Argentophilicity and solvent-induced structural diversity in double salts of silver acetylide with silver perfluoroalkyl carboxylates

A series of novel double salts of silver(I) were isolated by dissolving Ag(2)C(2) in a concentrated aqueous solution of R(F)CO(2)Ag (R(F) = CF(3), C(2)F(5)) and AgBF(4). Different ancillary solvento ligands such as H(2)O, CH(3)CN, and C(2)H(5)CN were found to affect the crystallization process that led to the assembly of various silver(I) cages with embedded C(2)(2-) ions. 2Ag(2)C(2) x 12CF(3)CO(2)Ag x 5H(2)O (1) consists of two independent C(2)@Ag(7) cages, each having the shape of a basket with a square base. Ag(2)C(2) x 6CF(3)CO(2)Ag x 3CH(3)CN (2) contains a zigzag chain of edge-sharing triangulated dodecahedra, and 4Ag(2)C(2) x 23CF(3)CO(2)Ag x 7C(2)H(5)CN x 2.5H(2)O (3) features an unusual double-walled silver column constructed from the fusion of four different kinds of irregular polyhedra. Ag(2)C(2) x 10C(2)F(5)CO(2)Ag x 9.5H(2)O (4), Ag(2)C(2) x 9C(2)F(5)CO(2)Ag x 3CH(3)CN x H(2)O (5), and Ag(2)C(2) x 6C(2)F(5)CO(2)Ag x 2C(2)H(5)CN (6) all contain an edge-sharing double cage with each single cage in the shape of a square antiprism, a capped square antiprism, and a triangulated dodecahedron, respectively.