NaFePO4 is Hausmannite-derived structured and 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 Fe(1)O6 pentagonal pyramids, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Fe(1)O6 pentagonal pyramids, and edges with two equivalent P(1)O4 tetrahedra. Fe(1) is bonded to one O(1), one O(3), and four equivalent O(2) atoms to form distorted FeO6 pentagonal pyramids that share corners with four equivalent Na(1)O6 octahedra, corners with four equivalent Fe(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 63-75°. P(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Fe(1)O6 pentagonal pyramids, edges with two equivalent Na(1)O6 octahedra, and  an edgeedge with one Fe(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 Fe(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Fe(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Fe(1), and one P(1) atom.
NaFePO4 is Hausmannite-derived structured and 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 Fe(1)O6 pentagonal pyramids, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Fe(1)O6 pentagonal pyramids, and edges with two equivalent P(1)O4 tetrahedra. Both Na(1)-O(1) bond lengths are 2.29 Å. Both Na(1)-O(2) bond lengths are 2.42 Å. Both Na(1)-O(3) bond lengths are 2.29 Å. Fe(1) is bonded to one O(1), one O(3), and four equivalent O(2) atoms to form distorted FeO6 pentagonal pyramids that share corners with four equivalent Na(1)O6 octahedra, corners with four equivalent Fe(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 63-75°. The Fe(1)-O(1) bond length is 2.14 Å. The Fe(1)-O(3) bond length is 2.08 Å. There are two shorter (2.07 Å) and two longer (2.34 Å) Fe(1)-O(2) bond lengths. P(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Fe(1)O6 pentagonal pyramids, edges with two equivalent Na(1)O6 octahedra, and  an edgeedge with one Fe(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 58°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(3) bond length is 1.54 Å. Both P(1)-O(2) bond lengths are 1.55 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 Fe(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Fe(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Fe(1), and one P(1) atom.