Li3Mn3(PO4)4 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 4-coordinate geometry to two equivalent O(4) and two equivalent O(5) atoms. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(7), and two equivalent O(8) atoms to form distorted LiO5 square pyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, and  an edgeedge with one Li(2)O5 square pyramid. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(2)O5 square pyramid. In the second Mn site, Mn(2) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and edges with four equivalent Mn(1)O6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Li(2)O5 square pyramids, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-57°. In the second P site, P(2) is bonded to one O(1), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with three equivalent Li(2)O5 square pyramids, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-60°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(2), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Mn(2) and two equivalent Mn(1) atoms. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Mn(1), one Mn(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Mn(1), one Mn(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one P(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Li(2) and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to two equivalent Li(2) and one P(2) atom.
Li3Mn3(PO4)4 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 4-coordinate geometry to two equivalent O(4) and two equivalent O(5) atoms. Both Li(1)-O(4) bond lengths are 2.29 Å. Both Li(1)-O(5) bond lengths are 2.60 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(7), and two equivalent O(8) atoms to form distorted LiO5 square pyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, and  an edgeedge with one Li(2)O5 square pyramid. The Li(2)-O(1) bond length is 2.27 Å. The Li(2)-O(2) bond length is 2.50 Å. The Li(2)-O(7) bond length is 1.93 Å. There is one shorter (1.98 Å) and one longer (2.20 Å) Li(2)-O(8) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(2)O5 square pyramid. The Mn(1)-O(1) bond length is 1.96 Å. The Mn(1)-O(2) bond length is 1.94 Å. The Mn(1)-O(4) bond length is 2.38 Å. The Mn(1)-O(5) bond length is 2.30 Å. There is one shorter (1.95 Å) and one longer (1.96 Å) Mn(1)-O(3) bond length. In the second Mn site, Mn(2) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and edges with four equivalent Mn(1)O6 octahedra. Both Mn(2)-O(3) bond lengths are 1.89 Å. Both Mn(2)-O(4) bond lengths are 2.24 Å. Both Mn(2)-O(5) bond lengths are 2.03 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Li(2)O5 square pyramids, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-57°. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.59 Å. The P(1)-O(6) bond length is 1.63 Å. The P(1)-O(7) bond length is 1.48 Å. In the second P site, P(2) is bonded to one O(1), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with three equivalent Li(2)O5 square pyramids, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-60°. The P(2)-O(1) bond length is 1.56 Å. The P(2)-O(4) bond length is 1.57 Å. The P(2)-O(6) bond length is 1.63 Å. The P(2)-O(8) bond length is 1.50 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(2), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Mn(2) and two equivalent Mn(1) atoms. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Mn(1), one Mn(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Mn(1), one Mn(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one P(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Li(2) and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to two equivalent Li(2) and one P(2) atom.