LiVAlO4 is Spinel-derived structured and crystallizes in the orthorhombic Imm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra and corners with six equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-62°. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form LiO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra and corners with six equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-62°. V(1) 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 Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. Al(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form AlO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, edges with two equivalent Al(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one V(1), and two equivalent Al(1) atoms to form distorted OLiAl2V tetrahedra that share  a cornercorner with one O(1)LiAl2V tetrahedra, corners with five equivalent O(2)LiAl2V tetrahedra, corners with two equivalent O(4)LiAlV2 trigonal pyramids, corners with four equivalent O(3)LiAlV2 trigonal pyramids,  an edgeedge with one O(1)LiAl2V tetrahedra, and edges with two equivalent O(4)LiAlV2 trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), one V(1), and two equivalent Al(1) atoms to form distorted OLiAl2V tetrahedra that share  a cornercorner with one O(2)LiAl2V tetrahedra, corners with five equivalent O(1)LiAl2V tetrahedra, corners with two equivalent O(3)LiAlV2 trigonal pyramids, corners with four equivalent O(4)LiAlV2 trigonal pyramids,  an edgeedge with one O(2)LiAl2V tetrahedra, and edges with two equivalent O(3)LiAlV2 trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), two equivalent V(1), and one Al(1) atom to form distorted OLiAlV2 trigonal pyramids that share corners with two equivalent O(2)LiAl2V tetrahedra, corners with four equivalent O(1)LiAl2V tetrahedra,  a cornercorner with one O(3)LiAlV2 trigonal pyramid, corners with five equivalent O(4)LiAlV2 trigonal pyramids, edges with two equivalent O(2)LiAl2V tetrahedra, and  an edgeedge with one O(3)LiAlV2 trigonal pyramid. In the fourth O site, O(4) is bonded to one Li(2), two equivalent V(1), and one Al(1) atom to form distorted OLiAlV2 trigonal pyramids that share corners with two equivalent O(1)LiAl2V tetrahedra, corners with four equivalent O(2)LiAl2V tetrahedra,  a cornercorner with one O(4)LiAlV2 trigonal pyramid, corners with five equivalent O(3)LiAlV2 trigonal pyramids, edges with two equivalent O(1)LiAl2V tetrahedra, and  an edgeedge with one O(4)LiAlV2 trigonal pyramid.
LiVAlO4 is Spinel-derived structured and crystallizes in the orthorhombic Imm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra and corners with six equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-62°. Both Li(1)-O(2) bond lengths are 2.00 Å. Both Li(1)-O(3) bond lengths are 1.97 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form LiO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra and corners with six equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-62°. Both Li(2)-O(1) bond lengths are 2.01 Å. Both Li(2)-O(4) bond lengths are 1.96 Å. V(1) 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 Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. The V(1)-O(1) bond length is 1.93 Å. The V(1)-O(2) bond length is 1.94 Å. Both V(1)-O(3) bond lengths are 1.99 Å. Both V(1)-O(4) bond lengths are 1.99 Å. Al(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form AlO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, edges with two equivalent Al(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The Al(1)-O(3) bond length is 1.92 Å. The Al(1)-O(4) bond length is 1.92 Å. Both Al(1)-O(1) bond lengths are 1.94 Å. Both Al(1)-O(2) bond lengths are 1.94 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one V(1), and two equivalent Al(1) atoms to form distorted OLiAl2V tetrahedra that share  a cornercorner with one O(1)LiAl2V tetrahedra, corners with five equivalent O(2)LiAl2V tetrahedra, corners with two equivalent O(4)LiAlV2 trigonal pyramids, corners with four equivalent O(3)LiAlV2 trigonal pyramids,  an edgeedge with one O(1)LiAl2V tetrahedra, and edges with two equivalent O(4)LiAlV2 trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), one V(1), and two equivalent Al(1) atoms to form distorted OLiAl2V tetrahedra that share  a cornercorner with one O(2)LiAl2V tetrahedra, corners with five equivalent O(1)LiAl2V tetrahedra, corners with two equivalent O(3)LiAlV2 trigonal pyramids, corners with four equivalent O(4)LiAlV2 trigonal pyramids,  an edgeedge with one O(2)LiAl2V tetrahedra, and edges with two equivalent O(3)LiAlV2 trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), two equivalent V(1), and one Al(1) atom to form distorted OLiAlV2 trigonal pyramids that share corners with two equivalent O(2)LiAl2V tetrahedra, corners with four equivalent O(1)LiAl2V tetrahedra,  a cornercorner with one O(3)LiAlV2 trigonal pyramid, corners with five equivalent O(4)LiAlV2 trigonal pyramids, edges with two equivalent O(2)LiAl2V tetrahedra, and  an edgeedge with one O(3)LiAlV2 trigonal pyramid. In the fourth O site, O(4) is bonded to one Li(2), two equivalent V(1), and one Al(1) atom to form distorted OLiAlV2 trigonal pyramids that share corners with two equivalent O(1)LiAl2V tetrahedra, corners with four equivalent O(2)LiAl2V tetrahedra,  a cornercorner with one O(4)LiAlV2 trigonal pyramid, corners with five equivalent O(3)LiAlV2 trigonal pyramids, edges with two equivalent O(1)LiAl2V tetrahedra, and  an edgeedge with one O(4)LiAlV2 trigonal pyramid.