Li3Mn4(PO4)6 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 6-coordinate geometry to one O(1), one O(11), one O(12), one O(3), one O(4), and one O(8) atom. In the second Li site, Li(2) is bonded to two equivalent O(12), two equivalent O(6), and two equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(4), one O(5), one O(6), and two equivalent O(2) atoms to form MnO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 56°. In the second Mn site, Mn(2) is bonded to one O(11), one O(3), one O(7), one O(9), and two equivalent O(10) atoms to form MnO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra, and  an edgeedge with one Mn(2)O6 octahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(6), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, 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 51-73°. In the second P site, P(2) is bonded to one O(1), one O(2), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and corners with three equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-59°. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and corners with three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-59°. There are twelve 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 distorted trigonal planar geometry to two equivalent Mn(1) and one P(2) atom. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Li(1), one Mn(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Mn(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one Mn(2) and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to two equivalent Mn(2) and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Mn(2), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(3) atom.
Li3Mn4(PO4)6 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 6-coordinate geometry to one O(1), one O(11), one O(12), one O(3), one O(4), and one O(8) atom. The Li(1)-O(1) bond length is 2.36 Å. The Li(1)-O(11) bond length is 2.61 Å. The Li(1)-O(12) bond length is 1.99 Å. The Li(1)-O(3) bond length is 2.25 Å. The Li(1)-O(4) bond length is 2.14 Å. The Li(1)-O(8) bond length is 2.02 Å. In the second Li site, Li(2) is bonded to two equivalent O(12), two equivalent O(6), and two equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. Both Li(2)-O(12) bond lengths are 2.03 Å. Both Li(2)-O(6) bond lengths are 2.23 Å. Both Li(2)-O(8) 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(4), one O(5), one O(6), and two equivalent O(2) atoms to form MnO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 56°. The Mn(1)-O(1) bond length is 1.94 Å. The Mn(1)-O(4) bond length is 1.99 Å. The Mn(1)-O(5) bond length is 1.95 Å. The Mn(1)-O(6) bond length is 2.01 Å. There is one shorter (2.02 Å) and one longer (2.11 Å) Mn(1)-O(2) bond length. In the second Mn site, Mn(2) is bonded to one O(11), one O(3), one O(7), one O(9), and two equivalent O(10) atoms to form MnO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra, and  an edgeedge with one Mn(2)O6 octahedra. The Mn(2)-O(11) bond length is 1.91 Å. The Mn(2)-O(3) bond length is 1.99 Å. The Mn(2)-O(7) bond length is 1.93 Å. The Mn(2)-O(9) bond length is 1.95 Å. There is one shorter (1.99 Å) and one longer (2.13 Å) Mn(2)-O(10) bond length. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(6), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, 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 51-73°. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.56 Å. The P(1)-O(9) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(1), one O(2), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and corners with three equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-59°. The P(2)-O(1) bond length is 1.57 Å. The P(2)-O(2) bond length is 1.61 Å. The P(2)-O(7) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.49 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and corners with three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-59°. The P(3)-O(10) bond length is 1.62 Å. The P(3)-O(11) bond length is 1.56 Å. The P(3)-O(12) bond length is 1.49 Å. The P(3)-O(5) bond length is 1.54 Å. There are twelve 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 distorted trigonal planar geometry to two equivalent Mn(1) and one P(2) atom. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Li(1), one Mn(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Mn(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one Mn(2) and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to two equivalent Mn(2) and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Mn(2), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(3) atom.