LiCoPO4 crystallizes in the trigonal P31c space group. Li(1) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with three equivalent Co(1)O5 trigonal bipyramids. Co(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form distorted CoO5 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 Li(1)O4 tetrahedra, and edges with two equivalent Co(1)O5 trigonal bipyramids. 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 three equivalent Li(1)O4 tetrahedra and corners with six equivalent Co(1)O5 trigonal bipyramids. In the second P site, P(2) is bonded to one O(6) and three equivalent O(5) atoms to form PO4 tetrahedra that share corners with six equivalent Li(1)O4 tetrahedra and corners with three equivalent Co(1)O5 trigonal bipyramids. In the third P site, P(3) is bonded to one O(3) and three equivalent O(1) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent Co(1)O5 trigonal bipyramids. There are six inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one Co(1), and one P(3) 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 4-coordinate geometry to three equivalent Co(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to three equivalent Co(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a tetrahedral geometry to three equivalent Li(1) and one P(2) atom.
LiCoPO4 crystallizes in the trigonal P31c space group. Li(1) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with three equivalent Co(1)O5 trigonal bipyramids. The Li(1)-O(1) bond length is 2.02 Å. The Li(1)-O(2) bond length is 2.02 Å. The Li(1)-O(5) bond length is 1.94 Å. The Li(1)-O(6) bond length is 1.96 Å. Co(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form distorted CoO5 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 Li(1)O4 tetrahedra, and edges with two equivalent Co(1)O5 trigonal bipyramids. The Co(1)-O(1) bond length is 2.04 Å. The Co(1)-O(2) bond length is 2.04 Å. The Co(1)-O(3) bond length is 2.24 Å. The Co(1)-O(4) bond length is 2.30 Å. The Co(1)-O(5) bond length is 2.00 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 three equivalent Li(1)O4 tetrahedra and corners with six equivalent Co(1)O5 trigonal bipyramids. The P(1)-O(4) bond length is 1.58 Å. All P(1)-O(2) bond lengths are 1.55 Å. In the second P site, P(2) is bonded to one O(6) and three equivalent O(5) atoms to form PO4 tetrahedra that share corners with six equivalent Li(1)O4 tetrahedra and corners with three equivalent Co(1)O5 trigonal bipyramids. The P(2)-O(6) bond length is 1.54 Å. All P(2)-O(5) bond lengths are 1.56 Å. In the third P site, P(3) is bonded to one O(3) and three equivalent O(1) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent Co(1)O5 trigonal bipyramids. The P(3)-O(3) bond length is 1.61 Å. All P(3)-O(1) bond lengths are 1.54 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one Co(1), and one P(3) 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 4-coordinate geometry to three equivalent Co(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to three equivalent Co(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a tetrahedral geometry to three equivalent Li(1) and one P(2) atom.