Co(PO3)3 crystallizes in the orthorhombic Pbcm space group. Co(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CoO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Co(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 47-54°. There are five inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to two equivalent P(2) atoms. In the second O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one P(1) atom. In the third O site, O(2) is bonded in a bent 120 degrees geometry to one Co(1) and one P(2) atom. In the fourth O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one P(2) atom. In the fifth O site, O(4) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom.
Co(PO3)3 crystallizes in the orthorhombic Pbcm space group. Co(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CoO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. Both Co(1)-O(1) bond lengths are 1.90 Å. Both Co(1)-O(2) bond lengths are 1.92 Å. Both Co(1)-O(3) bond lengths are 1.90 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. Both P(1)-O(1) bond lengths are 1.49 Å. Both P(1)-O(4) bond lengths are 1.58 Å. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Co(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 47-54°. The P(2)-O(2) bond length is 1.49 Å. The P(2)-O(3) bond length is 1.49 Å. The P(2)-O(4) bond length is 1.59 Å. The P(2)-O(5) bond length is 1.57 Å. There are five inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to two equivalent P(2) atoms. In the second O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one P(1) atom. In the third O site, O(2) is bonded in a bent 120 degrees geometry to one Co(1) and one P(2) atom. In the fourth O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one P(2) atom. In the fifth O site, O(4) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom.