Li4Mn8O13F3 is Spinel-derived structured and crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(12), one O(2), and one O(5) atom to form LiO4 tetrahedra that share  a cornercorner with one Mn(7)O4F2 octahedra,  a cornercorner with one Mn(8)O4F2 octahedra,  a cornercorner with one Mn(5)O6 octahedra, corners with two equivalent Mn(1)O5F octahedra, corners with two equivalent Mn(3)O5F octahedra, corners with two equivalent Mn(6)O6 octahedra, and corners with three equivalent Mn(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 51-62°. In the second Li site, Li(2) is bonded to one O(10), one O(8), one O(9), and one F(1) atom to form LiO3F tetrahedra that share  a cornercorner with one Mn(7)O4F2 octahedra,  a cornercorner with one Mn(8)O4F2 octahedra,  a cornercorner with one Mn(5)O6 octahedra, corners with two equivalent Mn(1)O5F octahedra, corners with two equivalent Mn(3)O5F octahedra, corners with two equivalent Mn(6)O6 octahedra, and corners with three equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 50-65°. In the third Li site, Li(3) is bonded to one O(4), one O(6), one O(7), and one F(2) atom to form LiO3F tetrahedra that share  a cornercorner with one Mn(1)O5F octahedra,  a cornercorner with one Mn(3)O5F octahedra,  a cornercorner with one Mn(6)O6 octahedra, corners with two equivalent Mn(7)O4F2 octahedra, corners with two equivalent Mn(8)O4F2 octahedra, corners with two equivalent Mn(5)O6 octahedra, and corners with three equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-64°. In the fourth Li site, Li(4) is bonded to one O(11), one O(13), one O(3), and one F(3) atom to form LiO3F tetrahedra that share  a cornercorner with one Mn(1)O5F octahedra,  a cornercorner with one Mn(3)O5F octahedra,  a cornercorner with one Mn(6)O6 octahedra, corners with two equivalent Mn(7)O4F2 octahedra, corners with two equivalent Mn(8)O4F2 octahedra, corners with two equivalent Mn(5)O6 octahedra, and corners with three equivalent Mn(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 47-66°. There are eight inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(7), one O(9), and one F(1) atom to form MnO5F octahedra that share  a cornercorner with one Li(3)O3F tetrahedra,  a cornercorner with one Li(4)O3F tetrahedra, corners with two equivalent Li(2)O3F tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Mn(4)O5F octahedra, edges with two equivalent Mn(3)O5F octahedra, and edges with two equivalent Mn(6)O6 octahedra. In the second Mn site, Mn(2) is bonded to one O(10), one O(4), one O(6), one O(9), one F(1), and one F(2) atom to form MnO4F2 octahedra that share corners with three equivalent Li(2)O3F tetrahedra, corners with three equivalent Li(3)O3F tetrahedra,  an edgeedge with one Mn(7)O4F2 octahedra,  an edgeedge with one Mn(8)O4F2 octahedra,  an edgeedge with one Mn(1)O5F octahedra,  an edgeedge with one Mn(3)O5F octahedra,  an edgeedge with one Mn(5)O6 octahedra, and  an edgeedge with one Mn(6)O6 octahedra. In the third Mn site, Mn(3) is bonded to one O(1), one O(10), one O(3), one O(5), one O(7), and one F(1) atom to form MnO5F octahedra that share  a cornercorner with one Li(3)O3F tetrahedra,  a cornercorner with one Li(4)O3F tetrahedra, corners with two equivalent Li(2)O3F tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Mn(4)O5F octahedra, edges with two equivalent Mn(1)O5F octahedra, and edges with two equivalent Mn(6)O6 octahedra. