LiCrO2 is Caswellsilverite-like structured and crystallizes in the orthorhombic Cmc2_1 space group. Li(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form LiO6 octahedra that share corners with nine equivalent Cr(1)O6 octahedra, edges with three equivalent Cr(1)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and  a faceface with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-48°. Cr(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form CrO6 octahedra that share corners with nine equivalent Li(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with six equivalent Cr(1)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-48°. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(1) and three equivalent Cr(1) atoms to form edge-sharing OLi3Cr3 octahedra. In the second O site, O(2) is bonded in a 6-coordinate geometry to three equivalent Li(1) and three equivalent Cr(1) atoms.
LiCrO2 is Caswellsilverite-like structured and crystallizes in the orthorhombic Cmc2_1 space group. Li(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form LiO6 octahedra that share corners with nine equivalent Cr(1)O6 octahedra, edges with three equivalent Cr(1)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and  a faceface with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-48°. There is one shorter (2.10 Å) and two longer (2.13 Å) Li(1)-O(1) bond lengths. All Li(1)-O(2) bond lengths are 2.25 Å. Cr(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form CrO6 octahedra that share corners with nine equivalent Li(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with six equivalent Cr(1)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-48°. All Cr(1)-O(1) bond lengths are 2.04 Å. All Cr(1)-O(2) bond lengths are 2.03 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(1) and three equivalent Cr(1) atoms to form edge-sharing OLi3Cr3 octahedra. In the second O site, O(2) is bonded in a 6-coordinate geometry to three equivalent Li(1) and three equivalent Cr(1) atoms.