Cu(PO3)3 crystallizes in the orthorhombic P2_12_12_1 space group. Cu(1) is bonded to one O(2), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form CuO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-57°. In the second P site, P(2) is bonded to one O(1), one O(2), one O(4), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-51°. In the third P site, P(3) is bonded to one O(3), one O(6), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-44°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Cu(1) and one P(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Cu(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Cu(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Cu(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Cu(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Cu(1) and one P(1) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom.
Cu(PO3)3 crystallizes in the orthorhombic P2_12_12_1 space group. Cu(1) is bonded to one O(2), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form CuO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The Cu(1)-O(2) bond length is 2.03 Å. The Cu(1)-O(4) bond length is 1.99 Å. The Cu(1)-O(5) bond length is 2.06 Å. The Cu(1)-O(6) bond length is 2.11 Å. The Cu(1)-O(7) bond length is 1.99 Å. The Cu(1)-O(8) bond length is 1.95 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-57°. The P(1)-O(1) bond length is 1.62 Å. The P(1)-O(3) bond length is 1.62 Å. The P(1)-O(5) bond length is 1.51 Å. The P(1)-O(8) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(1), one O(2), one O(4), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-51°. The P(2)-O(1) bond length is 1.61 Å. The P(2)-O(2) bond length is 1.50 Å. The P(2)-O(4) bond length is 1.51 Å. The P(2)-O(9) bond length is 1.61 Å. In the third P site, P(3) is bonded to one O(3), one O(6), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-44°. The P(3)-O(3) bond length is 1.63 Å. The P(3)-O(6) bond length is 1.52 Å. The P(3)-O(7) bond length is 1.50 Å. The P(3)-O(9) bond length is 1.60 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Cu(1) and one P(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Cu(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Cu(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Cu(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Cu(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Cu(1) and one P(1) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom.