NaPHO3 crystallizes in the triclinic P-1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form distorted NaO5 square pyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one Na(1)O5 square pyramid. In the second Na site, Na(2) is bonded in a distorted L-shaped geometry to one H(1), two equivalent H(2), one O(2), and one O(4) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent Na(1)O5 square pyramids and corners with two equivalent P(2)O4 tetrahedra. In the second P site, P(2) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Na(1)O5 square pyramids and corners with two equivalent P(1)O4 tetrahedra. There are two inequivalent H sites. In the first H site, H(1) is bonded in a distorted single-bond geometry to one Na(2) atom. In the second H site, H(2) is bonded in a 2-coordinate geometry to two equivalent Na(2) atoms. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one P(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Na(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom.
NaPHO3 crystallizes in the triclinic P-1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form distorted NaO5 square pyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one Na(1)O5 square pyramid. The Na(1)-O(2) bond length is 2.63 Å. The Na(1)-O(3) bond length is 2.36 Å. The Na(1)-O(4) bond length is 2.36 Å. There is one shorter (2.33 Å) and one longer (2.41 Å) Na(1)-O(5) bond length. In the second Na site, Na(2) is bonded in a distorted L-shaped geometry to one H(1), two equivalent H(2), one O(2), and one O(4) atom. The Na(2)-H(1) bond length is 2.62 Å. There is one shorter (2.71 Å) and one longer (2.77 Å) Na(2)-H(2) bond length. The Na(2)-O(2) bond length is 2.20 Å. The Na(2)-O(4) bond length is 2.20 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent Na(1)O5 square pyramids and corners with two equivalent P(2)O4 tetrahedra. The P(1)-O(1) bond length is 1.63 Å. The P(1)-O(4) bond length is 1.50 Å. The P(1)-O(5) bond length is 1.50 Å. The P(1)-O(6) bond length is 1.63 Å. In the second P site, P(2) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Na(1)O5 square pyramids and corners with two equivalent P(1)O4 tetrahedra. The P(2)-O(1) bond length is 1.64 Å. The P(2)-O(2) bond length is 1.50 Å. The P(2)-O(3) bond length is 1.49 Å. The P(2)-O(6) bond length is 1.63 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a distorted single-bond geometry to one Na(2) atom. In the second H site, H(2) is bonded in a 2-coordinate geometry to two equivalent Na(2) atoms. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one P(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Na(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom.