Cu(PO3)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted CuO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Cu(2)O6 octahedra. In the second Cu site, Cu(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(6) atoms to form CuO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Cu(1)O6 octahedra. There are two inequivalent P sites. In the first P site, 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  a cornercorner with one Cu(2)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-59°. In the second P site, P(2) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(1)O6 octahedra, corners with two equivalent Cu(2)O6 octahedra, and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-55°. There are six inequivalent O sites. In the first O site, O(6) is bonded in a bent 150 degrees geometry to one Cu(2) and one P(2) atom. In the second O site, O(1) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one P(2) atom. In the third O site, O(2) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one P(1) atom. In the fourth O site, O(3) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(4) is bonded in a bent 150 degrees geometry to one Cu(1) and one P(1) atom. In the sixth O site, O(5) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom.
Cu(PO3)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted CuO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Cu(2)O6 octahedra. Both Cu(1)-O(1) bond lengths are 2.53 Å. Both Cu(1)-O(2) bond lengths are 1.97 Å. Both Cu(1)-O(4) bond lengths are 1.92 Å. In the second Cu site, Cu(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(6) atoms to form CuO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Cu(1)O6 octahedra. Both Cu(2)-O(1) bond lengths are 1.97 Å. Both Cu(2)-O(2) bond lengths are 2.41 Å. Both Cu(2)-O(6) bond lengths are 1.92 Å. There are two inequivalent P sites. In the first P site, 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  a cornercorner with one Cu(2)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-59°. The P(1)-O(2) bond length is 1.50 Å. The P(1)-O(3) bond length is 1.59 Å. The P(1)-O(4) bond length is 1.47 Å. The P(1)-O(5) bond length is 1.59 Å. In the second P site, P(2) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(1)O6 octahedra, corners with two equivalent Cu(2)O6 octahedra, and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-55°. The P(2)-O(1) bond length is 1.50 Å. The P(2)-O(3) bond length is 1.60 Å. The P(2)-O(5) bond length is 1.59 Å. The P(2)-O(6) bond length is 1.47 Å. There are six inequivalent O sites. In the first O site, O(6) is bonded in a bent 150 degrees geometry to one Cu(2) and one P(2) atom. In the second O site, O(1) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one P(2) atom. In the third O site, O(2) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one P(1) atom. In the fourth O site, O(3) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(4) is bonded in a bent 150 degrees geometry to one Cu(1) and one P(1) atom. In the sixth O site, O(5) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom.