LiCr2O3 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c 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 two equivalent Cr(1)O6 octahedra, corners with four equivalent Cr(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, edges with three equivalent Cr(2)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. In the second Li site, Li(2) 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 two equivalent Cr(1)O6 octahedra, corners with four equivalent Cr(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Cr(2)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. There are three inequivalent Cr sites. In the first Cr site, 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 two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with six equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. In the second Cr site, Cr(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted CrO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with four equivalent Cr(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. In the third Cr site, Cr(3) 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 two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, edges with three equivalent Cr(1)O6 octahedra, and edges with three equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Li(1), one Li(2), one Cr(1), one Cr(2), and two equivalent Cr(3) atoms to form a mixture of corner and edge-sharing OLi2Cr4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second O site, O(1) is bonded to one Li(1), one Li(2), one Cr(1), one Cr(2), and two equivalent Cr(3) atoms to form a mixture of corner and edge-sharing OLi2Cr4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the third O site, O(2) is bonded to one Li(1), one Li(2), one Cr(1), one Cr(2), and two equivalent Cr(3) atoms to form a mixture of distorted corner and edge-sharing OLi2Cr4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°.
LiCr2O3 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c 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 two equivalent Cr(1)O6 octahedra, corners with four equivalent Cr(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, edges with three equivalent Cr(2)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. Both Li(1)-O(1) bond lengths are 2.17 Å. Both Li(1)-O(2) bond lengths are 2.25 Å. Both Li(1)-O(3) bond lengths are 2.27 Å. In the second Li site, Li(2) 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 two equivalent Cr(1)O6 octahedra, corners with four equivalent Cr(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Cr(2)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. Both Li(2)-O(1) bond lengths are 2.39 Å. Both Li(2)-O(2) bond lengths are 2.08 Å. Both Li(2)-O(3) bond lengths are 2.27 Å. There are three inequivalent Cr sites. In the first Cr site, 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 two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with six equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. Both Cr(1)-O(1) bond lengths are 2.26 Å. Both Cr(1)-O(2) bond lengths are 2.09 Å. Both Cr(1)-O(3) bond lengths are 2.20 Å. In the second Cr site, Cr(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted CrO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with four equivalent Cr(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. Both Cr(2)-O(1) bond lengths are 2.07 Å. Both Cr(2)-O(2) bond lengths are 2.44 Å. Both Cr(2)-O(3) bond lengths are 2.11 Å. In the third Cr site, Cr(3) 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 two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, edges with three equivalent Cr(1)O6 octahedra, and edges with three equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. There is one shorter (2.03 Å) and one longer (2.07 Å) Cr(3)-O(1) bond length. There is one shorter (2.03 Å) and one longer (2.04 Å) Cr(3)-O(2) bond length. There is one shorter (2.05 Å) and one longer (2.08 Å) Cr(3)-O(3) bond length. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Li(1), one Li(2), one Cr(1), one Cr(2), and two equivalent Cr(3) atoms to form a mixture of corner and edge-sharing OLi2Cr4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second O site, O(1) is bonded to one Li(1), one Li(2), one Cr(1), one Cr(2), and two equivalent Cr(3) atoms to form a mixture of corner and edge-sharing OLi2Cr4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the third O site, O(2) is bonded to one Li(1), one Li(2), one Cr(1), one Cr(2), and two equivalent Cr(3) atoms to form a mixture of distorted corner and edge-sharing OLi2Cr4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°.