LiCrAlO4 crystallizes in the orthorhombic P2_12_12_1 space group. Li(1) is bonded in a 3-coordinate geometry to one O(2), one O(3), and two equivalent O(4) atoms. Cr(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with three equivalent Al(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-53°. 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 Cr(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-53°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Cr(1) and three equivalent Al(1) atoms to form OAl3Cr trigonal pyramids that share  a cornercorner with one O(4)Li2AlCr2 square pyramid, corners with two equivalent O(1)Al3Cr trigonal pyramids, corners with five equivalent O(3)LiAl2Cr trigonal pyramids, edges with two equivalent O(4)Li2AlCr2 square pyramids,  an edgeedge with one O(3)LiAl2Cr trigonal pyramid, and edges with two equivalent O(1)Al3Cr trigonal pyramids. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1) and two equivalent Cr(1) atoms. In the third O site, O(3) is bonded to one Li(1), one Cr(1), and two equivalent Al(1) atoms to form distorted OLiAl2Cr trigonal pyramids that share corners with two equivalent O(4)Li2AlCr2 square pyramids, corners with two equivalent O(3)LiAl2Cr trigonal pyramids, corners with five equivalent O(1)Al3Cr trigonal pyramids, edges with two equivalent O(4)Li2AlCr2 square pyramids, and  an edgeedge with one O(1)Al3Cr trigonal pyramid. In the fourth O site, O(4) is bonded to two equivalent Li(1), two equivalent Cr(1), and one Al(1) atom to form OLi2AlCr2 square pyramids that share  a cornercorner with one O(1)Al3Cr trigonal pyramid, corners with two equivalent O(3)LiAl2Cr trigonal pyramids, edges with two equivalent O(4)Li2AlCr2 square pyramids, edges with two equivalent O(1)Al3Cr trigonal pyramids, and edges with two equivalent O(3)LiAl2Cr trigonal pyramids.
LiCrAlO4 crystallizes in the orthorhombic P2_12_12_1 space group. Li(1) is bonded in a 3-coordinate geometry to one O(2), one O(3), and two equivalent O(4) atoms. The Li(1)-O(2) bond length is 1.97 Å. The Li(1)-O(3) bond length is 2.53 Å. There is one shorter (2.05 Å) and one longer (2.08 Å) Li(1)-O(4) bond length. Cr(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with three equivalent Al(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-53°. The Cr(1)-O(1) bond length is 1.96 Å. The Cr(1)-O(3) bond length is 1.87 Å. There is one shorter (1.83 Å) and one longer (1.99 Å) Cr(1)-O(2) bond length. There is one shorter (2.03 Å) and one longer (2.05 Å) Cr(1)-O(4) bond length. 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 Cr(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-53°. The Al(1)-O(4) bond length is 1.92 Å. There is one shorter (1.87 Å) and one longer (1.88 Å) Al(1)-O(3) bond length. There are a spread of Al(1)-O(1) bond distances ranging from 1.90-1.97 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Cr(1) and three equivalent Al(1) atoms to form OAl3Cr trigonal pyramids that share  a cornercorner with one O(4)Li2AlCr2 square pyramid, corners with two equivalent O(1)Al3Cr trigonal pyramids, corners with five equivalent O(3)LiAl2Cr trigonal pyramids, edges with two equivalent O(4)Li2AlCr2 square pyramids,  an edgeedge with one O(3)LiAl2Cr trigonal pyramid, and edges with two equivalent O(1)Al3Cr trigonal pyramids. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1) and two equivalent Cr(1) atoms. In the third O site, O(3) is bonded to one Li(1), one Cr(1), and two equivalent Al(1) atoms to form distorted OLiAl2Cr trigonal pyramids that share corners with two equivalent O(4)Li2AlCr2 square pyramids, corners with two equivalent O(3)LiAl2Cr trigonal pyramids, corners with five equivalent O(1)Al3Cr trigonal pyramids, edges with two equivalent O(4)Li2AlCr2 square pyramids, and  an edgeedge with one O(1)Al3Cr trigonal pyramid. In the fourth O site, O(4) is bonded to two equivalent Li(1), two equivalent Cr(1), and one Al(1) atom to form OLi2AlCr2 square pyramids that share  a cornercorner with one O(1)Al3Cr trigonal pyramid, corners with two equivalent O(3)LiAl2Cr trigonal pyramids, edges with two equivalent O(4)Li2AlCr2 square pyramids, edges with two equivalent O(1)Al3Cr trigonal pyramids, and edges with two equivalent O(3)LiAl2Cr trigonal pyramids.