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(11), one O(13), one O(2), one O(5), and one F(3) atom to form MnO5F octahedra that share corners with three equivalent Li(4)O3F tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Mn(7)O4F2 octahedra,  an edgeedge with one Mn(8)O4F2 octahedra,  an edgeedge with one Mn(1)O5F octahedra,  an edgeedge with one Mn(3)O5F octahedra,  an edgeedge with one Mn(5)O6 octahedra, and  an edgeedge with one Mn(6)O6 octahedra. In the fifth Mn site, Mn(5) is bonded to one O(11), one O(12), one O(13), one O(4), one O(6), and one O(8) atom to form MnO6 octahedra that share  a cornercorner with one Li(2)O3F tetrahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(3)O3F tetrahedra, corners with two equivalent Li(4)O3F tetrahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Mn(4)O5F octahedra, edges with two equivalent Mn(7)O4F2 octahedra, and edges with two equivalent Mn(8)O4F2 octahedra. In the sixth Mn site, Mn(6) is bonded to one O(10), one O(2), one O(3), one O(5), one O(7), and one O(9) atom to form MnO6 octahedra that share  a cornercorner with one Li(3)O3F tetrahedra,  a cornercorner with one Li(4)O3F tetrahedra, corners with two equivalent Li(2)O3F tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Mn(4)O5F octahedra, edges with two equivalent Mn(1)O5F octahedra, and edges with two equivalent Mn(3)O5F octahedra. In the seventh Mn site, Mn(7) is bonded to one O(11), one O(12), one O(4), one O(8), one F(2), and one F(3) atom to form MnO4F2 octahedra that share  a cornercorner with one Li(2)O3F tetrahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(3)O3F tetrahedra, corners with two equivalent Li(4)O3F tetrahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Mn(4)O5F octahedra, edges with two equivalent Mn(8)O4F2 octahedra, and edges with two equivalent Mn(5)O6 octahedra. In the eighth Mn site, Mn(8) is bonded to one O(12), one O(13), one O(6), one O(8), one F(2), and one F(3) atom to form MnO4F2 octahedra that share  a cornercorner with one Li(2)O3F tetrahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(3)O3F tetrahedra, corners with two equivalent Li(4)O3F tetrahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Mn(4)O5F octahedra, edges with two equivalent Mn(7)O4F2 octahedra, and edges with two equivalent Mn(5)O6 octahedra. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom. In the second O site, O(2) is bonded to one Li(1), one Mn(1), one Mn(4), and one Mn(6) atom to form distorted corner-sharing OLiMn3 tetrahedra. In the third O site, O(3) is bonded to one Li(4), one Mn(1), one Mn(3), and one Mn(6) atom to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra. In the fourth O site, O(4) is bonded to one Li(3), one Mn(2), one Mn(5), and one Mn(7) atom to form a mixture of corner and edge-sharing OLiMn3 tetrahedra. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(3), one Mn(4), and one Mn(6) atom. In the sixth O site, O(6) is bonded to one Li(3), one Mn(2), one Mn(5), and one Mn(8) atom to form a mixture of corner and edge-sharing OLiMn3 tetrahedra. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Mn(1), one Mn(3), and one Mn(6) atom. In the eighth O site, O(8) is bonded to one Li(2), one Mn(5), one Mn(7), and one Mn(8) atom to form a mixture of distorted corner and edge-sharing OLiMn3 trigonal pyramids. In the ninth O site, O(9) is bonded to one Li(2), one Mn(1), one Mn(2), and one Mn(6) atom to form a mixture of corner and edge-sharing OLiMn3 tetrahedra. In the tenth O site, O(10) is bonded to one Li(2), one Mn(2), one Mn(3), and one Mn(6) atom to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra. In the eleventh O site, O(11) is bonded to one Li(4), one Mn(4), one Mn(5), and one Mn(7) atom to form a mixture of corner and edge-sharing OLiMn3 tetrahedra. In the twelfth O site, O(12) is bonded to one Li(1), one Mn(5), one Mn(7), and one Mn(8) atom to form a mixture of distorted corner and edge-sharing OLiMn3 trigonal pyramids. In the thirteenth O site, O(13) is bonded to one Li(4), one Mn(4), one Mn(5), and one Mn(8) atom to form a mixture of corner and edge-sharing OLiMn3 tetrahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(2), one Mn(1), one Mn(2), and one Mn(3) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(3), one Mn(2), one Mn(7), and one Mn(8) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(4), one Mn(4), one Mn(7), and one Mn(8) atom.
