LiCoPO4 is Spinel-derived structured and crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, corners with four equivalent Co(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, edges with two equivalent Co(1)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-68°. Co(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CoO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 58-68°. P(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-63°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Co(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Co(1), and one P(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one Co(1), and one P(1) atom.
LiCoPO4 is Spinel-derived structured and crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, corners with four equivalent Co(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, edges with two equivalent Co(1)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-68°. The Li(1)-O(1) bond length is 2.04 Å. The Li(1)-O(2) bond length is 2.37 Å. There are two shorter (2.15 Å) and two longer (2.32 Å) Li(1)-O(3) bond lengths. Co(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CoO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 58-68°. Both Co(1)-O(1) bond lengths are 2.10 Å. Both Co(1)-O(2) bond lengths are 2.15 Å. Both Co(1)-O(3) bond lengths are 2.17 Å. P(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-63°. The P(1)-O(1) bond length is 1.60 Å. The P(1)-O(2) bond length is 1.56 Å. Both P(1)-O(3) bond lengths are 1.55 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Co(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Co(1), and one P(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one Co(1), and one P(1) atom.