NaH(ZnPO4)2 crystallizes in the triclinic P-1 space group. Na(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form distorted NaO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent Zn(2)O4 tetrahedra, corners with three equivalent Zn(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(3), one O(4), one O(7), and one O(8) atom to form ZnO4 tetrahedra that share corners with three equivalent Na(1)O6 octahedra,  a cornercorner with one Zn(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 64-68°. In the second Zn site, Zn(2) is bonded to one O(1), one O(2), one O(5), and one O(8) atom to form ZnO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra,  a cornercorner with one Zn(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with three equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-73°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra, corners with two equivalent Zn(1)O4 tetrahedra, corners with three equivalent Zn(2)O4 tetrahedra, and  an edgeedge with one Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 62°. In the second P site, P(2) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Na(1)O6 octahedra,  a cornercorner with one Zn(2)O4 tetrahedra, and corners with two equivalent Zn(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-56°. H(1) is bonded in a distorted linear geometry to one O(5) and one O(6) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Zn(2), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Zn(2), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Na(1), one Zn(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Zn(2), one P(2), and one H(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Na(1), one P(2), and one H(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Na(1), one Zn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(2), and one P(1) atom.
NaH(ZnPO4)2 crystallizes in the triclinic P-1 space group. Na(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form distorted NaO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent Zn(2)O4 tetrahedra, corners with three equivalent Zn(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The Na(1)-O(1) bond length is 2.72 Å. The Na(1)-O(2) bond length is 2.56 Å. The Na(1)-O(3) bond length is 2.45 Å. The Na(1)-O(4) bond length is 2.47 Å. The Na(1)-O(6) bond length is 2.44 Å. The Na(1)-O(7) bond length is 2.48 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(3), one O(4), one O(7), and one O(8) atom to form ZnO4 tetrahedra that share corners with three equivalent Na(1)O6 octahedra,  a cornercorner with one Zn(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 64-68°. The Zn(1)-O(3) bond length is 1.93 Å. The Zn(1)-O(4) bond length is 1.97 Å. The Zn(1)-O(7) bond length is 1.99 Å. The Zn(1)-O(8) bond length is 2.00 Å. In the second Zn site, Zn(2) is bonded to one O(1), one O(2), one O(5), and one O(8) atom to form ZnO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra,  a cornercorner with one Zn(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with three equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-73°. The Zn(2)-O(1) bond length is 1.95 Å. The Zn(2)-O(2) bond length is 1.95 Å. The Zn(2)-O(5) bond length is 1.99 Å. The Zn(2)-O(8) bond length is 2.04 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra, corners with two equivalent Zn(1)O4 tetrahedra, corners with three equivalent Zn(2)O4 tetrahedra, and  an edgeedge with one Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 62°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(8) bond length is 1.59 Å. In the second P site, P(2) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Na(1)O6 octahedra,  a cornercorner with one Zn(2)O4 tetrahedra, and corners with two equivalent Zn(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-56°. The P(2)-O(4) bond length is 1.54 Å. The P(2)-O(5) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.60 Å. The P(2)-O(7) bond length is 1.54 Å. H(1) is bonded in a distorted linear geometry to one O(5) and one O(6) atom. The H(1)-O(5) bond length is 1.64 Å. The H(1)-O(6) bond length is 1.01 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Zn(2), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Zn(2), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Na(1), one Zn(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Zn(2), one P(2), and one H(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Na(1), one P(2), and one H(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Na(1), one Zn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(2), and one P(1) atom.