Li2Mn3(P2O7)2 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a T-shaped geometry to one O(1), one O(2), and one O(4) atom. In the second Li site, Li(2) is bonded in a distorted trigonal planar geometry to one O(12), one O(13), and one O(14) atom. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(7) atom. In the second Mn site, Mn(2) is bonded in a 4-coordinate geometry to one O(10), one O(11), one O(5), and one O(6) atom. In the third Mn site, Mn(3) is bonded in a 5-coordinate geometry to one O(10), one O(12), one O(13), one O(14), and one O(8) atom. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form corner-sharing PO4 tetrahedra. In the second P site, P(2) is bonded to one O(3), one O(4), one O(5), and one O(8) atom to form corner-sharing PO4 tetrahedra. In the third P site, P(3) is bonded to one O(11), one O(13), one O(7), and one O(9) atom to form corner-sharing PO4 tetrahedra. In the fourth P site, P(4) is bonded to one O(10), one O(12), one O(14), and one O(9) atom to form corner-sharing PO4 tetrahedra. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one Mn(1), 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 P(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), 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 Mn(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Mn(2) 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(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Mn(3) and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one P(3) and one P(4) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Mn(2), one Mn(3), 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(3) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Li(2), one Mn(3), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(2), one Mn(3), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a trigonal planar geometry to one Li(2), one Mn(3), and one P(4) atom.
Li2Mn3(P2O7)2 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a T-shaped geometry to one O(1), one O(2), and one O(4) atom. The Li(1)-O(1) bond length is 2.08 Å. The Li(1)-O(2) bond length is 1.99 Å. The Li(1)-O(4) bond length is 1.97 Å. In the second Li site, Li(2) is bonded in a distorted trigonal planar geometry to one O(12), one O(13), and one O(14) atom. The Li(2)-O(12) bond length is 1.96 Å. The Li(2)-O(13) bond length is 2.03 Å. The Li(2)-O(14) bond length is 2.06 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(7) atom. The Mn(1)-O(1) bond length is 2.07 Å. The Mn(1)-O(2) bond length is 2.34 Å. The Mn(1)-O(3) bond length is 2.20 Å. The Mn(1)-O(4) bond length is 2.09 Å. The Mn(1)-O(7) bond length is 2.02 Å. In the second Mn site, Mn(2) is bonded in a 4-coordinate geometry to one O(10), one O(11), one O(5), and one O(6) atom. The Mn(2)-O(10) bond length is 2.19 Å. The Mn(2)-O(11) bond length is 2.09 Å. The Mn(2)-O(5) bond length is 2.15 Å. The Mn(2)-O(6) bond length is 2.05 Å. In the third Mn site, Mn(3) is bonded in a 5-coordinate geometry to one O(10), one O(12), one O(13), one O(14), and one O(8) atom. The Mn(3)-O(10) bond length is 2.46 Å. The Mn(3)-O(12) bond length is 2.19 Å. The Mn(3)-O(13) bond length is 2.14 Å. The Mn(3)-O(14) bond length is 2.12 Å. The Mn(3)-O(8) bond length is 2.02 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form corner-sharing PO4 tetrahedra. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.68 Å. The P(1)-O(6) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(3), one O(4), one O(5), and one O(8) atom to form corner-sharing PO4 tetrahedra. The P(2)-O(3) bond length is 1.65 Å. The P(2)-O(4) bond length is 1.54 Å. The P(2)-O(5) bond length is 1.52 Å. The P(2)-O(8) bond length is 1.52 Å. In the third P site, P(3) is bonded to one O(11), one O(13), one O(7), and one O(9) atom to form corner-sharing PO4 tetrahedra. The P(3)-O(11) bond length is 1.53 Å. The P(3)-O(13) bond length is 1.54 Å. The P(3)-O(7) bond length is 1.52 Å. The P(3)-O(9) bond length is 1.65 Å. In the fourth P site, P(4) is bonded to one O(10), one O(12), one O(14), and one O(9) atom to form corner-sharing PO4 tetrahedra. The P(4)-O(10) bond length is 1.54 Å. The P(4)-O(12) bond length is 1.53 Å. The P(4)-O(14) bond length is 1.54 Å. The P(4)-O(9) bond length is 1.63 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one Mn(1), 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 P(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), 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 Mn(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Mn(2) 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(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Mn(3) and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one P(3) and one P(4) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Mn(2), one Mn(3), 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(3) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Li(2), one Mn(3), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(2), one Mn(3), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a trigonal planar geometry to one Li(2), one Mn(3), and one P(4) atom.