Co2(PO3)5 crystallizes in the monoclinic P2/c space group. Co(1) is bonded to one O(1), one O(2), one O(4), one O(6), and two equivalent O(3) atoms to form distorted CoO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one Co(1)O6 octahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Co(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 16-51°. In the second P site, P(2) 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 three 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 15-59°. In the third P site, P(3) is bonded to two equivalent O(6) and two equivalent O(7) atoms to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 39°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Co(1) and one P(2) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Co(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a linear geometry to one Co(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Co(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to two equivalent P(2) atoms.
Co2(PO3)5 crystallizes in the monoclinic P2/c space group. Co(1) is bonded to one O(1), one O(2), one O(4), one O(6), and two equivalent O(3) atoms to form distorted CoO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one Co(1)O6 octahedra. The Co(1)-O(1) bond length is 1.97 Å. The Co(1)-O(2) bond length is 2.03 Å. The Co(1)-O(4) bond length is 1.95 Å. The Co(1)-O(6) bond length is 2.05 Å. There is one shorter (2.11 Å) and one longer (2.41 Å) Co(1)-O(3) bond length. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Co(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 16-51°. The P(1)-O(2) bond length is 1.50 Å. The P(1)-O(4) bond length is 1.50 Å. The P(1)-O(5) bond length is 1.63 Å. The P(1)-O(7) bond length is 1.60 Å. In the second P site, P(2) 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 three 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 15-59°. The P(2)-O(1) bond length is 1.49 Å. The P(2)-O(3) bond length is 1.52 Å. The P(2)-O(5) bond length is 1.60 Å. The P(2)-O(8) bond length is 1.58 Å. In the third P site, P(3) is bonded to two equivalent O(6) and two equivalent O(7) atoms to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 39°. Both P(3)-O(6) bond lengths are 1.50 Å. Both P(3)-O(7) bond lengths are 1.62 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Co(1) and one P(2) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Co(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a linear geometry to one Co(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Co(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to two equivalent P(2) atoms.