(ZnP(HO)5)4O2 crystallizes in the triclinic P-1 space group. The structure consists of two water atoms inside a ZnP(HO)5 framework. In the ZnP(HO)5 framework, there are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent O(1), two equivalent O(7), and two equivalent O(8) atoms to form ZnO6 octahedra that share corners with two equivalent P(1)HO3 tetrahedra. In the second Zn site, Zn(2) is bonded to two equivalent O(10), two equivalent O(4), and two equivalent O(9) atoms to form ZnO6 octahedra that share corners with two equivalent P(2)HO3 tetrahedra. In the third Zn site, Zn(3) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form ZnO4 tetrahedra that share corners with two equivalent P(1)HO3 tetrahedra and corners with two equivalent P(2)HO3 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one H(1), one O(1), one O(2), and one O(3) atom to form distorted PHO3 tetrahedra that share  a cornercorner with one Zn(1)O6 octahedra and corners with two equivalent Zn(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 31°. In the second P site, P(2) is bonded to one H(2), one O(4), one O(5), and one O(6) atom to form distorted PHO3 tetrahedra that share  a cornercorner with one Zn(2)O6 octahedra and corners with two equivalent Zn(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 35°. There are ten inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one P(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one P(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one O(5) and one O(7) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(7) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one O(8) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one O(8) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one O(9) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one O(9) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one O(10) atom. In the tenth H site, H(10) is bonded in a single-bond geometry to one O(10) atom. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Zn(3) and one P(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Zn(3) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Zn(2) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Zn(3), one P(2), and one H(3) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Zn(3) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Zn(1), one H(3), and one H(4) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Zn(1), one H(5), and one H(6) atom. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one Zn(2), one H(7), and one H(8) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Zn(2), one H(10), and one H(9) atom.
(ZnP(HO)5)4O2 crystallizes in the triclinic P-1 space group. The structure consists of two water atoms inside a ZnP(HO)5 framework. In the ZnP(HO)5 framework, there are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent O(1), two equivalent O(7), and two equivalent O(8) atoms to form ZnO6 octahedra that share corners with two equivalent P(1)HO3 tetrahedra. Both Zn(1)-O(1) bond lengths are 2.04 Å. Both Zn(1)-O(7) bond lengths are 2.13 Å. Both Zn(1)-O(8) bond lengths are 2.17 Å. In the second Zn site, Zn(2) is bonded to two equivalent O(10), two equivalent O(4), and two equivalent O(9) atoms to form ZnO6 octahedra that share corners with two equivalent P(2)HO3 tetrahedra. Both Zn(2)-O(10) bond lengths are 2.15 Å. Both Zn(2)-O(4) bond lengths are 2.01 Å. Both Zn(2)-O(9) bond lengths are 2.16 Å. In the third Zn site, Zn(3) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form ZnO4 tetrahedra that share corners with two equivalent P(1)HO3 tetrahedra and corners with two equivalent P(2)HO3 tetrahedra. The Zn(3)-O(2) bond length is 1.97 Å. The Zn(3)-O(3) bond length is 2.02 Å. The Zn(3)-O(5) bond length is 2.00 Å. The Zn(3)-O(6) bond length is 2.00 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one H(1), one O(1), one O(2), and one O(3) atom to form distorted PHO3 tetrahedra that share  a cornercorner with one Zn(1)O6 octahedra and corners with two equivalent Zn(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 31°. The P(1)-H(1) bond length is 1.41 Å. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.57 Å. In the second P site, P(2) is bonded to one H(2), one O(4), one O(5), and one O(6) atom to form distorted PHO3 tetrahedra that share  a cornercorner with one Zn(2)O6 octahedra and corners with two equivalent Zn(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 35°. The P(2)-H(2) bond length is 1.41 Å. The P(2)-O(4) bond length is 1.52 Å. The P(2)-O(5) bond length is 1.54 Å. The P(2)-O(6) bond length is 1.57 Å. There are ten inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one P(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one P(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one O(5) and one O(7) atom. The H(3)-O(5) bond length is 1.73 Å. The H(3)-O(7) bond length is 1.00 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(7) atom. The H(4)-O(7) bond length is 0.99 Å. In the fifth H site, H(5) is bonded in a single-bond geometry to one O(8) atom. The H(5)-O(8) bond length is 0.99 Å. In the sixth H site, H(6) is bonded in a single-bond geometry to one O(8) atom. The H(6)-O(8) bond length is 0.99 Å. In the seventh H site, H(7) is bonded in a single-bond geometry to one O(9) atom. The H(7)-O(9) bond length is 0.99 Å. In the eighth H site, H(8) is bonded in a single-bond geometry to one O(9) atom. The H(8)-O(9) bond length is 1.00 Å. In the ninth H site, H(9) is bonded in a single-bond geometry to one O(10) atom. The H(9)-O(10) bond length is 0.99 Å. In the tenth H site, H(10) is bonded in a single-bond geometry to one O(10) atom. The H(10)-O(10) bond length is 0.98 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Zn(3) and one P(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Zn(3) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Zn(2) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Zn(3), one P(2), and one H(3) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Zn(3) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Zn(1), one H(3), and one H(4) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Zn(1), one H(5), and one H(6) atom. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one Zn(2), one H(7), and one H(8) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Zn(2), one H(10), and one H(9) atom.