Li3Mn2(PO4)3 crystallizes in the monoclinic C2/c 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(1), one O(2), one O(3), one O(4), and one O(6) atom. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms. Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted MnO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-50°. In the second P site, P(2) is bonded to two equivalent O(1) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-46°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Mn(1), and one P(1) atom to form distorted corner-sharing OLi2MnP trigonal pyramids. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one Mn(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(1), and one P(2) atom.
Li3Mn2(PO4)3 crystallizes in the monoclinic C2/c 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(1), one O(2), one O(3), one O(4), and one O(6) atom. The Li(1)-O(1) bond length is 2.34 Å. The Li(1)-O(2) bond length is 2.10 Å. The Li(1)-O(3) bond length is 2.27 Å. The Li(1)-O(4) bond length is 1.99 Å. The Li(1)-O(6) bond length is 2.06 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms. Both Li(2)-O(2) bond lengths are 2.49 Å. Both Li(2)-O(3) bond lengths are 2.18 Å. Both Li(2)-O(6) bond lengths are 2.12 Å. Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted MnO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. The Mn(1)-O(1) bond length is 1.91 Å. The Mn(1)-O(2) bond length is 1.96 Å. The Mn(1)-O(3) bond length is 1.95 Å. The Mn(1)-O(4) bond length is 2.19 Å. The Mn(1)-O(5) bond length is 1.87 Å. The Mn(1)-O(6) bond length is 2.44 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-50°. The P(1)-O(2) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.53 Å. The P(1)-O(5) bond length is 1.53 Å. In the second P site, P(2) is bonded to two equivalent O(1) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-46°. Both P(2)-O(1) bond lengths are 1.57 Å. Both P(2)-O(6) bond lengths are 1.54 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Mn(1), and one P(1) atom to form distorted corner-sharing OLi2MnP trigonal pyramids. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one Mn(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(1), and one P(2) atom.