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In the title complex, [Zn(C15H10ClN3)2](CF3SO3)2, the ZnII metal center is sixfold coordinated by three nitrogen atoms of each 4-chloroterpyridine ligand in a distorted octahedral geometry with triflouromethanesulfonate ions completing the outer coordination sphere of the complex. π–π stacking interactions between the pyridyl rings in adjacent molecules contribute to the alignment of the complexes in layers along the c axis.

The central AgI atom of the title salt, [Ag(INAM)2](CF3SO3)·2CH3CN, where INAM is isonicotinamide (C6H6N2O), is twofold coordinated by the pyridine N atoms of two isonicotinamide ligands creating a slightly distorted linear molecular geometry. The formation of polymeric chains {[Ag(INAM)2]+}n, held together by discrete hydrogen bonds through the amide group of the INAM ligand leaves voids for non-coordinating acetonitrile molecules that interact the silver metal center via regium bonds.