Zn(PO3)2 crystallizes in the monoclinic C2/c space group. Zn(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form ZnO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and edges with two equivalent Zn(1)O6 octahedra. P(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Zn(1)O6 octahedra and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-57°. There are three 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 trigonal planar geometry to two equivalent Zn(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent P(1) atoms.
Zn(PO3)2 crystallizes in the monoclinic C2/c space group. Zn(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form ZnO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and edges with two equivalent Zn(1)O6 octahedra. Both Zn(1)-O(1) bond lengths are 2.01 Å. There are two shorter (2.05 Å) and two longer (2.21 Å) Zn(1)-O(2) bond lengths. P(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Zn(1)O6 octahedra and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-57°. The P(1)-O(1) bond length is 1.48 Å. The P(1)-O(2) bond length is 1.50 Å. There is one shorter (1.59 Å) and one longer (1.60 Å) P(1)-O(3) bond length. There are three 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 trigonal planar geometry to two equivalent Zn(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent P(1) atoms.