Mn3(PO4)4 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(13), one O(14), one O(3), one O(7), and one O(9) atom to form distorted MnO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  a cornercorner with one Mn(3)O5 trigonal bipyramid. In the second Mn site, Mn(2) is bonded to one O(12), one O(16), one O(2), one O(5), one O(6), and one O(8) atom to form MnO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Mn(3)O5 trigonal bipyramid. In the third Mn site, Mn(3) is bonded to one O(10), one O(13), one O(15), one O(6), and one O(8) atom to form MnO5 trigonal bipyramids that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(13), one O(6), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and  an edgeedge with one Mn(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-55°. In the second P site, P(2) is bonded to one O(10), one O(12), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, and corners with two equivalent Mn(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 34-52°. In the third P site, P(3) is bonded to one O(15), one O(16), one O(2), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 33-44°. In the fourth P site, P(4) is bonded to one O(1), one O(14), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-52°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Mn(1) and one P(4) 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 distorted bent 150 degrees geometry to one Mn(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one P(4) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Mn(2) and one P(4) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Mn(2), one Mn(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Mn(2), one Mn(3), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one Mn(1) and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Mn(3) and one P(2) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Mn(2) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(3), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one Mn(1) and one P(4) atom. In the fifteenth O site, O(15) is bonded in a bent 120 degrees geometry to one Mn(3) and one P(3) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 150 degrees geometry to one Mn(2) and one P(3) atom.
Mn3(PO4)4 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(13), one O(14), one O(3), one O(7), and one O(9) atom to form distorted MnO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  a cornercorner with one Mn(3)O5 trigonal bipyramid. The Mn(1)-O(1) bond length is 1.85 Å. The Mn(1)-O(13) bond length is 2.46 Å. The Mn(1)-O(14) bond length is 1.84 Å. The Mn(1)-O(3) bond length is 1.92 Å. The Mn(1)-O(7) bond length is 1.94 Å. The Mn(1)-O(9) bond length is 1.91 Å. In the second Mn site, Mn(2) is bonded to one O(12), one O(16), one O(2), one O(5), one O(6), and one O(8) atom to form MnO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Mn(3)O5 trigonal bipyramid. The Mn(2)-O(12) bond length is 1.96 Å. The Mn(2)-O(16) bond length is 1.93 Å. The Mn(2)-O(2) bond length is 1.84 Å. The Mn(2)-O(5) bond length is 1.82 Å. The Mn(2)-O(6) bond length is 1.96 Å. The Mn(2)-O(8) bond length is 2.19 Å. In the third Mn site, Mn(3) is bonded to one O(10), one O(13), one O(15), one O(6), and one O(8) atom to form MnO5 trigonal bipyramids that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. The Mn(3)-O(10) bond length is 1.80 Å. The Mn(3)-O(13) bond length is 1.89 Å. The Mn(3)-O(15) bond length is 1.84 Å. The Mn(3)-O(6) bond length is 1.93 Å. The Mn(3)-O(8) bond length is 1.94 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(13), one O(6), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and  an edgeedge with one Mn(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-55°. The P(1)-O(11) bond length is 1.46 Å. The P(1)-O(13) bond length is 1.64 Å. The P(1)-O(6) bond length is 1.66 Å. The P(1)-O(9) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(10), one O(12), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, and corners with two equivalent Mn(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 34-52°. The P(2)-O(10) bond length is 1.55 Å. The P(2)-O(12) bond length is 1.53 Å. The P(2)-O(7) 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(15), one O(16), one O(2), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 33-44°. The P(3)-O(15) bond length is 1.57 Å. The P(3)-O(16) bond length is 1.55 Å. The P(3)-O(2) bond length is 1.55 Å. The P(3)-O(3) bond length is 1.54 Å. In the fourth P site, P(4) is bonded to one O(1), one O(14), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-52°. The P(4)-O(1) bond length is 1.58 Å. The P(4)-O(14) bond length is 1.59 Å. The P(4)-O(4) bond length is 1.47 Å. The P(4)-O(5) bond length is 1.60 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Mn(1) and one P(4) 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 distorted bent 150 degrees geometry to one Mn(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one P(4) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Mn(2) and one P(4) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Mn(2), one Mn(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Mn(2), one Mn(3), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one Mn(1) and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Mn(3) and one P(2) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Mn(2) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(3), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one Mn(1) and one P(4) atom. In the fifteenth O site, O(15) is bonded in a bent 120 degrees geometry to one Mn(3) and one P(3) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 150 degrees geometry to one Mn(2) and one P(3) atom.