Structural variations in bipyridine silver(I) complexes: Role of the substituents and counterions

4,4'-Disubstituted-2,2'-bipyri dines 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 NO3-, ClO4- and Sac (saccharinate, C7H4NO3S-), 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](CIO4)(2) and [(L1)(2)Ag](CIO4), while 1:1 and 2:1 species formed when the nitrate was used ([(L1)Ag(NO3)](infinity) and [(L1)(2)Ag](NO3). 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.