Studies of the anion effects on the molecular construction of a series of AgX complexes with bis(4-pyridyl)dimethylsilane (L) (X- = NO2-, NO3-, CF3SO3-, and PF6-) have been carried out. Formation of the skeletal bonds appears to be primarily associated with a suitable combination of bidentate N-donors of L and a variety of coordination georretries of Ag(l) ions. The L:Ag(l) ratios of the products are dependent on the nature of the polyatomic anions. The 1:1 adduct Ag(l)-L for NO2-, 3:4 adduct for NO3-, 2:3 adduct for CF3SO3-, and 1:2 adduct for PF6- have been obtained. A linear relationship between the ratio of ligand to metal and the coordinating ability of anions was observed. [Ag(NO2)(L)] has a unique sheet structure consisting of double helices, and [Ag-3(L)(4)](NO3)(3) is a 2 nm thick interwoven sheet structure consisting of nanotubes. The compound [Ag-2(L)(3)](CF3SO3)(2) affords a characteristic ladder-type channel structure, and [Ag(L)(2)](PF6) is a simple 2D grid structure.