LiFeAlO4 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. Fe(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with three equivalent Al(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-53°. 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 Fe(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-53°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Fe(1) and three equivalent Al(1) atoms to form OAl3Fe trigonal pyramids that share  a cornercorner with one O(4)Li2AlFe2 trigonal bipyramid, corners with two equivalent O(1)Al3Fe trigonal pyramids, edges with two equivalent O(4)Li2AlFe2 trigonal bipyramids, and edges with two equivalent O(1)Al3Fe trigonal pyramids. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1) and two equivalent Fe(1) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Fe(1) and two equivalent Al(1) atoms. In the fourth O site, O(4) is bonded to two equivalent Li(1), two equivalent Fe(1), and one Al(1) atom to form distorted OLi2AlFe2 trigonal bipyramids that share  a cornercorner with one O(1)Al3Fe trigonal pyramid, edges with two equivalent O(4)Li2AlFe2 trigonal bipyramids, and edges with two equivalent O(1)Al3Fe trigonal pyramids.
LiFeAlO4 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 1.96 Å. Both Li(1)-O(4) bond lengths are 2.10 Å. Fe(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with three equivalent Al(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-53°. The Fe(1)-O(1) bond length is 2.00 Å. The Fe(1)-O(3) bond length is 1.91 Å. Both Fe(1)-O(2) bond lengths are 1.94 Å. Both Fe(1)-O(4) bond lengths are 2.07 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 Fe(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-53°. The Al(1)-O(4) bond length is 1.91 Å. Both Al(1)-O(3) bond lengths are 1.85 Å. There is one shorter (1.92 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 Fe(1) and three equivalent Al(1) atoms to form OAl3Fe trigonal pyramids that share  a cornercorner with one O(4)Li2AlFe2 trigonal bipyramid, corners with two equivalent O(1)Al3Fe trigonal pyramids, edges with two equivalent O(4)Li2AlFe2 trigonal bipyramids, and edges with two equivalent O(1)Al3Fe trigonal pyramids. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1) and two equivalent Fe(1) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Fe(1) and two equivalent Al(1) atoms. In the fourth O site, O(4) is bonded to two equivalent Li(1), two equivalent Fe(1), and one Al(1) atom to form distorted OLi2AlFe2 trigonal bipyramids that share  a cornercorner with one O(1)Al3Fe trigonal pyramid, edges with two equivalent O(4)Li2AlFe2 trigonal bipyramids, and edges with two equivalent O(1)Al3Fe trigonal pyramids.