Li2FeAlO4 is Stannite-like structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent Al(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent Fe(1)O4 tetrahedra, and  an edgeedge with one Li(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 Li(1)O4 tetrahedra, corners with four equivalent Fe(1)O4 tetrahedra, and corners with four equivalent Al(1)O4 tetrahedra. Fe(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form FeO4 tetrahedra that share corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, and corners with four equivalent Al(1)O4 tetrahedra. Al(1) is bonded to one O(2), one O(3), and two equivalent O(4) atoms to form AlO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent Fe(1)O4 tetrahedra, and  an edgeedge with one Al(1)O4 tetrahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), and one Fe(1) atom to form OLi3Fe tetrahedra that share corners with two equivalent O(4)LiAl2Fe tetrahedra, corners with four equivalent O(2)Li2AlFe tetrahedra, corners with four equivalent O(3)Li2AlFe tetrahedra, and  an edgeedge with one O(1)Li3Fe tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Fe(1), and one Al(1) atom to form OLi2AlFe tetrahedra that share corners with four equivalent O(3)Li2AlFe tetrahedra, corners with four equivalent O(1)Li3Fe tetrahedra, and corners with four equivalent O(4)LiAl2Fe tetrahedra. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Fe(1), and one Al(1) atom to form OLi2AlFe tetrahedra that share corners with four equivalent O(2)Li2AlFe tetrahedra, corners with four equivalent O(1)Li3Fe tetrahedra, and corners with four equivalent O(4)LiAl2Fe tetrahedra. In the fourth O site, O(4) is bonded to one Li(2), one Fe(1), and two equivalent Al(1) atoms to form OLiAl2Fe tetrahedra that share corners with two equivalent O(1)Li3Fe tetrahedra, corners with four equivalent O(2)Li2AlFe tetrahedra, corners with four equivalent O(3)Li2AlFe tetrahedra, and  an edgeedge with one O(4)LiAl2Fe tetrahedra.
Li2FeAlO4 is Stannite-like structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent Al(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent Fe(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The Li(1)-O(2) bond length is 2.04 Å. The Li(1)-O(3) bond length is 2.06 Å. There is one shorter (1.96 Å) and one longer (1.99 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 Li(1)O4 tetrahedra, corners with four equivalent Fe(1)O4 tetrahedra, and corners with four equivalent Al(1)O4 tetrahedra. The Li(2)-O(1) bond length is 1.89 Å. The Li(2)-O(2) bond length is 2.06 Å. The Li(2)-O(3) bond length is 2.01 Å. The Li(2)-O(4) bond length is 2.11 Å. Fe(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form FeO4 tetrahedra that share corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, and corners with four equivalent Al(1)O4 tetrahedra. The Fe(1)-O(1) bond length is 1.80 Å. The Fe(1)-O(2) bond length is 1.92 Å. The Fe(1)-O(3) bond length is 1.93 Å. The Fe(1)-O(4) bond length is 2.01 Å. Al(1) is bonded to one O(2), one O(3), and two equivalent O(4) atoms to form AlO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent Fe(1)O4 tetrahedra, and  an edgeedge with one Al(1)O4 tetrahedra. The Al(1)-O(2) bond length is 1.75 Å. The Al(1)-O(3) bond length is 1.75 Å. There is one shorter (1.83 Å) and one longer (1.84 Å) Al(1)-O(4) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), and one Fe(1) atom to form OLi3Fe tetrahedra that share corners with two equivalent O(4)LiAl2Fe tetrahedra, corners with four equivalent O(2)Li2AlFe tetrahedra, corners with four equivalent O(3)Li2AlFe tetrahedra, and  an edgeedge with one O(1)Li3Fe tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Fe(1), and one Al(1) atom to form OLi2AlFe tetrahedra that share corners with four equivalent O(3)Li2AlFe tetrahedra, corners with four equivalent O(1)Li3Fe tetrahedra, and corners with four equivalent O(4)LiAl2Fe tetrahedra. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Fe(1), and one Al(1) atom to form OLi2AlFe tetrahedra that share corners with four equivalent O(2)Li2AlFe tetrahedra, corners with four equivalent O(1)Li3Fe tetrahedra, and corners with four equivalent O(4)LiAl2Fe tetrahedra. In the fourth O site, O(4) is bonded to one Li(2), one Fe(1), and two equivalent Al(1) atoms to form OLiAl2Fe tetrahedra that share corners with two equivalent O(1)Li3Fe tetrahedra, corners with four equivalent O(2)Li2AlFe tetrahedra, corners with four equivalent O(3)Li2AlFe tetrahedra, and  an edgeedge with one O(4)LiAl2Fe tetrahedra.