Silver(I) salts demonstrate a strong preference for forming linear complexes when reacted with 4-(phenylethynyl)pyridine (pep). The packing of these complexes was found to be strongly influenced by the counteranions, namely PF 6 -, BF 4 -, NO 2 -, NO 3 -, MeCO 2 -, CF 3 CO 2 -, MeSO 3 -, Tosand SCN -. This study evaluates a family of twelve solid-state structures that exhibit varying metal-to-ligand ratios, [Ag(pep) 2 ][PF 6 ]· MeCN, [Ag(pep) 2 ][PF 6 ], [Ag(pep) 2 ][BF 4 ], [Ag(pep) 2 ][Ag(NO 2 ) 2 ], [Ag(pep) 2 ][NO 3 ]·2H 2 O, [Ag(pep) 2 ][Ag(NO 3 ) 2 ], [Ag(pep) 2 (MeCO 2 )]· [a]