Li3Mn4(PO4)6 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(11), one O(5), two equivalent O(10), and two equivalent O(7) atoms. In the second Li site, Li(2) is bonded in a square co-planar geometry to two equivalent O(4) and two equivalent O(6) atoms. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(12), one O(2), one O(4), one O(5), and one O(8) atom to form MnO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Mn(2)O6 octahedra. In the second Mn site, Mn(2) is bonded to one O(11), one O(2), one O(3), one O(6), one O(8), and one O(9) atom to form MnO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)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. There are four inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(3) and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-54°. In the second P site, P(2) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. In the third P site, P(3) is bonded to one O(10), one O(4), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-57°. In the fourth P site, P(4) is bonded to two equivalent O(11) and two equivalent O(12) atoms to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-53°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Mn(1) and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one P(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Mn(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Li(2), one Mn(1), and one P(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one P(3) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one Mn(2) and one P(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(2), and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one Mn(1) and one P(4) atom.
Li3Mn4(PO4)6 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(11), one O(5), two equivalent O(10), and two equivalent O(7) atoms. The Li(1)-O(11) bond length is 2.35 Å. The Li(1)-O(5) bond length is 2.36 Å. There is one shorter (2.02 Å) and one longer (2.36 Å) Li(1)-O(10) bond length. There is one shorter (2.02 Å) and one longer (2.35 Å) Li(1)-O(7) bond length. In the second Li site, Li(2) is bonded in a square co-planar geometry to two equivalent O(4) and two equivalent O(6) atoms. Both Li(2)-O(4) bond lengths are 2.25 Å. Both Li(2)-O(6) bond lengths are 2.32 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(12), one O(2), one O(4), one O(5), and one O(8) atom to form MnO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Mn(2)O6 octahedra. The Mn(1)-O(1) bond length is 1.89 Å. The Mn(1)-O(12) bond length is 1.94 Å. The Mn(1)-O(2) bond length is 1.98 Å. The Mn(1)-O(4) bond length is 2.05 Å. The Mn(1)-O(5) bond length is 1.97 Å. The Mn(1)-O(8) bond length is 2.24 Å. In the second Mn site, Mn(2) is bonded to one O(11), one O(2), one O(3), one O(6), one O(8), and one O(9) atom to form MnO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)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(11) bond length is 1.98 Å. The Mn(2)-O(2) bond length is 2.21 Å. The Mn(2)-O(3) bond length is 1.94 Å. The Mn(2)-O(6) bond length is 2.07 Å. The Mn(2)-O(8) bond length is 1.97 Å. The Mn(2)-O(9) bond length is 1.91 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(3) and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-54°. Both P(1)-O(3) bond lengths are 1.55 Å. Both P(1)-O(5) bond lengths are 1.56 Å. In the second P site, P(2) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. The P(2)-O(1) bond length is 1.55 Å. The P(2)-O(2) bond length is 1.59 Å. The P(2)-O(6) bond length is 1.56 Å. The P(2)-O(7) bond length is 1.50 Å. In the third P site, P(3) is bonded to one O(10), one O(4), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-57°. The P(3)-O(10) bond length is 1.50 Å. The P(3)-O(4) bond length is 1.56 Å. The P(3)-O(8) bond length is 1.59 Å. The P(3)-O(9) bond length is 1.56 Å. In the fourth P site, P(4) is bonded to two equivalent O(11) and two equivalent O(12) atoms to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-53°. Both P(4)-O(11) bond lengths are 1.56 Å. Both P(4)-O(12) bond lengths are 1.55 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Mn(1) and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one P(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Mn(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Li(2), one Mn(1), and one P(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one P(3) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one Mn(2) and one P(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(2), and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one Mn(1) and one P(4) atom.