Mn3(P2O7)2 crystallizes in the triclinic P1 space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a rectangular see-saw-like geometry to one O(10), one O(5), one O(6), and one O(9) atom. In the second Mn site, Mn(2) is bonded to one O(1), one O(11), one O(14), one O(2), and one O(4) atom to form MnO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one Mn(3)O5 trigonal bipyramid. In the third Mn site, Mn(3) is bonded to one O(1), one O(12), one O(13), one O(2), and one O(3) atom to form MnO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Mn(2)O5 trigonal bipyramid. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(12), one O(14), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one Mn(2)O5 trigonal bipyramid, and  a cornercorner with one Mn(3)O5 trigonal bipyramid. In the second P site, P(2) is bonded to one O(11), one O(13), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one Mn(2)O5 trigonal bipyramid, and  a cornercorner with one Mn(3)O5 trigonal bipyramid. In the third P site, P(3) is bonded to one O(1), one O(10), one O(3), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one Mn(2)O5 trigonal bipyramid, and corners with two equivalent Mn(3)O5 trigonal bipyramids. In the fourth P site, P(4) is bonded to one O(2), one O(4), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one Mn(3)O5 trigonal bipyramid, and corners with two equivalent Mn(2)O5 trigonal bipyramids. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(3), 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(3), and one P(4) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Mn(3) and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Mn(2) and one P(4) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(1) and one P(4) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Mn(1) and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to 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(3) and one P(1) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one Mn(3) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one Mn(2) and one P(1) atom.
Mn3(P2O7)2 crystallizes in the triclinic P1 space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a rectangular see-saw-like geometry to one O(10), one O(5), one O(6), and one O(9) atom. The Mn(1)-O(10) bond length is 1.93 Å. The Mn(1)-O(5) bond length is 1.93 Å. The Mn(1)-O(6) bond length is 1.92 Å. The Mn(1)-O(9) bond length is 1.94 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(11), one O(14), one O(2), and one O(4) atom to form MnO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one Mn(3)O5 trigonal bipyramid. The Mn(2)-O(1) bond length is 2.17 Å. The Mn(2)-O(11) bond length is 2.04 Å. The Mn(2)-O(14) bond length is 2.14 Å. The Mn(2)-O(2) bond length is 2.19 Å. The Mn(2)-O(4) bond length is 2.07 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(12), one O(13), one O(2), and one O(3) atom to form MnO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Mn(2)O5 trigonal bipyramid. The Mn(3)-O(1) bond length is 2.01 Å. The Mn(3)-O(12) bond length is 1.89 Å. The Mn(3)-O(13) bond length is 1.97 Å. The Mn(3)-O(2) bond length is 1.99 Å. The Mn(3)-O(3) bond length is 2.07 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(12), one O(14), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one Mn(2)O5 trigonal bipyramid, and  a cornercorner with one Mn(3)O5 trigonal bipyramid. The P(1)-O(12) bond length is 1.54 Å. The P(1)-O(14) bond length is 1.52 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.62 Å. In the second P site, P(2) is bonded to one O(11), one O(13), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one Mn(2)O5 trigonal bipyramid, and  a cornercorner with one Mn(3)O5 trigonal bipyramid. The P(2)-O(11) bond length is 1.50 Å. The P(2)-O(13) bond length is 1.54 Å. The P(2)-O(6) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.63 Å. In the third P site, P(3) is bonded to one O(1), one O(10), one O(3), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one Mn(2)O5 trigonal bipyramid, and corners with two equivalent Mn(3)O5 trigonal bipyramids. The P(3)-O(1) bond length is 1.57 Å. The P(3)-O(10) bond length is 1.53 Å. The P(3)-O(3) bond length is 1.51 Å. The P(3)-O(8) bond length is 1.61 Å. In the fourth P site, P(4) is bonded to one O(2), one O(4), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one Mn(3)O5 trigonal bipyramid, and corners with two equivalent Mn(2)O5 trigonal bipyramids. The P(4)-O(2) bond length is 1.58 Å. The P(4)-O(4) bond length is 1.50 Å. The P(4)-O(7) bond length is 1.62 Å. The P(4)-O(9) bond length is 1.53 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(3), 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(3), and one P(4) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Mn(3) and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Mn(2) and one P(4) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(1) and one P(4) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Mn(1) and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to 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(3) and one P(1) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one Mn(3) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one Mn(2) and one P(1) atom.