Li2CrO3 is Caswellsilverite-like structured and crystallizes in the orthorhombic Pnna space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Cr(1)O6 octahedra, corners with six equivalent Li(2)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and faces with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-51°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, corners with six equivalent Cr(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Cr(1)O6 octahedra, and faces with two equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. 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 Cr(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, corners with six equivalent Li(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and faces with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-52°. There are two 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 a mixture of distorted corner and edge-sharing OLi4Cr2 pentagonal pyramids. In the second O site, O(2) is bonded in a 6-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and two equivalent Cr(1) atoms.
Li2CrO3 is Caswellsilverite-like structured and crystallizes in the orthorhombic Pnna space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Cr(1)O6 octahedra, corners with six equivalent Li(2)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and faces with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-51°. Both Li(1)-O(1) bond lengths are 2.06 Å. There are two shorter (2.02 Å) and two longer (2.17 Å) Li(1)-O(2) bond lengths. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, corners with six equivalent Cr(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Cr(1)O6 octahedra, and faces with two equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. Both Li(2)-O(1) bond lengths are 2.17 Å. There are two shorter (2.10 Å) and two longer (2.13 Å) Li(2)-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 Cr(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, corners with six equivalent Li(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and faces with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-52°. Both Cr(1)-O(1) bond lengths are 1.97 Å. There are two shorter (1.91 Å) and two longer (1.99 Å) Cr(1)-O(2) bond lengths. There are two 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 a mixture of distorted corner and edge-sharing OLi4Cr2 pentagonal pyramids. In the second O site, O(2) is bonded in a 6-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and two equivalent Cr(1) atoms.