AlV2O4 is Spinel-like structured and crystallizes in the trigonal R-3m space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to six equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent Al(2)O4 tetrahedra and edges with six equivalent V(3)O6 octahedra. In the second V site, V(2) is bonded to six equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Al(1)O4 tetrahedra and edges with six equivalent V(3)O6 octahedra. In the third V site, V(3) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent Al(1)O4 tetrahedra, corners with three equivalent Al(2)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with four equivalent V(3)O6 octahedra. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1) and three equivalent O(3) atoms to form AlO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra and corners with nine equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-59°. In the second Al site, Al(2) is bonded to one O(2) and three equivalent O(4) atoms to form AlO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra and corners with nine equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-59°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal pyramidal geometry to three equivalent V(3) and one Al(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to three equivalent V(3) and one Al(2) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one V(2), two equivalent V(3), and one Al(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one V(1), two equivalent V(3), and one Al(2) atom.
AlV2O4 is Spinel-like structured and crystallizes in the trigonal R-3m space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to six equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent Al(2)O4 tetrahedra and edges with six equivalent V(3)O6 octahedra. All V(1)-O(4) bond lengths are 2.16 Å. In the second V site, V(2) is bonded to six equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Al(1)O4 tetrahedra and edges with six equivalent V(3)O6 octahedra. All V(2)-O(3) bond lengths are 2.10 Å. In the third V site, V(3) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent Al(1)O4 tetrahedra, corners with three equivalent Al(2)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with four equivalent V(3)O6 octahedra. The V(3)-O(1) bond length is 2.16 Å. The V(3)-O(2) bond length is 2.09 Å. Both V(3)-O(3) bond lengths are 2.05 Å. Both V(3)-O(4) bond lengths are 2.10 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1) and three equivalent O(3) atoms to form AlO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra and corners with nine equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-59°. The Al(1)-O(1) bond length is 1.82 Å. All Al(1)-O(3) bond lengths are 1.78 Å. In the second Al site, Al(2) is bonded to one O(2) and three equivalent O(4) atoms to form AlO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra and corners with nine equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-59°. The Al(2)-O(2) bond length is 1.82 Å. All Al(2)-O(4) bond lengths are 1.79 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal pyramidal geometry to three equivalent V(3) and one Al(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to three equivalent V(3) and one Al(2) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one V(2), two equivalent V(3), and one Al(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one V(1), two equivalent V(3), and one Al(2) atom.