AlV2O4 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with six equivalent V(2)O6 octahedra and corners with six equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-64°. In the second V site, V(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent V(1)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. Al(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form AlO6 octahedra that share corners with six equivalent V(1)O4 tetrahedra, edges with two equivalent Al(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one V(1), two equivalent V(2), and one Al(1) atom. In the second O site, O(2) is bonded to one V(1), one V(2), and two equivalent Al(1) atoms to form a mixture of distorted corner and edge-sharing OAl2V2 trigonal pyramids.
AlV2O4 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with six equivalent V(2)O6 octahedra and corners with six equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-64°. Both V(1)-O(1) bond lengths are 1.99 Å. Both V(1)-O(2) bond lengths are 2.02 Å. In the second V site, V(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent V(1)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. Both V(2)-O(2) bond lengths are 2.13 Å. All V(2)-O(1) bond lengths are 2.09 Å. Al(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form AlO6 octahedra that share corners with six equivalent V(1)O4 tetrahedra, edges with two equivalent Al(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. Both Al(1)-O(1) bond lengths are 1.92 Å. All Al(1)-O(2) bond lengths are 1.96 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one V(1), two equivalent V(2), and one Al(1) atom. In the second O site, O(2) is bonded to one V(1), one V(2), and two equivalent Al(1) atoms to form a mixture of distorted corner and edge-sharing OAl2V2 trigonal pyramids.