Syntheses, Crystal Structures and Characterizations of New Vanadium Arsenites andArsenates. -The structures of (III), (IV), (VII), and (VIII) are determined by single crystal XRD. α-(III) crystallizes in the monoclinic space group C2/m with Z = 2 and β-(IV) in the tetragonal space group P4bm with Z = 2. The structure of α-(III) features a three-dimensional framework of corner-or edge-sharing VO6 octahedra with one-dimensional tunnels formed by 6-membered rings. The walls of the tunnels are capped by AsO3 groups. The β-polymorph (IV) exhibits a two-dimensional layer of corner-or edge-sharing VO5 square pyramids with AsO3 trigonal pyramids capping the same side of the layer. (VII) crystallizes in the triclinic space group P1 with Z = 2. Its structure shows a pillard layered architecture composed of vanadium oxide layers bridged by arsenate anions. (VIII) crystallizes in the orthorhombic space group P2 1 2 1 2 1 with Z = 4. Its three-dimensional structure contains corner-and edge-sharing VO6 octahedra, forming one-dimensional tunnels of 8-membered rings which are filled by AsO4 tetrahedra. α-(III) is a soft ferromagnet with a Curie temperature of 65 K. -(LIU, J.-H.; HE, Z.-Z.; KONG, F.; XU, X.; SUN, C.-F.; MAO*, J.-G.; J. Solid State Chem. 192 (2012) 263-272, http://dx.