Li4CrO5 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form LiO5 trigonal bipyramids that share  a cornercorner with one Cr(1)O5 trigonal bipyramid, corners with three equivalent Li(1)O5 trigonal bipyramids, corners with four equivalent Li(2)O5 trigonal bipyramids,  an edgeedge with one Li(1)O5 trigonal bipyramid, edges with two equivalent Cr(1)O5 trigonal bipyramids, and edges with three equivalent Li(2)O5 trigonal bipyramids. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form LiO5 trigonal bipyramids that share  a cornercorner with one Li(2)O5 trigonal bipyramid, corners with three equivalent Cr(1)O5 trigonal bipyramids, corners with four equivalent Li(1)O5 trigonal bipyramids,  an edgeedge with one Cr(1)O5 trigonal bipyramid, edges with two equivalent Li(2)O5 trigonal bipyramids, and edges with three equivalent Li(1)O5 trigonal bipyramids. Cr(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form CrO5 trigonal bipyramids that share corners with two equivalent Li(1)O5 trigonal bipyramids, corners with six equivalent Li(2)O5 trigonal bipyramids, edges with two equivalent Li(2)O5 trigonal bipyramids, and edges with four equivalent Li(1)O5 trigonal bipyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one Cr(1) atom to form a mixture of edge and corner-sharing OLi4Cr trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and one Cr(1) atom to form a mixture of edge and corner-sharing OLi4Cr trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Li(1), two equivalent Li(2), and one Cr(1) atom to form a mixture of edge and corner-sharing OLi4Cr trigonal bipyramids.
Li4CrO5 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form LiO5 trigonal bipyramids that share  a cornercorner with one Cr(1)O5 trigonal bipyramid, corners with three equivalent Li(1)O5 trigonal bipyramids, corners with four equivalent Li(2)O5 trigonal bipyramids,  an edgeedge with one Li(1)O5 trigonal bipyramid, edges with two equivalent Cr(1)O5 trigonal bipyramids, and edges with three equivalent Li(2)O5 trigonal bipyramids. The Li(1)-O(3) bond length is 2.03 Å. There is one shorter (1.96 Å) and one longer (1.98 Å) Li(1)-O(1) bond length. There is one shorter (2.03 Å) and one longer (2.09 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form LiO5 trigonal bipyramids that share  a cornercorner with one Li(2)O5 trigonal bipyramid, corners with three equivalent Cr(1)O5 trigonal bipyramids, corners with four equivalent Li(1)O5 trigonal bipyramids,  an edgeedge with one Cr(1)O5 trigonal bipyramid, edges with two equivalent Li(2)O5 trigonal bipyramids, and edges with three equivalent Li(1)O5 trigonal bipyramids. The Li(2)-O(3) bond length is 2.05 Å. There is one shorter (1.96 Å) and one longer (2.12 Å) Li(2)-O(1) bond length. There is one shorter (2.06 Å) and one longer (2.10 Å) Li(2)-O(2) bond length. Cr(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form CrO5 trigonal bipyramids that share corners with two equivalent Li(1)O5 trigonal bipyramids, corners with six equivalent Li(2)O5 trigonal bipyramids, edges with two equivalent Li(2)O5 trigonal bipyramids, and edges with four equivalent Li(1)O5 trigonal bipyramids. The Cr(1)-O(3) bond length is 1.75 Å. Both Cr(1)-O(1) bond lengths are 1.83 Å. Both Cr(1)-O(2) bond lengths are 1.74 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one Cr(1) atom to form a mixture of edge and corner-sharing OLi4Cr trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and one Cr(1) atom to form a mixture of edge and corner-sharing OLi4Cr trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Li(1), two equivalent Li(2), and one Cr(1) atom to form a mixture of edge and corner-sharing OLi4Cr trigonal bipyramids.