Abstract: | The ditopic ligand 1, 2‐bis(benzimidazol‐1‐ylmethyl)benzene (L1) as well as its silver(I) complexes [Ag2L12(CF3CO2)2] ( 1 ) and [Ag2L12](CF3SO3)2 · (L1) · 2H2O · 0.5C2H5OH ( 2 ) were prepared and structures characterized by X‐ray crystallography. The AgI atoms in 1 are trigonally coordinated by two NBIm atoms from the arms of L1 and by one O atom of the anion CF3CO2—, while those in 2 are only linearly ligated by NBIm. Different silver salts of CF3CO2— and CF3SO3— lead to different configurations of the dimeric unit [Ag2L12]2+: chair‐form in ( 1 ) but boat‐form in ( 2 ). The discrete molecules in both 1 and 2 are assembled into network structures through face‐to‐face π · · · π stacking and edge‐to‐face C—H · · · π interactions in the crystalline state, as well as N—H · · · O and C—H · · · O hydrogen bonds. Solution 1H NMR studies showed the formation of one sole species in solution or a rapid equilibrium was established on the NMR time scale at room temperature. |