Li3Ni2(PO4)3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to two equivalent O(3) and four equivalent O(1) atoms. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(5) and four equivalent O(4) atoms. Ni(1) is bonded to one O(1), one O(3), one O(5), one O(6), and two equivalent O(2) atoms to form NiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Ni(1)O6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-57°. In the second P site, P(2) is bonded to two equivalent O(5) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-57°. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), 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 3-coordinate geometry to two equivalent Ni(1) and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Ni(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent Li(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(3), one Ni(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Ni(1), and one P(2) atom.
Li3Ni2(PO4)3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to two equivalent O(3) and four equivalent O(1) atoms. Both Li(1)-O(3) bond lengths are 2.58 Å. There are two shorter (2.23 Å) and two longer (2.29 Å) Li(1)-O(1) bond lengths. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms. Both Li(2)-O(3) bond lengths are 2.40 Å. Both Li(2)-O(4) bond lengths are 2.17 Å. Both Li(2)-O(6) bond lengths are 2.17 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(5) and four equivalent O(4) atoms. Both Li(3)-O(5) bond lengths are 2.23 Å. There are two shorter (2.11 Å) and two longer (2.46 Å) Li(3)-O(4) bond lengths. Ni(1) is bonded to one O(1), one O(3), one O(5), one O(6), and two equivalent O(2) atoms to form NiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Ni(1)O6 octahedra. The Ni(1)-O(1) bond length is 2.11 Å. The Ni(1)-O(3) bond length is 1.98 Å. The Ni(1)-O(5) bond length is 1.99 Å. The Ni(1)-O(6) bond length is 1.98 Å. There is one shorter (1.99 Å) and one longer (2.15 Å) Ni(1)-O(2) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-57°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.52 Å. In the second P site, P(2) is bonded to two equivalent O(5) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-57°. Both P(2)-O(5) bond lengths are 1.56 Å. Both P(2)-O(6) bond lengths are 1.55 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), 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 3-coordinate geometry to two equivalent Ni(1) and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Ni(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent Li(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(3), one Ni(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Ni(1), and one P(2) atom.