Chair‐ and Boat‐Configurations of Silver(I) Complexes of Ditopic Ligand Involving Benzimidazolyl Substituents

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 Ag^I atoms in 1 are trigonally coordinated by two N_BIm atoms from the arms of L¹ and by one O atom of the anion CF₃CO₂^—, while those in 2 are only linearly ligated by N_BIm. 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.