Na2ZnPHO5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms. In the second Na site, Na(2) is bonded to one O(3), one O(4), and two equivalent O(5) atoms to form NaO4 trigonal pyramids that share  a cornercorner with one Zn(1)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and corners with two equivalent Na(2)O4 trigonal pyramids. Zn(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form ZnO4 tetrahedra that share corners with two equivalent Zn(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  a cornercorner with one Na(2)O4 trigonal pyramid. P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Zn(1)O4 tetrahedra and corners with four equivalent Na(2)O4 trigonal pyramids. H(1) is bonded in a single-bond geometry to one O(1) atom. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Na(1), two equivalent Zn(1), and one H(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Na(1), one Zn(1), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Zn(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one P(1) atom.
Na2ZnPHO5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms. The Na(1)-O(1) bond length is 2.45 Å. The Na(1)-O(2) bond length is 2.88 Å. The Na(1)-O(3) bond length is 2.53 Å. The Na(1)-O(5) bond length is 2.37 Å. There is one shorter (2.34 Å) and one longer (2.45 Å) Na(1)-O(4) bond length. In the second Na site, Na(2) is bonded to one O(3), one O(4), and two equivalent O(5) atoms to form NaO4 trigonal pyramids that share  a cornercorner with one Zn(1)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and corners with two equivalent Na(2)O4 trigonal pyramids. The Na(2)-O(3) bond length is 2.38 Å. The Na(2)-O(4) bond length is 2.30 Å. There is one shorter (2.32 Å) and one longer (2.37 Å) Na(2)-O(5) bond length. Zn(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form ZnO4 tetrahedra that share corners with two equivalent Zn(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  a cornercorner with one Na(2)O4 trigonal pyramid. The Zn(1)-O(2) bond length is 1.97 Å. The Zn(1)-O(3) bond length is 1.99 Å. There is one shorter (1.96 Å) and one longer (2.01 Å) Zn(1)-O(1) bond length. P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Zn(1)O4 tetrahedra and corners with four equivalent Na(2)O4 trigonal pyramids. The P(1)-O(2) bond length is 1.59 Å. The P(1)-O(3) bond length is 1.59 Å. The P(1)-O(4) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.54 Å. H(1) is bonded in a single-bond geometry to one O(1) atom. The H(1)-O(1) bond length is 0.99 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Na(1), two equivalent Zn(1), and one H(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Na(1), one Zn(1), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Zn(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one P(1) atom.