LiCoPO4 crystallizes in the trigonal P31c space group. Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(6) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with three equivalent Co(1)O4 trigonal pyramids, and edges with two equivalent Li(1)O5 trigonal bipyramids. Co(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form distorted CoO4 trigonal pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent Li(1)O5 trigonal bipyramids, and corners with two equivalent Co(1)O4 trigonal pyramids. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(4) and three equivalent O(2) atoms to form PO4 tetrahedra that share corners with six equivalent Li(1)O5 trigonal bipyramids and corners with three equivalent Co(1)O4 trigonal pyramids. In the second P site, P(2) is bonded to one O(5) and three equivalent O(1) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O5 trigonal bipyramids and corners with six equivalent Co(1)O4 trigonal pyramids. In the third P site, P(3) is bonded to one O(6) and three equivalent O(3) atoms to form PO4 tetrahedra that share corners with six equivalent Li(1)O5 trigonal bipyramids and corners with three equivalent Co(1)O4 trigonal pyramids. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(1), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(1), and one P(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one Co(1), and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Li(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted tetrahedral geometry to three equivalent Co(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Li(1) and one P(3) atom.
LiCoPO4 crystallizes in the trigonal P31c space group. Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(6) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with three equivalent Co(1)O4 trigonal pyramids, and edges with two equivalent Li(1)O5 trigonal bipyramids. The Li(1)-O(1) bond length is 2.01 Å. The Li(1)-O(2) bond length is 2.24 Å. The Li(1)-O(3) bond length is 2.16 Å. The Li(1)-O(4) bond length is 2.33 Å. The Li(1)-O(6) bond length is 2.24 Å. Co(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form distorted CoO4 trigonal pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent Li(1)O5 trigonal bipyramids, and corners with two equivalent Co(1)O4 trigonal pyramids. The Co(1)-O(1) bond length is 1.99 Å. The Co(1)-O(2) bond length is 1.96 Å. The Co(1)-O(3) bond length is 1.93 Å. The Co(1)-O(5) bond length is 2.16 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(4) and three equivalent O(2) atoms to form PO4 tetrahedra that share corners with six equivalent Li(1)O5 trigonal bipyramids and corners with three equivalent Co(1)O4 trigonal pyramids. The P(1)-O(4) bond length is 1.54 Å. All P(1)-O(2) bond lengths are 1.56 Å. In the second P site, P(2) is bonded to one O(5) and three equivalent O(1) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O5 trigonal bipyramids and corners with six equivalent Co(1)O4 trigonal pyramids. The P(2)-O(5) bond length is 1.60 Å. All P(2)-O(1) bond lengths are 1.55 Å. In the third P site, P(3) is bonded to one O(6) and three equivalent O(3) atoms to form PO4 tetrahedra that share corners with six equivalent Li(1)O5 trigonal bipyramids and corners with three equivalent Co(1)O4 trigonal pyramids. The P(3)-O(6) bond length is 1.54 Å. All P(3)-O(3) bond lengths are 1.56 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(1), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(1), and one P(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one Co(1), and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Li(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted tetrahedral geometry to three equivalent Co(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Li(1) and one P(3) atom.