LiVAlO4 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a 3-coordinate geometry to one O(2) and two equivalent O(4) atoms. V(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent Al(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-51°. Al(1) is bonded to one O(4), two equivalent O(3), and three equivalent O(1) atoms to form AlO6 octahedra that share corners with three equivalent V(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-51°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one V(1) and three equivalent Al(1) atoms to form OAl3V trigonal pyramids that share  a cornercorner with one O(4)Li2AlV2 square pyramid, corners with two equivalent O(1)Al3V trigonal pyramids, edges with two equivalent O(4)Li2AlV2 square pyramids, and edges with two equivalent O(1)Al3V trigonal pyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(1) and two equivalent Al(1) atoms. In the fourth O site, O(4) is bonded to two equivalent Li(1), two equivalent V(1), and one Al(1) atom to form distorted OLi2AlV2 square pyramids that share  a cornercorner with one O(1)Al3V trigonal pyramid, edges with two equivalent O(4)Li2AlV2 square pyramids, and edges with two equivalent O(1)Al3V trigonal pyramids.
LiVAlO4 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a 3-coordinate geometry to one O(2) and two equivalent O(4) atoms. The Li(1)-O(2) bond length is 1.94 Å. Both Li(1)-O(4) bond lengths are 2.06 Å. V(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent Al(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-51°. The V(1)-O(1) bond length is 2.00 Å. The V(1)-O(3) bond length is 1.86 Å. Both V(1)-O(2) bond lengths are 1.92 Å. Both V(1)-O(4) bond lengths are 2.08 Å. Al(1) is bonded to one O(4), two equivalent O(3), and three equivalent O(1) atoms to form AlO6 octahedra that share corners with three equivalent V(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-51°. The Al(1)-O(4) bond length is 1.90 Å. Both Al(1)-O(3) bond lengths are 1.90 Å. There is one shorter (1.89 Å) and two longer (1.97 Å) Al(1)-O(1) bond lengths. There are four inequivalent O sites. In the first O site, O(1) is bonded to one V(1) and three equivalent Al(1) atoms to form OAl3V trigonal pyramids that share  a cornercorner with one O(4)Li2AlV2 square pyramid, corners with two equivalent O(1)Al3V trigonal pyramids, edges with two equivalent O(4)Li2AlV2 square pyramids, and edges with two equivalent O(1)Al3V trigonal pyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(1) and two equivalent Al(1) atoms. In the fourth O site, O(4) is bonded to two equivalent Li(1), two equivalent V(1), and one Al(1) atom to form distorted OLi2AlV2 square pyramids that share  a cornercorner with one O(1)Al3V trigonal pyramid, edges with two equivalent O(4)Li2AlV2 square pyramids, and edges with two equivalent O(1)Al3V trigonal pyramids.