LiNiPO4 crystallizes in the hexagonal P6_3 space group. Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Ni(2)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-73°. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form distorted NiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra, edges with three equivalent Li(1)O4 tetrahedra, and  a faceface with one Ni(2)O6 octahedra. In the second Ni site, Ni(2) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form NiO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and  a faceface with one Ni(1)O6 octahedra. In the third Ni site, Ni(3) is bonded in a distorted T-shaped geometry to three equivalent O(1) atoms. 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 two equivalent Ni(1)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra, and corners with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-57°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one Ni(3), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Ni(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Ni(2), and one P(1) atom. In the fourth O site, O(4) is bonded to one Li(1), one Ni(1), one Ni(2), and one P(1) atom to form distorted edge-sharing OLiNi2P trigonal pyramids.
LiNiPO4 crystallizes in the hexagonal P6_3 space group. Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Ni(2)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-73°. The Li(1)-O(1) bond length is 1.94 Å. The Li(1)-O(2) bond length is 1.92 Å. The Li(1)-O(3) bond length is 2.03 Å. The Li(1)-O(4) bond length is 1.94 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form distorted NiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra, edges with three equivalent Li(1)O4 tetrahedra, and  a faceface with one Ni(2)O6 octahedra. All Ni(1)-O(2) bond lengths are 2.04 Å. All Ni(1)-O(4) bond lengths are 2.19 Å. In the second Ni site, Ni(2) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form NiO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and  a faceface with one Ni(1)O6 octahedra. All Ni(2)-O(3) bond lengths are 2.06 Å. All Ni(2)-O(4) bond lengths are 2.21 Å. In the third Ni site, Ni(3) is bonded in a distorted T-shaped geometry to three equivalent O(1) atoms. All Ni(3)-O(1) bond lengths are 1.90 Å. 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 two equivalent Ni(1)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra, and corners with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-57°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.56 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one Ni(3), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Ni(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Ni(2), and one P(1) atom. In the fourth O site, O(4) is bonded to one Li(1), one Ni(1), one Ni(2), and one P(1) atom to form distorted edge-sharing OLiNi2P trigonal pyramids.