Li3CrO3 crystallizes in the trigonal P-31c space group. Li(1) is bonded to four equivalent O(1) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, corners with six equivalent Li(1)O4 tetrahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra, and edges with three equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-60°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to six equivalent O(1) atoms to form CrO6 octahedra that share corners with twelve equivalent Li(1)O4 tetrahedra, edges with three equivalent Cr(2)O6 octahedra, and edges with six equivalent Li(1)O4 tetrahedra. In the second Cr site, Cr(2) is bonded to six equivalent O(1) atoms to form CrO6 octahedra that share corners with twelve equivalent Li(1)O4 tetrahedra, edges with three equivalent Cr(1)O6 octahedra, and edges with six equivalent Li(1)O4 tetrahedra. O(1) is bonded in a 6-coordinate geometry to four equivalent Li(1), one Cr(1), and one Cr(2) atom.
Li3CrO3 crystallizes in the trigonal P-31c space group. Li(1) is bonded to four equivalent O(1) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, corners with six equivalent Li(1)O4 tetrahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra, and edges with three equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-60°. There are a spread of Li(1)-O(1) bond distances ranging from 1.88-2.07 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to six equivalent O(1) atoms to form CrO6 octahedra that share corners with twelve equivalent Li(1)O4 tetrahedra, edges with three equivalent Cr(2)O6 octahedra, and edges with six equivalent Li(1)O4 tetrahedra. All Cr(1)-O(1) bond lengths are 2.06 Å. In the second Cr site, Cr(2) is bonded to six equivalent O(1) atoms to form CrO6 octahedra that share corners with twelve equivalent Li(1)O4 tetrahedra, edges with three equivalent Cr(1)O6 octahedra, and edges with six equivalent Li(1)O4 tetrahedra. All Cr(2)-O(1) bond lengths are 2.09 Å. O(1) is bonded in a 6-coordinate geometry to four equivalent Li(1), one Cr(1), and one Cr(2) atom.