Argentophilic Infinite Chain, Column, and Layer Structures Assembled with the Multinuclear Silver(I)–Phenylethynide Supramolecular Synthon

Nine silver­(I) complexes bearing the phenylethynide ligand and different ancillary anions, namely, double salts AgCCPh·AgNO3 (1), 2AgCCPh·AgNO3 (2), [Ag5(CCPh)4(DMSO)2]­X [X = BF4 (3A), ClO4 (3B), PF6 (3C), AsF6 (3D), SbF6 (3E)], 2AgCCPh·5AgO2CCF3·4DMSO (4), and a triple salt 10AgCCPh·2AgOTf·AgNO3·3DMSO (5), have been synthesized and shown to possess coordination frameworks that are assembled with the supramolecular synthon Ph–CC⊃Agn (n = 3, 4, 5). Different argentophilic layers are found in nitrate complexes 1 and 2, which are crystallized from water and mixed water/DMSO, respectively. Difficulty was encountered in growing quality crystals of complexes 3A–3E, 4, and 5 bearing weakly coordinating anions, but DMSO proved to be a good solvent for crystallization by functioning as a coligand. The isostructural compounds 3A–3E exhibit the same type of pseudohexagonal packing of infinite silver columns, with the ancillary anionic component filling the intervening space and linking adjacent columns via weak hydrogen bonds. Three-dimensional supramolecular frameworks based on similar packing of silver chains and columns, respectively, are found in double salt 4 and triple salt 5.