Li2VAlO4 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted LiO5 trigonal bipyramids that share corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent Al(1)O4 tetrahedra, corners with two equivalent Li(1)O5 trigonal bipyramids,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one V(1)O4 tetrahedra, and  an edgeedge with one Al(1)O4 tetrahedra. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form LiO4 tetrahedra that share corners with four equivalent V(1)O4 tetrahedra, corners with four equivalent Al(1)O4 tetrahedra, corners with three equivalent Li(1)O5 trigonal bipyramids, and  an edgeedge with one Li(1)O5 trigonal bipyramid. V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form VO4 tetrahedra that share corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent Al(1)O4 tetrahedra, corners with three equivalent Li(1)O5 trigonal bipyramids, and  an edgeedge with one Li(1)O5 trigonal bipyramid. Al(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form AlO4 tetrahedra that share corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, corners with three equivalent Li(1)O5 trigonal bipyramids, and  an edgeedge with one Li(1)O5 trigonal bipyramid. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), one V(1), and one Al(1) atom to form distorted OLi3AlV trigonal bipyramids that share corners with three equivalent O(2)Li2AlV tetrahedra, corners with three equivalent O(3)Li2AlV tetrahedra, corners with three equivalent O(4)Li2AlV tetrahedra, corners with two equivalent O(1)Li3AlV trigonal bipyramids,  an edgeedge with one O(2)Li2AlV tetrahedra,  an edgeedge with one O(3)Li2AlV tetrahedra, and  an edgeedge with one O(4)Li2AlV tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), and one Al(1) atom to form OLi2AlV tetrahedra that share corners with four equivalent O(3)Li2AlV tetrahedra, corners with four equivalent O(4)Li2AlV tetrahedra, corners with three equivalent O(1)Li3AlV trigonal bipyramids, and  an edgeedge with one O(1)Li3AlV trigonal bipyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), one V(1), and one Al(1) atom to form OLi2AlV tetrahedra that share corners with four equivalent O(2)Li2AlV tetrahedra, corners with four equivalent O(4)Li2AlV tetrahedra, corners with three equivalent O(1)Li3AlV trigonal bipyramids, and  an edgeedge with one O(1)Li3AlV trigonal bipyramid. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one V(1), and one Al(1) atom to form OLi2AlV tetrahedra that share corners with four equivalent O(2)Li2AlV tetrahedra, corners with four equivalent O(3)Li2AlV tetrahedra, corners with three equivalent O(1)Li3AlV trigonal bipyramids, and  an edgeedge with one O(1)Li3AlV trigonal bipyramid.
Li2VAlO4 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted LiO5 trigonal bipyramids that share corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent Al(1)O4 tetrahedra, corners with two equivalent Li(1)O5 trigonal bipyramids,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one V(1)O4 tetrahedra, and  an edgeedge with one Al(1)O4 tetrahedra. The Li(1)-O(2) bond length is 1.98 Å. The Li(1)-O(3) bond length is 2.01 Å. The Li(1)-O(4) bond length is 2.01 Å. There is one shorter (2.53 Å) and one longer (2.56 Å) Li(1)-O(1) bond length. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form LiO4 tetrahedra that share corners with four equivalent V(1)O4 tetrahedra, corners with four equivalent Al(1)O4 tetrahedra, corners with three equivalent Li(1)O5 trigonal bipyramids, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The Li(2)-O(1) bond length is 1.97 Å. The Li(2)-O(2) bond length is 1.98 Å. The Li(2)-O(3) bond length is 2.06 Å. The Li(2)-O(4) bond length is 2.03 Å. V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form VO4 tetrahedra that share corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent Al(1)O4 tetrahedra, corners with three equivalent Li(1)O5 trigonal bipyramids, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The V(1)-O(1) bond length is 1.92 Å. The V(1)-O(2) bond length is 1.93 Å. The V(1)-O(3) bond length is 1.97 Å. The V(1)-O(4) bond length is 1.94 Å. Al(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form AlO4 tetrahedra that share corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, corners with three equivalent Li(1)O5 trigonal bipyramids, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The Al(1)-O(1) bond length is 1.77 Å. The Al(1)-O(2) bond length is 1.79 Å. The Al(1)-O(3) bond length is 1.78 Å. The Al(1)-O(4) bond length is 1.79 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), one V(1), and one Al(1) atom to form distorted OLi3AlV trigonal bipyramids that share corners with three equivalent O(2)Li2AlV tetrahedra, corners with three equivalent O(3)Li2AlV tetrahedra, corners with three equivalent O(4)Li2AlV tetrahedra, corners with two equivalent O(1)Li3AlV trigonal bipyramids,  an edgeedge with one O(2)Li2AlV tetrahedra,  an edgeedge with one O(3)Li2AlV tetrahedra, and  an edgeedge with one O(4)Li2AlV tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), and one Al(1) atom to form OLi2AlV tetrahedra that share corners with four equivalent O(3)Li2AlV tetrahedra, corners with four equivalent O(4)Li2AlV tetrahedra, corners with three equivalent O(1)Li3AlV trigonal bipyramids, and  an edgeedge with one O(1)Li3AlV trigonal bipyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), one V(1), and one Al(1) atom to form OLi2AlV tetrahedra that share corners with four equivalent O(2)Li2AlV tetrahedra, corners with four equivalent O(4)Li2AlV tetrahedra, corners with three equivalent O(1)Li3AlV trigonal bipyramids, and  an edgeedge with one O(1)Li3AlV trigonal bipyramid. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one V(1), and one Al(1) atom to form OLi2AlV tetrahedra that share corners with four equivalent O(2)Li2AlV tetrahedra, corners with four equivalent O(3)Li2AlV tetrahedra, corners with three equivalent O(1)Li3AlV trigonal bipyramids, and  an edgeedge with one O(1)Li3AlV trigonal bipyramid.