LiCoVO4 is Hausmannite-derived structured and crystallizes in the orthorhombic Pnma space group. 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 four equivalent Co(1)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-60°. V(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Co(1)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra, and edges with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-61°. Co(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form CoO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, corners with four equivalent Co(1)O6 octahedra, corners with four equivalent V(1)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, and  an edgeedge with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-60°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), and two equivalent Co(1) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one V(1), and one Co(1) atom. In the third O site, O(3) is bonded to two equivalent Li(1), one V(1), and one Co(1) atom to form distorted corner-sharing OLi2VCo tetrahedra.
LiCoVO4 is Hausmannite-derived structured and crystallizes in the orthorhombic Pnma space group. 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 four equivalent Co(1)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-60°. Both Li(1)-O(1) bond lengths are 2.27 Å. Both Li(1)-O(2) bond lengths are 2.19 Å. Both Li(1)-O(3) bond lengths are 2.11 Å. V(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Co(1)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra, and edges with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-61°. The V(1)-O(2) bond length is 1.73 Å. The V(1)-O(3) bond length is 1.74 Å. Both V(1)-O(1) bond lengths are 1.77 Å. Co(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form CoO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, corners with four equivalent Co(1)O6 octahedra, corners with four equivalent V(1)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, and  an edgeedge with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-60°. The Co(1)-O(2) bond length is 2.12 Å. The Co(1)-O(3) bond length is 2.12 Å. There are two shorter (2.06 Å) and two longer (2.25 Å) Co(1)-O(1) bond lengths. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), and two equivalent Co(1) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one V(1), and one Co(1) atom. In the third O site, O(3) is bonded to two equivalent Li(1), one V(1), and one Co(1) atom to form distorted corner-sharing OLi2VCo tetrahedra.