Li2Mn3(P2O7)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(10), one O(14), one O(7), and two equivalent O(8) atoms. In the second Li site, Li(2) is bonded in a distorted trigonal non-coplanar geometry to one O(14), one O(7), and one O(8) atom. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(12), one O(13), one O(2), one O(5), and one O(9) atom to form distorted MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 pentagonal pyramids. In the second Mn site, Mn(2) is bonded to one O(10), one O(12), one O(14), one O(3), one O(7), and one O(9) atom to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Mn(1)O6 octahedra. In the third Mn site, Mn(3) is bonded to one O(1), one O(13), one O(2), one O(5), and two equivalent O(6) atoms to form distorted MnO6 pentagonal pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with four equivalent P(4)O4 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, and  an edgeedge with one Mn(3)O6 pentagonal pyramid. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(12), one O(4), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 pentagonal pyramid, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-59°. In the second P site, P(2) is bonded to one O(10), one O(14), one O(4), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Mn(2)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-54°. In the third P site, P(3) is bonded to one O(11), one O(13), one O(3), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 pentagonal pyramid, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-52°. In the fourth P site, P(4) is bonded to one O(11), one O(2), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Mn(3)O6 pentagonal pyramids, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-51°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(3), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one P(4) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Mn(2) and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(3), and one P(4) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Mn(3) and one P(4) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(2), and one P(1) atom. In the eighth O site, O(8) is bonded to one Li(2), two equivalent Li(1), and one P(2) atom to form edge-sharing OLi3P trigonal pyramids. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(2), and one P(2) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one P(3) and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(1) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(2), and one P(2) atom.
Li2Mn3(P2O7)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(10), one O(14), one O(7), and two equivalent O(8) atoms. The Li(1)-O(10) bond length is 2.01 Å. The Li(1)-O(14) bond length is 2.59 Å. The Li(1)-O(7) bond length is 2.54 Å. There is one shorter (2.13 Å) and one longer (2.28 Å) Li(1)-O(8) bond length. In the second Li site, Li(2) is bonded in a distorted trigonal non-coplanar geometry to one O(14), one O(7), and one O(8) atom. The Li(2)-O(14) bond length is 2.13 Å. The Li(2)-O(7) bond length is 2.02 Å. The Li(2)-O(8) bond length is 2.00 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(12), one O(13), one O(2), one O(5), and one O(9) atom to form distorted MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 pentagonal pyramids. The Mn(1)-O(1) bond length is 2.18 Å. The Mn(1)-O(12) bond length is 2.28 Å. The Mn(1)-O(13) bond length is 2.20 Å. The Mn(1)-O(2) bond length is 2.22 Å. The Mn(1)-O(5) bond length is 2.22 Å. The Mn(1)-O(9) bond length is 2.18 Å. In the second Mn site, Mn(2) is bonded to one O(10), one O(12), one O(14), one O(3), one O(7), and one O(9) atom to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Mn(1)O6 octahedra. The Mn(2)-O(10) bond length is 2.30 Å. The Mn(2)-O(12) bond length is 2.21 Å. The Mn(2)-O(14) bond length is 2.24 Å. The Mn(2)-O(3) bond length is 2.10 Å. The Mn(2)-O(7) bond length is 2.21 Å. The Mn(2)-O(9) bond length is 2.20 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(13), one O(2), one O(5), and two equivalent O(6) atoms to form distorted MnO6 pentagonal pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with four equivalent P(4)O4 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, and  an edgeedge with one Mn(3)O6 pentagonal pyramid. The Mn(3)-O(1) bond length is 2.40 Å. The Mn(3)-O(13) bond length is 2.13 Å. The Mn(3)-O(2) bond length is 2.14 Å. The Mn(3)-O(5) bond length is 2.19 Å. There is one shorter (2.16 Å) and one longer (2.44 Å) Mn(3)-O(6) bond length. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(12), one O(4), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 pentagonal pyramid, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-59°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(12) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.62 Å. The P(1)-O(7) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(10), one O(14), one O(4), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Mn(2)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-54°. The P(2)-O(10) bond length is 1.54 Å. The P(2)-O(14) bond length is 1.54 Å. The P(2)-O(4) bond length is 1.62 Å. The P(2)-O(8) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(11), one O(13), one O(3), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 pentagonal pyramid, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-52°. The P(3)-O(11) bond length is 1.61 Å. The P(3)-O(13) bond length is 1.53 Å. The P(3)-O(3) bond length is 1.51 Å. The P(3)-O(9) bond length is 1.54 Å. In the fourth P site, P(4) is bonded to one O(11), one O(2), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Mn(3)O6 pentagonal pyramids, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-51°. The P(4)-O(11) bond length is 1.61 Å. The P(4)-O(2) bond length is 1.54 Å. The P(4)-O(5) bond length is 1.53 Å. The P(4)-O(6) bond length is 1.53 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(3), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one P(4) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Mn(2) and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(3), and one P(4) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Mn(3) and one P(4) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(2), and one P(1) atom. In the eighth O site, O(8) is bonded to one Li(2), two equivalent Li(1), and one P(2) atom to form edge-sharing OLi3P trigonal pyramids. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(2), and one P(2) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one P(3) and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(1) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(2), and one P(2) atom.