Two silver(I) coordination solids in a single crystallization: Flexible metallacyclodimer versus helical channel network

Abstract

Studies on the self-assembly of AgClO 4 with 1,2-bis(dimethyl(4-pyridyl)silyl)ethane (L) were carried out. The slow diffusion of an organic solution of L into an aqueous solution of AgClO 4 affords two different single crystalline solids, block and thin-plate crystals. The block crystal consists of metallacyclodimers of, [Ag(L)] 2(ClO 4) 2 whereas the thin-plate crystal consists of unique ligand-induced helical channel networks, [Ag 2(L) 3](ClO 4) 2. The block and thin-plate crystals form in a ratio of 1:9, respectively, in a mixture of water and ethanol, but the ratio is depending on solvents and concentrations. In addition, the block crystal has two significantly different metallacyclodimeric structures in a unit cell, presumably owing to the flexible 26-membered cyclodimer including a flexible transannular argentophilic interaction. Such subtle effects may be ascribed to the existence of a variety of eclipsed, gauche, or anti-conformers of L.