Three binuclear AgI complexes based on -diketonate and N-donor ligands, [Ag2(2,3- bpp)2(btfa)2] (1) and [Ag2(2,3-bpp)2(cbtfa)2] (2), and [Ag2(2,3-bpp)2(mbtfa)2] (3), where 2,3-bpp is 2,3-bis(2-pyridyl)pyrazine, Hbtfa is benzoyltrifluoroacetone, Hcbtfa is 4-chlorobenzoyltrifluoroacetone, and Hmbtfa is 4-methoxybenzoyltrifluoroacetone, were prepared and characterized by elemental analysis, IR, and 1H NMR spectroscopy and X-ray crystallography. Thermal and electrochemical properties were also studied. The complexes are structurally quite similar. Three nitrogen atoms of 2,3-bpp in 1, 2, and 3 are donors toward two silver(I) ions in syn-conformation. Abundant weak interactions, such as pi-pi C–H F, and C–H O interactions, provide additional assembly forces, leading to 3-D supramolecular networks for 1–3.