NaCoPO4 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with four equivalent Co(1)O6 pentagonal pyramids, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Co(1)O6 pentagonal pyramids, and edges with two equivalent P(1)O4 tetrahedra. Co(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form distorted CoO6 pentagonal pyramids that share corners with four equivalent Na(1)O6 octahedra, corners with four equivalent Co(1)O6 pentagonal pyramids, corners with four equivalent P(1)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 63-72°. 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 Na(1)O6 octahedra, corners with four equivalent Co(1)O6 pentagonal pyramids, edges with two equivalent Na(1)O6 octahedra, and  an edgeedge with one Co(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 58°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Co(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Co(1), and one P(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Na(1), two equivalent Co(1), and one P(1) atom.
NaCoPO4 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with four equivalent Co(1)O6 pentagonal pyramids, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Co(1)O6 pentagonal pyramids, and edges with two equivalent P(1)O4 tetrahedra. Both Na(1)-O(1) bond lengths are 2.34 Å. Both Na(1)-O(2) bond lengths are 2.35 Å. Both Na(1)-O(3) bond lengths are 2.37 Å. Co(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form distorted CoO6 pentagonal pyramids that share corners with four equivalent Na(1)O6 octahedra, corners with four equivalent Co(1)O6 pentagonal pyramids, corners with four equivalent P(1)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 63-72°. The Co(1)-O(1) bond length is 2.05 Å. The Co(1)-O(2) bond length is 2.12 Å. There are two shorter (2.18 Å) and two longer (2.25 Å) Co(1)-O(3) bond lengths. 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 Na(1)O6 octahedra, corners with four equivalent Co(1)O6 pentagonal pyramids, edges with two equivalent Na(1)O6 octahedra, and  an edgeedge with one Co(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 58°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.54 Å. Both P(1)-O(3) bond lengths are 1.57 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Co(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Co(1), and one P(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Na(1), two equivalent Co(1), and one P(1) atom.