The　hydrothermal　reactions　of　pyridine-3,5-dicarboxylic　acid　(H(2)pydc)　with　AgNO3　in　the　mixed　solvent　of　acetonitrile　and　water　with　different　ratios　lead　to　the　formation　of　two　three-dimensional　network　complexes,　[Ag-5(pydc)(2)(CN)](n)　(1)　and　{[Ag-4(pydc)(2)]CH3CN}(n)　(2),　which　have　been　characterized　by　IR,　single-crystal　X-ray　diffraction　and　thermogravimetric　analyses.　It　has　been　demonstrated　that　the　ratio　of　acetonitrile　and　water　have　great　effect　on　the　structures　of　products.　The　high　ratio　of　acetonitrile　and　water　is　favorable　for　the　formation　of　complex　1,　while　the　low　volume　ratio　is　Propitious　to　complex　2.　The　luminescent　properties　of　complex　1　and　2　have　been　further　investigated,　and　show　that　the　luminescence　intensity　of　2　is　much　stronger　than　that　of　1　probably　due　to　the　direct　metal-metal　interactions　and　a　larger　HOMO-LUMO　gap　in　complex　2.　(C)　2009　Elsevier　Inc.　All　rights　reserved.