Cr(PO3)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted CrO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Cr(2)O6 octahedra. In the second Cr site, Cr(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Cr(1)O6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 24-52°. In the second P site, P(2) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-59°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Cr(2) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Cr(1), one Cr(2), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Cr(1), one Cr(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom.
Cr(PO3)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted CrO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Cr(2)O6 octahedra. Both Cr(1)-O(2) bond lengths are 2.05 Å. Both Cr(1)-O(4) bond lengths are 2.62 Å. Both Cr(1)-O(5) bond lengths are 1.99 Å. In the second Cr site, Cr(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Cr(1)O6 octahedra. Both Cr(2)-O(1) bond lengths are 2.00 Å. Both Cr(2)-O(2) bond lengths are 2.49 Å. Both Cr(2)-O(4) bond lengths are 2.03 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 24-52°. The P(1)-O(1) bond length is 1.47 Å. The P(1)-O(3) bond length is 1.60 Å. The P(1)-O(4) bond length is 1.49 Å. The P(1)-O(6) bond length is 1.59 Å. In the second P site, P(2) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-59°. The P(2)-O(2) 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 1.47 Å. The P(2)-O(6) bond length is 1.59 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Cr(2) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Cr(1), one Cr(2), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Cr(1), one Cr(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom.