NaPH4O5 crystallizes in the orthorhombic Pna2_1 space group. Na(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form distorted NaO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra and edges with two equivalent Na(1)O6 octahedra. P(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-59°. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(3) atom. In the second H site, H(2) is bonded in a distorted linear geometry to one O(4) and one O(5) atom. In the third H site, H(3) is bonded in a single-bond geometry to one O(3) atom. In the fourth H site, H(4) is bonded in a linear geometry to one O(2) and one O(5) atom. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one P(1), and one H(4) atom. In the third O site, O(3) is bonded in a distorted water-like geometry to two equivalent Na(1), one H(1), and one H(3) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one P(1), and one H(2) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one P(1), one H(2), and one H(4) atom.
NaPH4O5 crystallizes in the orthorhombic Pna2_1 space group. Na(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form distorted NaO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra and edges with two equivalent Na(1)O6 octahedra. The Na(1)-O(2) bond length is 2.39 Å. The Na(1)-O(4) bond length is 2.40 Å. There is one shorter (2.54 Å) and one longer (2.60 Å) Na(1)-O(1) bond length. There is one shorter (2.47 Å) and one longer (2.63 Å) Na(1)-O(3) bond length. P(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-59°. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(2) bond length is 1.60 Å. The P(1)-O(4) bond length is 1.59 Å. The P(1)-O(5) bond length is 1.54 Å. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(3) atom. The H(1)-O(3) bond length is 0.99 Å. In the second H site, H(2) is bonded in a distorted linear geometry to one O(4) and one O(5) atom. The H(2)-O(4) bond length is 1.03 Å. The H(2)-O(5) bond length is 1.57 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(3) atom. The H(3)-O(3) bond length is 0.98 Å. In the fourth H site, H(4) is bonded in a linear geometry to one O(2) and one O(5) atom. The H(4)-O(2) bond length is 1.02 Å. The H(4)-O(5) bond length is 1.57 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one P(1), and one H(4) atom. In the third O site, O(3) is bonded in a distorted water-like geometry to two equivalent Na(1), one H(1), and one H(3) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one P(1), and one H(2) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one P(1), one H(2), and one H(4) atom.