A　rare　porous　zinc-organic　framework　with　ultrahigh　thermal　stability　over　500　degrees　C　was　obtained,　which　exhibits　a　CaF2-type　topology　formed　by　8-connected　tetranuclear　Zn-4　clusters　and　4-connected　phosphonocarboxylate　ligands.　Interestingly,　the　similar　reactions　to　the　zinc-organic　framework　but　in　the　absence　of　H2O　or　by　the　replacement　of　Zn2+　with　Co2+　can　yield　three　different　3D　cluster-based　frameworks　but　with　the　same　CaF2-type　topology.　(C)　2017　Chinese　Chemical　Society　and　Institute　of　Materia　Medica,　Chinese　Academy　of　Medical　Sciences.　Published　by　Elsevier　B.V.　All　rights　reserved.