Li3CrO4 is Caswellsilverite-like structured and crystallizes in the orthorhombic Immm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Cr(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with eight equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second Li site, Li(2) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-12°. Cr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with eight equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. 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 two equivalent Cr(1) atoms to form OLi4Cr2 octahedra that share corners with six equivalent O(2)Li4Cr2 octahedra, edges with two equivalent O(1)Li4Cr2 octahedra, edges with two equivalent O(2)Li4Cr2 octahedra, and edges with eight equivalent O(3)Li5Cr octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Cr(1) atoms to form OLi4Cr2 octahedra that share corners with six equivalent O(1)Li4Cr2 octahedra, edges with two equivalent O(1)Li4Cr2 octahedra, edges with two equivalent O(2)Li4Cr2 octahedra, and edges with eight equivalent O(3)Li5Cr octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one Li(1), four equivalent Li(2), and one Cr(1) atom to form OLi5Cr octahedra that share corners with six equivalent O(3)Li5Cr octahedra, edges with four equivalent O(1)Li4Cr2 octahedra, edges with four equivalent O(2)Li4Cr2 octahedra, and edges with four equivalent O(3)Li5Cr octahedra. The corner-sharing octahedra are not tilted.
Li3CrO4 is Caswellsilverite-like structured and crystallizes in the orthorhombic Immm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Cr(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with eight equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. Both Li(1)-O(1) bond lengths are 2.17 Å. Both Li(1)-O(2) bond lengths are 2.16 Å. Both Li(1)-O(3) bond lengths are 2.22 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-12°. The Li(2)-O(1) bond length is 2.01 Å. The Li(2)-O(2) bond length is 2.01 Å. There are two shorter (2.08 Å) and two longer (2.09 Å) Li(2)-O(3) bond lengths. Cr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with eight equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. Both Cr(1)-O(1) bond lengths are 1.98 Å. Both Cr(1)-O(2) bond lengths are 1.98 Å. Both Cr(1)-O(3) bond lengths are 1.78 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 two equivalent Cr(1) atoms to form OLi4Cr2 octahedra that share corners with six equivalent O(2)Li4Cr2 octahedra, edges with two equivalent O(1)Li4Cr2 octahedra, edges with two equivalent O(2)Li4Cr2 octahedra, and edges with eight equivalent O(3)Li5Cr octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Cr(1) atoms to form OLi4Cr2 octahedra that share corners with six equivalent O(1)Li4Cr2 octahedra, edges with two equivalent O(1)Li4Cr2 octahedra, edges with two equivalent O(2)Li4Cr2 octahedra, and edges with eight equivalent O(3)Li5Cr octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one Li(1), four equivalent Li(2), and one Cr(1) atom to form OLi5Cr octahedra that share corners with six equivalent O(3)Li5Cr octahedra, edges with four equivalent O(1)Li4Cr2 octahedra, edges with four equivalent O(2)Li4Cr2 octahedra, and edges with four equivalent O(3)Li5Cr octahedra. The corner-sharing octahedra are not tilted.