Structural Variations in Bipyridine Silver(I) Complexes: Role of the Substituents and Counterions

4,4′-Disubstituted-2,2′-bipyridines have been used for the generation of various Ag(I) derivatives, where the nature of the counteranions in the reacting Ag(I) salt, such as NO 3 −, ClO 4 − and Sac (saccharinate, C 7 H 4 NO 3 S − ), plays a fundamental role in the stoichiometry of the reaction, dictating the ligand/metal ratio in the fulfilling of the Ag(I) coordination sphere. A competition between the anion coordinating capabilities and its shape and dimension led to only neutral and only ionic derivatives with saccharinate and perchlorate salts (ligand/metal ratios 1:1, 3:2 and 2:1: [(L1)Ag(Sac)], [(L1) 3 Ag 2 ](ClO 4 ) 2 and [(L1) 2 Ag](ClO 4 ), while 1:1 and 2:1 species formed when the nitrate was used ( [(L1)Ag(NO 3 )] ∞ and [(L1) 2 Ag](NO 3 ). Moreover, from the systematic structural investigation conducted on the crystalline solid state of the new Ag(I) complexes, it became clear that the presence of 4,4′-substituents on the bypiridine framework is a further significant factor in both the reciprocal combination between ligand and metal ion and the construction of their supramolecular organizations.