A　novel　three-dimensional　molybdenum(V)　phosphate　decorated　with　zinc　complex　cations,　Zn[Mo6O12(OH)3(PO　4)4]2{Zn4(H2O)　5(2,2′-bipy)2}2·2H2O　(2,2′-bipy=2,2′-bipyridine)　1,　has　been　hydrothermally　synthesized　and　characterized　by　single　crystal　X-ray　diffraction,　IR,　TGA　and　EPR　spectrum.　The　crystal　data　are　triclinic,　space　group　P1̄,　a=13.0842(7)　Å,　b=14.0065(11)　Å,　c=14.3344(10)　Å,　α=64.445(3)°,　β=88.805(3)°,　γ=74.099(3)°,　V=2264.9(3)　Å3,　Z=1,　R=0.0283,　wR=0.0749.　The　Zn[Mo6P4]2　units　are　connected　together　via　additional　zinc　coordination　complex　ions　to　give　a　novel　three-dimensional　molybdenum(V)　phosphate　framework.　©　2005　Elsevier　B.V.　All　rights　reserved.