Li3Mn2P2O8F3 crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 7-coordinate geometry to one O(5), one O(6), one O(7), one O(8), one F(1), one F(2), and one F(3) atom. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(2), one O(4), one O(5), one O(7), and one F(1) atom. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(6), one O(8), and one F(1) atom. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(4), one O(5), one O(6), one F(1), and one F(2) atom to form distorted MnO4F2 octahedra that share  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 9°. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(7), one O(8), one F(1), and one F(3) atom to form distorted MnO4F2 octahedra that share  a cornercorner with one Mn(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 9°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O4F2 octahedra and corners with two equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. In the second P site, P(2) is bonded to one O(2), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O4F2 octahedra and corners with two equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. There are eight inequivalent O sites. In the first O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(1), and one P(1) atom. In the second O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Mn(1), and one P(2) atom. In the third 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 fourth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Mn(2), and one P(2) atom. In the fifth O site, O(1) is bonded in a distorted T-shaped geometry to one Li(3), one Mn(2), and one P(1) atom. In the sixth O site, O(2) is bonded in a distorted T-shaped geometry to one Li(2), one Mn(2), and one P(2) atom. In the seventh O site, O(3) is bonded in a distorted T-shaped geometry to one Li(3), one Mn(1), and one P(1) atom. In the eighth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(2), one Mn(1), and one P(2) atom. There are three inequivalent F sites. In the first F site, F(3) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(2) atom. In the second F site, F(1) is bonded in a distorted square pyramidal geometry to one Li(1), one Li(2), one Li(3), one Mn(1), and one Mn(2) atom. In the third F site, F(2) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(1) atom.
Li3Mn2P2O8F3 crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 7-coordinate geometry to one O(5), one O(6), one O(7), one O(8), one F(1), one F(2), and one F(3) atom. The Li(1)-O(5) bond length is 2.53 Å. The Li(1)-O(6) bond length is 2.53 Å. The Li(1)-O(7) bond length is 2.53 Å. The Li(1)-O(8) bond length is 2.53 Å. The Li(1)-F(1) bond length is 2.36 Å. The Li(1)-F(2) bond length is 1.98 Å. The Li(1)-F(3) bond length is 1.97 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(2), one O(4), one O(5), one O(7), and one F(1) atom. The Li(2)-O(2) bond length is 2.12 Å. The Li(2)-O(4) bond length is 2.12 Å. The Li(2)-O(5) bond length is 2.43 Å. The Li(2)-O(7) bond length is 2.43 Å. The Li(2)-F(1) bond length is 1.99 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(6), one O(8), and one F(1) atom. The Li(3)-O(1) bond length is 2.11 Å. The Li(3)-O(3) bond length is 2.12 Å. The Li(3)-O(6) bond length is 2.44 Å. The Li(3)-O(8) bond length is 2.44 Å. The Li(3)-F(1) bond length is 1.98 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(4), one O(5), one O(6), one F(1), and one F(2) atom to form distorted MnO4F2 octahedra that share  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 9°. The Mn(1)-O(3) bond length is 1.99 Å. The Mn(1)-O(4) bond length is 1.99 Å. The Mn(1)-O(5) bond length is 1.98 Å. The Mn(1)-O(6) bond length is 1.98 Å. The Mn(1)-F(1) bond length is 2.13 Å. The Mn(1)-F(2) bond length is 2.01 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(7), one O(8), one F(1), and one F(3) atom to form distorted MnO4F2 octahedra that share  a cornercorner with one Mn(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 9°. The Mn(2)-O(1) bond length is 1.99 Å. The Mn(2)-O(2) bond length is 1.99 Å. The Mn(2)-O(7) bond length is 1.99 Å. The Mn(2)-O(8) bond length is 1.98 Å. The Mn(2)-F(1) bond length is 2.13 Å. The Mn(2)-F(3) bond length is 2.01 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O4F2 octahedra and corners with two equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(7) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(2), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O4F2 octahedra and corners with two equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. The P(2)-O(2) bond length is 1.55 Å. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.55 Å. There are eight inequivalent O sites. In the first O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(1), and one P(1) atom. In the second O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Mn(1), and one P(2) atom. In the third 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 fourth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Mn(2), and one P(2) atom. In the fifth O site, O(1) is bonded in a distorted T-shaped geometry to one Li(3), one Mn(2), and one P(1) atom. In the sixth O site, O(2) is bonded in a distorted T-shaped geometry to one Li(2), one Mn(2), and one P(2) atom. In the seventh O site, O(3) is bonded in a distorted T-shaped geometry to one Li(3), one Mn(1), and one P(1) atom. In the eighth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(2), one Mn(1), and one P(2) atom. There are three inequivalent F sites. In the first F site, F(3) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(2) atom. In the second F site, F(1) is bonded in a distorted square pyramidal geometry to one Li(1), one Li(2), one Li(3), one Mn(1), and one Mn(2) atom. In the third F site, F(2) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(1) atom.