NaNiPO4 is Ilmenite-derived structured and crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form distorted NaO6 octahedra that share corners with four equivalent Na(1)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, edges with two equivalent Ni(1)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 59-67°. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with four equivalent Na(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 59-66°. P(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with four equivalent Na(1)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-68°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), two equivalent Ni(1), and one P(1) atom to form distorted corner-sharing ONaNi2P trigonal pyramids. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Ni(1), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ni(1), and one P(1) atom.
NaNiPO4 is Ilmenite-derived structured and crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form distorted NaO6 octahedra that share corners with four equivalent Na(1)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, edges with two equivalent Ni(1)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 59-67°. The Na(1)-O(1) bond length is 2.36 Å. The Na(1)-O(2) bond length is 2.60 Å. There are two shorter (2.34 Å) and two longer (2.50 Å) Na(1)-O(3) bond lengths. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with four equivalent Na(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 59-66°. Both Ni(1)-O(1) bond lengths are 2.08 Å. Both Ni(1)-O(2) bond lengths are 2.19 Å. Both Ni(1)-O(3) bond lengths are 2.11 Å. P(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with four equivalent Na(1)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-68°. The P(1)-O(1) bond length is 1.60 Å. The P(1)-O(2) bond length is 1.55 Å. Both P(1)-O(3) bond lengths are 1.55 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), two equivalent Ni(1), and one P(1) atom to form distorted corner-sharing ONaNi2P trigonal pyramids. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Ni(1), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ni(1), and one P(1) atom.