Li3Ni(PO4)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Li(2)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with two equivalent Ni(1)O6 octahedra. In the second Li site, Li(2) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 68-82°. Ni(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NiO6 octahedra that share corners with six equivalent Li(2)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. P(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra, corners with two equivalent Li(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-53°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Ni(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing OLi2NiP tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(2), one Ni(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom.
Li3Ni(PO4)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Li(2)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with two equivalent Ni(1)O6 octahedra. Both Li(1)-O(3) bond lengths are 2.11 Å. All Li(1)-O(1) bond lengths are 2.21 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 68-82°. The Li(2)-O(2) bond length is 1.99 Å. The Li(2)-O(3) bond length is 1.94 Å. Both Li(2)-O(1) bond lengths are 2.11 Å. Ni(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NiO6 octahedra that share corners with six equivalent Li(2)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. Both Ni(1)-O(2) bond lengths are 2.06 Å. All Ni(1)-O(1) bond lengths are 2.10 Å. P(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra, corners with two equivalent Li(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-53°. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.54 Å. Both P(1)-O(1) bond lengths are 1.57 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Ni(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing OLi2NiP tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(2), one Ni(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom.