Li3Co2P5O16 crystallizes in the monoclinic P2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(5), one O(6), and one O(8) atom to form distorted LiO4 trigonal pyramids that share corners with four equivalent Co(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 60-70°. In the second Li site, Li(2) is bonded in a see-saw-like geometry to two equivalent O(2) and two equivalent O(4) atoms. Co(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(8) atom to form CoO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra, and corners with four equivalent Li(1)O4 trigonal pyramids. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(5), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 52-59°. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. In the third P site, P(3) is bonded to one O(1), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Co(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and corners with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 52-55°. There are eight 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(2), one Co(1), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(2), one Co(1), and one P(3) 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(1) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(1), one Co(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Co(1), and one P(1) atom.
Li3Co2P5O16 crystallizes in the monoclinic P2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(5), one O(6), and one O(8) atom to form distorted LiO4 trigonal pyramids that share corners with four equivalent Co(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 60-70°. The Li(1)-O(1) bond length is 2.10 Å. The Li(1)-O(5) bond length is 2.23 Å. The Li(1)-O(6) bond length is 2.03 Å. The Li(1)-O(8) bond length is 2.08 Å. In the second Li site, Li(2) is bonded in a see-saw-like geometry to two equivalent O(2) and two equivalent O(4) atoms. Both Li(2)-O(2) bond lengths are 1.99 Å. Both Li(2)-O(4) bond lengths are 2.29 Å. Co(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(8) atom to form CoO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra, and corners with four equivalent Li(1)O4 trigonal pyramids. The Co(1)-O(1) bond length is 2.07 Å. The Co(1)-O(2) bond length is 2.12 Å. The Co(1)-O(4) bond length is 2.17 Å. The Co(1)-O(5) bond length is 2.12 Å. The Co(1)-O(6) bond length is 2.08 Å. The Co(1)-O(8) bond length is 2.31 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(5), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 52-59°. The P(1)-O(3) bond length is 1.60 Å. The P(1)-O(5) bond length is 1.51 Å. The P(1)-O(7) bond length is 1.59 Å. The P(1)-O(8) bond length is 1.51 Å. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. Both P(2)-O(2) bond lengths are 1.50 Å. Both P(2)-O(3) bond lengths are 1.59 Å. In the third P site, P(3) is bonded to one O(1), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Co(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and corners with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 52-55°. The P(3)-O(1) bond length is 1.53 Å. The P(3)-O(4) bond length is 1.53 Å. The P(3)-O(6) bond length is 1.54 Å. The P(3)-O(7) bond length is 1.65 Å. There are eight 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(2), one Co(1), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(2), one Co(1), and one P(3) 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(1) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(1), one Co(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Co(1), and one P(1) atom.