LiNi4(PO4)3 crystallizes in the monoclinic C2/c space group. Li(1) is bonded in a distorted square co-planar geometry to four equivalent O(1) atoms. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(3), one O(4), 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,  an edgeedge with one Ni(1)O6 octahedra, and  an edgeedge with one Ni(3)O6 octahedra. In the second Ni site, Ni(2) is bonded in a rectangular see-saw-like geometry to two equivalent O(4) and two equivalent O(5) atoms. In the third Ni site, Ni(3) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form distorted NiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent 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(5) atom to form PO4 tetrahedra that share corners with two equivalent Ni(3)O6 octahedra and corners with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-56°. In the second P site, P(2) is bonded to two equivalent O(4) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with two equivalent Ni(3)O6 octahedra and corners with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-59°. 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 trigonal pyramids. 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 3-coordinate geometry to one Ni(1), one Ni(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Ni(1), one Ni(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Ni(2), one Ni(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Ni(1), one Ni(3), and one P(2) atom.
LiNi4(PO4)3 crystallizes in the monoclinic C2/c space group. Li(1) is bonded in a distorted square co-planar geometry to four equivalent O(1) atoms. There are two shorter (2.27 Å) and two longer (2.41 Å) Li(1)-O(1) bond lengths. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(3), one O(4), 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,  an edgeedge with one Ni(1)O6 octahedra, and  an edgeedge with one Ni(3)O6 octahedra. The Ni(1)-O(1) bond length is 2.10 Å. The Ni(1)-O(3) bond length is 2.06 Å. The Ni(1)-O(4) bond length is 2.00 Å. The Ni(1)-O(6) bond length is 2.04 Å. There is one shorter (2.08 Å) and one longer (2.16 Å) Ni(1)-O(2) bond length. In the second Ni site, Ni(2) is bonded in a rectangular see-saw-like geometry to two equivalent O(4) and two equivalent O(5) atoms. Both Ni(2)-O(4) bond lengths are 1.91 Å. Both Ni(2)-O(5) bond lengths are 1.91 Å. In the third Ni site, Ni(3) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form distorted NiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Ni(1)O6 octahedra. Both Ni(3)-O(3) bond lengths are 2.07 Å. Both Ni(3)-O(5) bond lengths are 2.16 Å. Both Ni(3)-O(6) bond lengths are 2.12 Å. 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(5) atom to form PO4 tetrahedra that share corners with two equivalent Ni(3)O6 octahedra and corners with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-56°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.58 Å. In the second P site, P(2) is bonded to two equivalent O(4) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with two equivalent Ni(3)O6 octahedra and corners with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-59°. Both P(2)-O(4) bond lengths are 1.58 Å. Both P(2)-O(6) bond lengths are 1.54 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 trigonal pyramids. 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 3-coordinate geometry to one Ni(1), one Ni(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Ni(1), one Ni(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Ni(2), one Ni(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Ni(1), one Ni(3), and one P(2) atom.