Li3Ni2(PO4)3 crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(7), and two equivalent O(6) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Li(3)O6 octahedra, corners with three equivalent Ni(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 70-80°. In the second Li site, Li(2) is bonded to one O(1), one O(5), and two equivalent O(4) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Li(3)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 70-80°. In the third Li site, Li(3) is bonded to one O(2), one O(5), two equivalent O(4), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Ni(1)O6 octahedra, and  an edgeedge with one Ni(3)O6 octahedra. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(9), two equivalent O(4), and two equivalent O(8) atoms to form NiO6 octahedra that share corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Li(3)O6 octahedra, and  an edgeedge with one Ni(2)O6 octahedra. In the second Ni site, Ni(2) is bonded to two equivalent O(3) and four equivalent O(8) atoms to form NiO6 octahedra that share corners with six equivalent P(2)O4 tetrahedra and edges with two equivalent Ni(1)O6 octahedra. In the third Ni site, Ni(3) is bonded to two equivalent O(7) and four equivalent O(6) atoms to form NiO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with two equivalent Li(3)O6 octahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(5), one O(7), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with three equivalent Li(3)O6 octahedra, corners with three equivalent Ni(3)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-54°. In the second P site, P(2) is bonded to one O(1), one O(3), and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with three equivalent Ni(1)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra, and  a cornercorner with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-52°. In the third P site, P(3) is bonded to one O(2), one O(9), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with three equivalent Li(3)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-55°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(2), one Ni(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 Li(3), and one P(3) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Ni(2) and one P(2) atom. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Ni(1), and one P(3) atom to form a mixture of distorted edge and corner-sharing OLi2NiP tetrahedra. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one P(1) atom. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one Ni(3), and one P(1) atom to form a mixture of distorted edge and corner-sharing OLi2NiP tetrahedra. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one Ni(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Ni(1), one Ni(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Ni(1) and one P(3) atom.
Li3Ni2(PO4)3 crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(7), and two equivalent O(6) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Li(3)O6 octahedra, corners with three equivalent Ni(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 70-80°. The Li(1)-O(2) bond length is 1.94 Å. The Li(1)-O(7) bond length is 1.97 Å. Both Li(1)-O(6) bond lengths are 2.08 Å. In the second Li site, Li(2) is bonded to one O(1), one O(5), and two equivalent O(4) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Li(3)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 70-80°. The Li(2)-O(1) bond length is 1.97 Å. The Li(2)-O(5) bond length is 1.94 Å. Both Li(2)-O(4) bond lengths are 2.09 Å. In the third Li site, Li(3) is bonded to one O(2), one O(5), two equivalent O(4), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Ni(1)O6 octahedra, and  an edgeedge with one Ni(3)O6 octahedra. The Li(3)-O(2) bond length is 2.13 Å. The Li(3)-O(5) bond length is 2.11 Å. Both Li(3)-O(4) bond lengths are 2.18 Å. Both Li(3)-O(6) bond lengths are 2.17 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(9), two equivalent O(4), and two equivalent O(8) atoms to form NiO6 octahedra that share corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Li(3)O6 octahedra, and  an edgeedge with one Ni(2)O6 octahedra. The Ni(1)-O(1) bond length is 2.09 Å. The Ni(1)-O(9) bond length is 2.01 Å. Both Ni(1)-O(4) bond lengths are 2.09 Å. Both Ni(1)-O(8) bond lengths are 2.10 Å. In the second Ni site, Ni(2) is bonded to two equivalent O(3) and four equivalent O(8) atoms to form NiO6 octahedra that share corners with six equivalent P(2)O4 tetrahedra and edges with two equivalent Ni(1)O6 octahedra. Both Ni(2)-O(3) bond lengths are 2.05 Å. All Ni(2)-O(8) bond lengths are 2.11 Å. In the third Ni site, Ni(3) is bonded to two equivalent O(7) and four equivalent O(6) atoms to form NiO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with two equivalent Li(3)O6 octahedra. Both Ni(3)-O(7) bond lengths are 2.04 Å. All Ni(3)-O(6) bond lengths are 2.08 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(5), one O(7), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with three equivalent Li(3)O6 octahedra, corners with three equivalent Ni(3)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-54°. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.54 Å. Both P(1)-O(6) bond lengths are 1.56 Å. In the second P site, P(2) is bonded to one O(1), one O(3), and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with three equivalent Ni(1)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra, and  a cornercorner with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-52°. The P(2)-O(1) bond length is 1.56 Å. The P(2)-O(3) bond length is 1.55 Å. Both P(2)-O(8) bond lengths are 1.56 Å. In the third P site, P(3) is bonded to one O(2), one O(9), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with three equivalent Li(3)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-55°. The P(3)-O(2) bond length is 1.55 Å. The P(3)-O(9) bond length is 1.54 Å. Both P(3)-O(4) bond lengths are 1.56 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(2), one Ni(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 Li(3), and one P(3) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Ni(2) and one P(2) atom. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Ni(1), and one P(3) atom to form a mixture of distorted edge and corner-sharing OLi2NiP tetrahedra. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one P(1) atom. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one Ni(3), and one P(1) atom to form a mixture of distorted edge and corner-sharing OLi2NiP tetrahedra. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one Ni(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Ni(1), one Ni(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Ni(1) and one P(3) atom.