⋯π interactions via bpy ligands, and argentophilic Ag⋯Ag interactions. The structure contains five crystallographically independent Ag atoms with coordination numbers 3, 4, 5.