Mn4(PO4)3 crystallizes in the monoclinic Cc space group. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(3), one O(4), one O(5), and one O(6) atom. In the second Mn site, Mn(2) is bonded to one O(10), one O(11), one O(12), one O(2), one O(4), and one O(9) atom to form distorted MnO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one O(3), one O(7), two equivalent O(8), and two equivalent O(9) atoms. In the fourth Mn site, Mn(4) is bonded in a 6-coordinate geometry to one O(10), one O(2), one O(5), one O(6), one O(7), and one O(8) atom. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(5), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-56°. In the second P site, P(2) is bonded to one O(10), one O(11), one O(12), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-51°. In the third P site, P(3) is bonded to one O(1), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles are 58°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(4), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one P(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(4), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(4), and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Mn(3), one Mn(4), and one P(3) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Mn(4), two equivalent Mn(3), and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Mn(2), two equivalent Mn(3), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(4), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(2) atom.
Mn4(PO4)3 crystallizes in the monoclinic Cc space group. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(3), one O(4), one O(5), and one O(6) atom. The Mn(1)-O(1) bond length is 2.02 Å. The Mn(1)-O(11) bond length is 2.54 Å. The Mn(1)-O(3) bond length is 2.15 Å. The Mn(1)-O(4) bond length is 2.05 Å. The Mn(1)-O(5) bond length is 2.10 Å. The Mn(1)-O(6) bond length is 2.07 Å. In the second Mn site, Mn(2) is bonded to one O(10), one O(11), one O(12), one O(2), one O(4), and one O(9) atom to form distorted MnO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. The Mn(2)-O(10) bond length is 2.06 Å. The Mn(2)-O(11) bond length is 2.04 Å. The Mn(2)-O(12) bond length is 2.02 Å. The Mn(2)-O(2) bond length is 2.12 Å. The Mn(2)-O(4) bond length is 2.46 Å. The Mn(2)-O(9) bond length is 2.21 Å. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one O(3), one O(7), two equivalent O(8), and two equivalent O(9) atoms. The Mn(3)-O(3) bond length is 2.24 Å. The Mn(3)-O(7) bond length is 2.18 Å. There is one shorter (2.24 Å) and one longer (2.37 Å) Mn(3)-O(8) bond length. There is one shorter (2.26 Å) and one longer (2.55 Å) Mn(3)-O(9) bond length. In the fourth Mn site, Mn(4) is bonded in a 6-coordinate geometry to one O(10), one O(2), one O(5), one O(6), one O(7), and one O(8) atom. The Mn(4)-O(10) bond length is 2.27 Å. The Mn(4)-O(2) bond length is 2.16 Å. The Mn(4)-O(5) bond length is 2.14 Å. The Mn(4)-O(6) bond length is 2.32 Å. The Mn(4)-O(7) bond length is 2.27 Å. The Mn(4)-O(8) bond length is 2.38 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(5), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-56°. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(9) bond length is 1.58 Å. In the second P site, P(2) is bonded to one O(10), one O(11), one O(12), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-51°. The P(2)-O(10) bond length is 1.56 Å. The P(2)-O(11) bond length is 1.55 Å. The P(2)-O(12) bond length is 1.52 Å. The P(2)-O(8) bond length is 1.60 Å. In the third P site, P(3) is bonded to one O(1), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles are 58°. The P(3)-O(1) bond length is 1.52 Å. The P(3)-O(4) bond length is 1.57 Å. The P(3)-O(6) bond length is 1.57 Å. The P(3)-O(7) bond length is 1.58 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(4), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one P(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(4), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(4), and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Mn(3), one Mn(4), and one P(3) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Mn(4), two equivalent Mn(3), and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Mn(2), two equivalent Mn(3), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(4), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(2) atom.