KV4O8 crystallizes in the tetragonal I4/m space group. K(1) is bonded in a distorted body-centered cubic geometry to eight equivalent O(1) atoms. V(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 48°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent K(1) and three equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to three equivalent V(1) atoms.
KV4O8 crystallizes in the tetragonal I4/m space group. K(1) is bonded in a distorted body-centered cubic geometry to eight equivalent O(1) atoms. All K(1)-O(1) bond lengths are 2.97 Å. V(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 48°. There are two shorter (1.99 Å) and one longer (2.04 Å) V(1)-O(1) bond length. There is one shorter (1.93 Å) and two longer (1.97 Å) V(1)-O(2) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent K(1) and three equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to three equivalent V(1) atoms.