Mn(PO3)3 crystallizes in the orthorhombic Pccn space group. Mn(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Mn(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 36-37°. In the second P site, P(2) is bonded to two equivalent O(4) and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 36°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to two equivalent P(1) atoms. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom.
Mn(PO3)3 crystallizes in the orthorhombic Pccn space group. Mn(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. Both Mn(1)-O(2) bond lengths are 1.96 Å. Both Mn(1)-O(3) bond lengths are 2.21 Å. Both Mn(1)-O(4) bond lengths are 1.94 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Mn(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 36-37°. The P(1)-O(1) bond length is 1.62 Å. The P(1)-O(2) bond length is 1.51 Å. The P(1)-O(3) bond length is 1.49 Å. The P(1)-O(5) bond length is 1.61 Å. In the second P site, P(2) is bonded to two equivalent O(4) and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 36°. Both P(2)-O(4) bond lengths are 1.50 Å. Both P(2)-O(5) bond lengths are 1.58 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to two equivalent P(1) atoms. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom.