LiCoVO4 is Spinel-derived structured and crystallizes in the tetragonal P4_322 space group. Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Co(1)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted VO6 octahedra that share corners with six equivalent Co(1)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. Co(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form CoO4 tetrahedra that share corners with six equivalent Li(1)O6 octahedra and corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-66°. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one V(1), and one Co(1) atom to form distorted OLi2VCo trigonal pyramids that share corners with six equivalent O(1)Li2VCo trigonal pyramids, corners with six equivalent O(2)LiV2Co trigonal pyramids,  an edgeedge with one O(1)Li2VCo trigonal pyramid, and edges with two equivalent O(2)LiV2Co trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), two equivalent V(1), and one Co(1) atom to form distorted OLiV2Co trigonal pyramids that share corners with six equivalent O(1)Li2VCo trigonal pyramids, corners with six equivalent O(2)LiV2Co trigonal pyramids,  an edgeedge with one O(2)LiV2Co trigonal pyramid, and edges with two equivalent O(1)Li2VCo trigonal pyramids.
LiCoVO4 is Spinel-derived structured and crystallizes in the tetragonal P4_322 space group. Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Co(1)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. Both Li(1)-O(2) bond lengths are 2.17 Å. There are two shorter (2.07 Å) and two longer (2.14 Å) Li(1)-O(1) bond lengths. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted VO6 octahedra that share corners with six equivalent Co(1)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. Both V(1)-O(1) bond lengths are 1.77 Å. There are two shorter (1.90 Å) and two longer (2.11 Å) V(1)-O(2) bond lengths. Co(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form CoO4 tetrahedra that share corners with six equivalent Li(1)O6 octahedra and corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-66°. Both Co(1)-O(1) bond lengths are 1.97 Å. Both Co(1)-O(2) bond lengths are 1.96 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one V(1), and one Co(1) atom to form distorted OLi2VCo trigonal pyramids that share corners with six equivalent O(1)Li2VCo trigonal pyramids, corners with six equivalent O(2)LiV2Co trigonal pyramids,  an edgeedge with one O(1)Li2VCo trigonal pyramid, and edges with two equivalent O(2)LiV2Co trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), two equivalent V(1), and one Co(1) atom to form distorted OLiV2Co trigonal pyramids that share corners with six equivalent O(1)Li2VCo trigonal pyramids, corners with six equivalent O(2)LiV2Co trigonal pyramids,  an edgeedge with one O(2)LiV2Co trigonal pyramid, and edges with two equivalent O(1)Li2VCo trigonal pyramids.