Li3Co3(PO4)4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), one O(6), one O(7), and one O(8) atom to form LiO5 trigonal bipyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  a cornercorner with one Co(2)O5 trigonal bipyramid,  an edgeedge with one Co(1)O6 octahedra, and  an edgeedge with one Co(2)O5 trigonal bipyramid. In the second Li site, Li(2) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form CoO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Li(1)O5 trigonal bipyramids. In the second Co site, Co(2) is bonded to one O(1), one O(3), one O(5), one O(7), and one O(8) atom to form distorted CoO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one Li(1)O5 trigonal bipyramid. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O5 trigonal bipyramids, and corners with three equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 36-48°. In the second P site, P(2) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, and corners with three equivalent Co(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 51°. There are eight inequivalent O sites. In the first O site, O(7) is bonded in a 3-coordinate geometry to one Li(1), one Co(2), and one P(1) atom. In the second O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(2), and one P(1) atom. In the third O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Co(2), and one P(2) atom. In the fourth O site, O(2) is bonded in a bent 150 degrees geometry to one Co(1) and one P(1) atom. In the fifth O site, O(3) is bonded to one Li(1), one Li(2), one Co(2), and one P(2) atom to form distorted corner-sharing OLi2CoP trigonal pyramids. In the sixth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(1), and one P(2) atom. In the seventh O site, O(5) is bonded in a bent 150 degrees geometry to one Co(2) and one P(2) atom. In the eighth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(1), and one P(1) atom.
Li3Co3(PO4)4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), one O(6), one O(7), and one O(8) atom to form LiO5 trigonal bipyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  a cornercorner with one Co(2)O5 trigonal bipyramid,  an edgeedge with one Co(1)O6 octahedra, and  an edgeedge with one Co(2)O5 trigonal bipyramid. The Li(1)-O(3) bond length is 2.07 Å. The Li(1)-O(4) bond length is 2.06 Å. The Li(1)-O(6) bond length is 2.09 Å. The Li(1)-O(7) bond length is 2.06 Å. The Li(1)-O(8) bond length is 2.02 Å. In the second Li site, Li(2) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. Both Li(2)-O(1) bond lengths are 1.94 Å. Both Li(2)-O(3) bond lengths are 2.13 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form CoO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Li(1)O5 trigonal bipyramids. Both Co(1)-O(2) bond lengths are 1.86 Å. Both Co(1)-O(4) bond lengths are 1.93 Å. Both Co(1)-O(6) bond lengths are 2.05 Å. In the second Co site, Co(2) is bonded to one O(1), one O(3), one O(5), one O(7), and one O(8) atom to form distorted CoO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The Co(2)-O(1) bond length is 2.17 Å. The Co(2)-O(3) bond length is 1.97 Å. The Co(2)-O(5) bond length is 1.81 Å. The Co(2)-O(7) bond length is 2.08 Å. The Co(2)-O(8) bond length is 1.90 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O5 trigonal bipyramids, and corners with three equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 36-48°. The P(1)-O(2) bond length is 1.52 Å. The P(1)-O(6) bond length is 1.55 Å. The P(1)-O(7) bond length is 1.56 Å. The P(1)-O(8) bond length is 1.59 Å. In the second P site, P(2) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, and corners with three equivalent Co(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 51°. The P(2)-O(1) bond length is 1.53 Å. The P(2)-O(3) bond length is 1.57 Å. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(5) bond length is 1.56 Å. There are eight inequivalent O sites. In the first O site, O(7) is bonded in a 3-coordinate geometry to one Li(1), one Co(2), and one P(1) atom. In the second O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(2), and one P(1) atom. In the third O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Co(2), and one P(2) atom. In the fourth O site, O(2) is bonded in a bent 150 degrees geometry to one Co(1) and one P(1) atom. In the fifth O site, O(3) is bonded to one Li(1), one Li(2), one Co(2), and one P(2) atom to form distorted corner-sharing OLi2CoP trigonal pyramids. In the sixth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(1), and one P(2) atom. In the seventh O site, O(5) is bonded in a bent 150 degrees geometry to one Co(2) and one P(2) atom. In the eighth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(1), and one P(1) atom.