Na2PH3O5 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(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form NaO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra and  an edgeedge with one Na(1)O6 octahedra. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), and two 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 four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-63°. There are three inequivalent H sites. In the first H site, H(1) is bonded in a distorted single-bond geometry to one O(2) and one O(4) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(2) and one O(5) atom. In the third H site, H(3) is bonded in a single-bond geometry to one O(5) atom. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one P(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one P(1), one H(1), and one H(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one P(1), and one H(1) atom. In the fifth O site, O(5) is bonded in a distorted water-like geometry to two equivalent Na(1), one H(2), and one H(3) atom.
Na2PH3O5 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(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form NaO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra and  an edgeedge with one Na(1)O6 octahedra. The Na(1)-O(1) bond length is 2.41 Å. The Na(1)-O(2) bond length is 2.60 Å. The Na(1)-O(3) bond length is 2.41 Å. The Na(1)-O(4) bond length is 2.51 Å. There is one shorter (2.36 Å) and one longer (2.38 Å) Na(1)-O(5) bond length. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(1) atoms. The Na(2)-O(2) bond length is 2.62 Å. The Na(2)-O(3) bond length is 2.32 Å. The Na(2)-O(4) bond length is 2.53 Å. There is one shorter (2.35 Å) and one longer (2.49 Å) Na(2)-O(1) bond length. 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 four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-63°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.64 Å. There are three inequivalent H sites. In the first H site, H(1) is bonded in a distorted single-bond geometry to one O(2) and one O(4) atom. The H(1)-O(2) bond length is 1.67 Å. The H(1)-O(4) bond length is 1.01 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(2) and one O(5) atom. The H(2)-O(2) bond length is 1.75 Å. The H(2)-O(5) bond length is 0.99 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(5) atom. The H(3)-O(5) bond length is 0.99 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one P(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one P(1), one H(1), and one H(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one P(1), and one H(1) atom. In the fifth O site, O(5) is bonded in a distorted water-like geometry to two equivalent Na(1), one H(2), and one H(3) atom.