Li3CrO4 is Caswellsilverite-like structured and crystallizes in the tetragonal P4_122 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)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 10-11°. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Cr(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. In the third Li site, Li(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)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 are 11°. Cr(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CrO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Cr(1) atom to form OLi5Cr octahedra that share corners with two equivalent O(1)Li5Cr octahedra, corners with four equivalent O(2)Li4Cr2 octahedra, edges with six equivalent O(2)Li4Cr2 octahedra, and edges with six equivalent O(1)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the second O site, O(2) is bonded to one Li(1), one Li(2), two equivalent Li(3), and two equivalent Cr(1) atoms to form OLi4Cr2 octahedra that share corners with two equivalent O(2)Li4Cr2 octahedra, corners with four equivalent O(1)Li5Cr octahedra, edges with six equivalent O(2)Li4Cr2 octahedra, and edges with six equivalent O(1)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 5-16°.
Li3CrO4 is Caswellsilverite-like structured and crystallizes in the tetragonal P4_122 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)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 10-11°. Both Li(1)-O(2) bond lengths are 2.11 Å. There are two shorter (2.06 Å) and two longer (2.12 Å) Li(1)-O(1) bond lengths. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Cr(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. Both Li(2)-O(2) bond lengths are 2.17 Å. There are two shorter (2.01 Å) and two longer (2.22 Å) Li(2)-O(1) bond lengths. In the third Li site, Li(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)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 are 11°. Both Li(3)-O(1) bond lengths are 2.07 Å. There are two shorter (2.00 Å) and two longer (2.23 Å) Li(3)-O(2) bond lengths. Cr(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CrO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. Both Cr(1)-O(1) bond lengths are 1.77 Å. There are two shorter (1.91 Å) and two longer (2.05 Å) Cr(1)-O(2) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Cr(1) atom to form OLi5Cr octahedra that share corners with two equivalent O(1)Li5Cr octahedra, corners with four equivalent O(2)Li4Cr2 octahedra, edges with six equivalent O(2)Li4Cr2 octahedra, and edges with six equivalent O(1)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the second O site, O(2) is bonded to one Li(1), one Li(2), two equivalent Li(3), and two equivalent Cr(1) atoms to form OLi4Cr2 octahedra that share corners with two equivalent O(2)Li4Cr2 octahedra, corners with four equivalent O(1)Li5Cr octahedra, edges with six equivalent O(2)Li4Cr2 octahedra, and edges with six equivalent O(1)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 5-16°.