Li3Co3(PO4)4 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(13), one O(14), one O(2), and one O(3) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one Co(2)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 52°. In the second Li site, Li(2) is bonded to one O(11), one O(16), one O(4), one O(5), and one O(7) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Co(3)O6 octahedra,  an edgeedge with one P(4)O4 tetrahedra, and  an edgeedge with one Co(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 59°. In the third Li site, Li(3) is bonded to one O(1), one O(10), one O(14), one O(15), and one O(3) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Co(2)O6 octahedra,  an edgeedge with one P(3)O4 tetrahedra, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 54°. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(11), one O(4), one O(6), one O(8), and one O(9) atom to form CoO5 trigonal bipyramids that share  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Co(3)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 56°. In the second Co site, Co(2) is bonded to one O(1), one O(13), one O(15), one O(16), one O(2), and one O(8) atom to form distorted CoO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Co(1)O5 trigonal bipyramid,  an edgeedge with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. In the third Co site, Co(3) is bonded to one O(10), one O(12), one O(5), one O(6), one O(7), and one O(9) atom to form CoO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid,  an edgeedge with one Li(2)O5 trigonal bipyramid, and  an edgeedge with one Co(1)O5 trigonal bipyramid. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(13), one O(3), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid, corners with two equivalent Li(1)O5 trigonal bipyramids, and  an edgeedge with one Co(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 39-53°. In the second P site, P(2) is bonded to one O(12), one O(2), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent Co(3)O6 octahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid, corners with two equivalent Co(1)O5 trigonal bipyramids, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 35-53°. In the third P site, P(3) is bonded to one O(1), one O(10), one O(11), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent Co(3)O6 octahedra,  a cornercorner with one Co(1)O5 trigonal bipyramid, corners with two equivalent Li(2)O5 trigonal bipyramids, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 38-50°. In the fourth P site, P(4) is bonded to one O(14), one O(15), one O(16), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, corners with two equivalent Li(3)O5 trigonal bipyramids, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 41-55°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one Li(3), one Co(2), and one P(3) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one Li(1), one Co(2), and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(1) 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(2) atom. In the fifth O site, O(5) is bonded in a T-shaped geometry to one Li(2), one Co(3), and one P(4) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(3), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Co(3), and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Co(1), one Co(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Co(1), one Co(3), and one P(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(3), one Co(3), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(2), one Co(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(1), one Co(3), and one P(2) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(2), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Li(3), one Co(2), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Li(2), one Co(2), and one P(4) atom.
Li3Co3(PO4)4 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(13), one O(14), one O(2), and one O(3) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one Co(2)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 52°. The Li(1)-O(12) bond length is 2.18 Å. The Li(1)-O(13) bond length is 2.03 Å. The Li(1)-O(14) bond length is 1.92 Å. The Li(1)-O(2) bond length is 2.08 Å. The Li(1)-O(3) bond length is 1.87 Å. In the second Li site, Li(2) is bonded to one O(11), one O(16), one O(4), one O(5), and one O(7) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Co(3)O6 octahedra,  an edgeedge with one P(4)O4 tetrahedra, and  an edgeedge with one Co(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 59°. The Li(2)-O(11) bond length is 1.91 Å. The Li(2)-O(16) bond length is 2.02 Å. The Li(2)-O(4) bond length is 1.99 Å. The Li(2)-O(5) bond length is 2.11 Å. The Li(2)-O(7) bond length is 1.98 Å. In the third Li site, Li(3) is bonded to one O(1), one O(10), one O(14), one O(15), and one O(3) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Co(2)O6 octahedra,  an edgeedge with one P(3)O4 tetrahedra, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 54°. The Li(3)-O(1) bond length is 2.13 Å. The Li(3)-O(10) bond length is 2.16 Å. The Li(3)-O(14) bond length is 1.84 Å. The Li(3)-O(15) bond length is 2.01 Å. The Li(3)-O(3) bond length is 1.98 Å. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(11), one O(4), one O(6), one O(8), and one O(9) atom to form CoO5 trigonal bipyramids that share  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Co(3)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 56°. The Co(1)-O(11) bond length is 1.90 Å. The Co(1)-O(4) bond length is 1.87 Å. The Co(1)-O(6) bond length is 1.99 Å. The Co(1)-O(8) bond length is 1.89 Å. The Co(1)-O(9) bond length is 1.94 Å. In the second Co site, Co(2) is bonded to one O(1), one O(13), one O(15), one O(16), one O(2), and one O(8) atom to form distorted CoO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Co(1)O5 trigonal bipyramid,  an edgeedge with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The Co(2)-O(1) bond length is 1.98 Å. The Co(2)-O(13) bond length is 1.95 Å. The Co(2)-O(15) bond length is 1.89 Å. The Co(2)-O(16) bond length is 2.05 Å. The Co(2)-O(2) bond length is 2.00 Å. The Co(2)-O(8) bond length is 2.48 Å. In the third Co site, Co(3) is bonded to one O(10), one O(12), one O(5), one O(6), one O(7), and one O(9) atom to form CoO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid,  an edgeedge with one Li(2)O5 trigonal bipyramid, and  an edgeedge with one Co(1)O5 trigonal bipyramid. The Co(3)-O(10) bond length is 2.06 Å. The Co(3)-O(12) bond length is 2.06 Å. The Co(3)-O(5) bond length is 1.88 Å. The Co(3)-O(6) bond length is 2.03 Å. The Co(3)-O(7) bond length is 1.96 Å. The Co(3)-O(9) bond length is 1.95 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(13), one O(3), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid, corners with two equivalent Li(1)O5 trigonal bipyramids, and  an edgeedge with one Co(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 39-53°. The P(1)-O(13) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.49 Å. The P(1)-O(8) bond length is 1.59 Å. The P(1)-O(9) bond length is 1.62 Å. In the second P site, P(2) is bonded to one O(12), one O(2), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent Co(3)O6 octahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid, corners with two equivalent Co(1)O5 trigonal bipyramids, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 35-53°. The P(2)-O(12) bond length is 1.55 Å. The P(2)-O(2) bond length is 1.54 Å. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.59 Å. In the third P site, P(3) is bonded to one O(1), one O(10), one O(11), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent Co(3)O6 octahedra,  a cornercorner with one Co(1)O5 trigonal bipyramid, corners with two equivalent Li(2)O5 trigonal bipyramids, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 38-50°. The P(3)-O(1) bond length is 1.56 Å. The P(3)-O(10) bond length is 1.56 Å. The P(3)-O(11) bond length is 1.55 Å. The P(3)-O(7) bond length is 1.56 Å. In the fourth P site, P(4) is bonded to one O(14), one O(15), one O(16), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, corners with two equivalent Li(3)O5 trigonal bipyramids, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 41-55°. The P(4)-O(14) bond length is 1.50 Å. The P(4)-O(15) bond length is 1.58 Å. The P(4)-O(16) bond length is 1.55 Å. The P(4)-O(5) bond length is 1.57 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one Li(3), one Co(2), and one P(3) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one Li(1), one Co(2), and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(1) 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(2) atom. In the fifth O site, O(5) is bonded in a T-shaped geometry to one Li(2), one Co(3), and one P(4) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(3), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Co(3), and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Co(1), one Co(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Co(1), one Co(3), and one P(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(3), one Co(3), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(2), one Co(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(1), one Co(3), and one P(2) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(2), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Li(3), one Co(2), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Li(2), one Co(2), and one P(4) atom.