Mn(PO3)4 crystallizes in the triclinic P-1 space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(10), two equivalent O(4), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. In the second Mn site, Mn(2) is bonded to two equivalent O(11), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(12), one O(3), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra and corners with two equivalent P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. In the second P site, P(2) is bonded to one O(1), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. In the third P site, P(3) is bonded to one O(2), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-47°. In the fourth P site, P(4) is bonded to one O(10), one O(11), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-46°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(3) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Mn(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Mn(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one P(1) and one P(4) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one P(1) and one P(4) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Mn(2) and one P(4) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to one P(1) atom.
Mn(PO3)4 crystallizes in the triclinic P-1 space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(10), two equivalent O(4), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. Both Mn(1)-O(10) bond lengths are 1.96 Å. Both Mn(1)-O(4) bond lengths are 1.93 Å. Both Mn(1)-O(6) bond lengths are 1.95 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(11), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. Both Mn(2)-O(11) bond lengths are 1.99 Å. Both Mn(2)-O(2) bond lengths are 2.20 Å. Both Mn(2)-O(3) bond lengths are 1.95 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(12), one O(3), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra and corners with two equivalent P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. The P(1)-O(12) bond length is 1.48 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(8) bond length is 1.62 Å. The P(1)-O(9) bond length is 1.64 Å. In the second P site, P(2) is bonded to one O(1), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. The P(2)-O(1) bond length is 1.48 Å. The P(2)-O(4) bond length is 1.54 Å. The P(2)-O(5) bond length is 1.63 Å. The P(2)-O(7) bond length is 1.61 Å. In the third P site, P(3) is bonded to one O(2), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-47°. The P(3)-O(2) bond length is 1.48 Å. The P(3)-O(5) bond length is 1.60 Å. The P(3)-O(6) bond length is 1.53 Å. The P(3)-O(7) bond length is 1.61 Å. In the fourth P site, P(4) is bonded to one O(10), one O(11), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-46°. The P(4)-O(10) bond length is 1.51 Å. The P(4)-O(11) bond length is 1.51 Å. The P(4)-O(8) bond length is 1.60 Å. The P(4)-O(9) bond length is 1.60 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(3) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Mn(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Mn(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one P(1) and one P(4) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one P(1) and one P(4) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Mn(2) and one P(4) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to one P(1) atom.