Li3CrO4 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-12°. In the second Li site, Li(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one 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(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-14°. In the third Li site, Li(3) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, corners with four equivalent Cr(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. Cr(1) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form CrO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), two equivalent Li(2), and two equivalent Cr(1) atoms to form OLi4Cr2 octahedra that share  a cornercorner with one O(4)Li4Cr2 octahedra,  a cornercorner with one O(3)Li5Cr octahedra, corners with four equivalent O(2)Li5Cr octahedra, edges with two equivalent O(1)Li4Cr2 octahedra, edges with two equivalent O(2)Li5Cr octahedra, edges with four equivalent O(4)Li4Cr2 octahedra, and edges with four equivalent O(3)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 3-17°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(3), and one Cr(1) atom to form OLi5Cr octahedra that share  a cornercorner with one O(4)Li4Cr2 octahedra,  a cornercorner with one O(3)Li5Cr octahedra, corners with four equivalent O(1)Li4Cr2 octahedra, edges with two equivalent O(1)Li4Cr2 octahedra, edges with two equivalent O(2)Li5Cr octahedra, edges with four equivalent O(4)Li4Cr2 octahedra, and edges with four equivalent O(3)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 3-12°. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), two equivalent Li(3), and one Cr(1) atom to form OLi5Cr octahedra that share  a cornercorner with one O(1)Li4Cr2 octahedra,  a cornercorner with one O(2)Li5Cr octahedra, corners with four equivalent O(4)Li4Cr2 octahedra, edges with two equivalent O(4)Li4Cr2 octahedra, edges with two equivalent O(3)Li5Cr octahedra, edges with four equivalent O(1)Li4Cr2 octahedra, and edges with four equivalent O(2)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 4-12°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), two equivalent Li(1), and two equivalent Cr(1) atoms to form OLi4Cr2 octahedra that share  a cornercorner with one O(1)Li4Cr2 octahedra,  a cornercorner with one O(2)Li5Cr octahedra, corners with four equivalent O(3)Li5Cr octahedra, edges with two equivalent O(4)Li4Cr2 octahedra, edges with two equivalent O(3)Li5Cr octahedra, edges with four equivalent O(1)Li4Cr2 octahedra, and edges with four equivalent O(2)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 4-17°.
Li3CrO4 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-12°. The Li(1)-O(1) bond length is 2.00 Å. The Li(1)-O(3) bond length is 2.06 Å. There is one shorter (2.08 Å) and one longer (2.18 Å) Li(1)-O(2) bond length. There is one shorter (2.08 Å) and one longer (2.15 Å) Li(1)-O(4) bond length. In the second Li site, Li(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one 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(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-14°. The Li(2)-O(2) bond length is 2.09 Å. The Li(2)-O(4) bond length is 2.03 Å. There is one shorter (2.08 Å) and one longer (2.17 Å) Li(2)-O(1) bond length. There is one shorter (2.06 Å) and one longer (2.16 Å) Li(2)-O(3) bond length. In the third Li site, Li(3) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, corners with four equivalent Cr(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. The Li(3)-O(1) bond length is 2.27 Å. The Li(3)-O(4) bond length is 2.25 Å. There is one shorter (2.01 Å) and one longer (2.15 Å) Li(3)-O(2) bond length. There is one shorter (1.99 Å) and one longer (2.14 Å) Li(3)-O(3) bond length. Cr(1) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form CrO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. The Cr(1)-O(2) bond length is 1.76 Å. The Cr(1)-O(3) bond length is 1.79 Å. There is one shorter (1.92 Å) and one longer (2.04 Å) Cr(1)-O(1) bond length. There is one shorter (1.89 Å) and one longer (2.06 Å) Cr(1)-O(4) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), two equivalent Li(2), and two equivalent Cr(1) atoms to form OLi4Cr2 octahedra that share  a cornercorner with one O(4)Li4Cr2 octahedra,  a cornercorner with one O(3)Li5Cr octahedra, corners with four equivalent O(2)Li5Cr octahedra, edges with two equivalent O(1)Li4Cr2 octahedra, edges with two equivalent O(2)Li5Cr octahedra, edges with four equivalent O(4)Li4Cr2 octahedra, and edges with four equivalent O(3)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 3-17°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(3), and one Cr(1) atom to form OLi5Cr octahedra that share  a cornercorner with one O(4)Li4Cr2 octahedra,  a cornercorner with one O(3)Li5Cr octahedra, corners with four equivalent O(1)Li4Cr2 octahedra, edges with two equivalent O(1)Li4Cr2 octahedra, edges with two equivalent O(2)Li5Cr octahedra, edges with four equivalent O(4)Li4Cr2 octahedra, and edges with four equivalent O(3)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 3-12°. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), two equivalent Li(3), and one Cr(1) atom to form OLi5Cr octahedra that share  a cornercorner with one O(1)Li4Cr2 octahedra,  a cornercorner with one O(2)Li5Cr octahedra, corners with four equivalent O(4)Li4Cr2 octahedra, edges with two equivalent O(4)Li4Cr2 octahedra, edges with two equivalent O(3)Li5Cr octahedra, edges with four equivalent O(1)Li4Cr2 octahedra, and edges with four equivalent O(2)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 4-12°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), two equivalent Li(1), and two equivalent Cr(1) atoms to form OLi4Cr2 octahedra that share  a cornercorner with one O(1)Li4Cr2 octahedra,  a cornercorner with one O(2)Li5Cr octahedra, corners with four equivalent O(3)Li5Cr octahedra, edges with two equivalent O(4)Li4Cr2 octahedra, edges with two equivalent O(3)Li5Cr octahedra, edges with four equivalent O(1)Li4Cr2 octahedra, and edges with four equivalent O(2)Li5Cr octahedra. The corner-sharing octahedral tilt angles range from 4-17°.