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.