The　low-temperature　alpha-form　and　the　high-temperature　beta-form　of　Zn3B2O6　have　been　prepared　by　solid-state　reactions.　The　X-ray　structural　analysis　showed　that　alpha-Zn3B2O6　crystallizes　in　a　triclinic　space　group　P1　with　a=6.302(2)angstrom,　b=8.248(1)angstrom,　c=10.020(1)angstrom,　alpha=89.85(1)degrees,　beta=89.79(1)degrees,　gamma=73.25(1)degrees,　Z=4　and　beta-Zn3B2O6　in　a　monoclinic　group　C2/c　with　a=23.840(1)angstrom,　b=5.049(1)angstrom,　c=8.388(1)angstrom,　beta=102.905(9)degrees,　Z=8.　alpha-Zn3B2O6　represents　a　new　structure　type　in　which　ZnO4　tetrahedra　are　connected　to　each　other　and　also　to　BO3　triangles　by　common　corners　giving　rise　to　a　three-dimensional　framework,　while　beta-Zn3B2O6　is　characterized　by　a　three-dimensional　network　built　from　corner-　and　edge-sharing　ZnO4　tetrahedra　as　well　as　corner-sharing　ZnO4　tetrahedra　and　BO3　triangles.　It　is　the　difference　in　the　orientation　of　the　BO3　groups　as　well　as　the　variation　of　the　connection　modes　of　ZnO4　groups　that　is　responsible　for　the　structural　differences　between　alpha-　and　beta-Zn3B2O6.　(c)　2006　Elsevier　B.V.　All　rights　reserved.