Li4Mn8O13F3 is Spinel-derived structured and crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(12), one O(2), and one O(5) atom to form LiO4 tetrahedra that share  a cornercorner with one Mn(7)O4F2 octahedra,  a cornercorner with one Mn(8)O4F2 octahedra,  a cornercorner with one Mn(5)O6 octahedra, corners with two equivalent Mn(1)O5F octahedra, corners with two equivalent Mn(3)O5F octahedra, corners with two equivalent Mn(6)O6 octahedra, and corners with three equivalent Mn(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 51-62°. The Li(1)-O(1) bond length is 1.98 Å. The Li(1)-O(12) bond length is 2.03 Å. The Li(1)-O(2) bond length is 2.08 Å. The Li(1)-O(5) bond length is 2.10 Å. In the second Li site, Li(2) is bonded to one O(10), one O(8), one O(9), and one F(1) atom to form LiO3F tetrahedra that share  a cornercorner with one Mn(7)O4F2 octahedra,  a cornercorner with one Mn(8)O4F2 octahedra,  a cornercorner with one Mn(5)O6 octahedra, corners with two equivalent Mn(1)O5F octahedra, corners with two equivalent Mn(3)O5F octahedra, corners with two equivalent Mn(6)O6 octahedra, and corners with three equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 50-65°. The Li(2)-O(10) bond length is 2.05 Å. The Li(2)-O(8) bond length is 2.01 Å. The Li(2)-O(9) bond length is 2.08 Å. The Li(2)-F(1) bond length is 1.98 Å. In the third Li site, Li(3) is bonded to one O(4), one O(6), one O(7), and one F(2) atom to form LiO3F tetrahedra that share  a cornercorner with one Mn(1)O5F octahedra,  a cornercorner with one Mn(3)O5F octahedra,  a cornercorner with one Mn(6)O6 octahedra, corners with two equivalent Mn(7)O4F2 octahedra, corners with two equivalent Mn(8)O4F2 octahedra, corners with two equivalent Mn(5)O6 octahedra, and corners with three equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-64°. The Li(3)-O(4) bond length is 2.08 Å. The Li(3)-O(6) bond length is 2.05 Å. The Li(3)-O(7) bond length is 2.03 Å. The Li(3)-F(2) bond length is 1.92 Å. In the fourth Li site, Li(4) is bonded to one O(11), one O(13), one O(3), and one F(3) atom to form LiO3F tetrahedra that share  a cornercorner with one Mn(1)O5F octahedra,  a cornercorner with one Mn(3)O5F octahedra,  a cornercorner with one Mn(6)O6 octahedra, corners with two equivalent Mn(7)O4F2 octahedra, corners with two equivalent Mn(8)O4F2 octahedra, corners with two equivalent Mn(5)O6 octahedra, and corners with three equivalent Mn(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 47-66°. The Li(4)-O(11) bond length is 2.08 Å. The Li(4)-O(13) bond length is 2.05 Å. The Li(4)-O(3) bond length is 2.03 Å. The Li(4)-F(3) bond length is 1.92 Å. There are eight inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(7), one O(9), and one F(1) atom to form MnO5F octahedra that share  a cornercorner with one Li(3)O3F tetrahedra,  a cornercorner with one Li(4)O3F tetrahedra, corners with two equivalent Li(2)O3F tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Mn(4)O5F octahedra, edges with two equivalent Mn(3)O5F octahedra, and edges with two equivalent Mn(6)O6 octahedra. The Mn(1)-O(1) bond length is 2.17 Å. The Mn(1)-O(2) bond length is 2.00 Å. The Mn(1)-O(3) bond length is 1.95 Å. The Mn(1)-O(7) bond length is 1.96 Å. The Mn(1)-O(9) bond length is 2.00 Å. The Mn(1)-F(1) bond length is 2.32 Å. In the second Mn site, Mn(2) is bonded to one O(10), one O(4), one O(6), one O(9), one F(1), and one F(2) atom to form MnO4F2 octahedra that share corners with three equivalent Li(2)O3F tetrahedra, corners with three equivalent Li(3)O3F tetrahedra,  an edgeedge with one Mn(7)O4F2 octahedra,  an edgeedge with one Mn(8)O4F2 octahedra,  an edgeedge with one Mn(1)O5F octahedra,  an edgeedge with one Mn(3)O5F octahedra,  an edgeedge with one Mn(5)O6 octahedra, and  an edgeedge with one Mn(6)O6 octahedra. The Mn(2)-O(10) bond length is 1.96 Å. The Mn(2)-O(4) bond length is 1.96 Å. The Mn(2)-O(6) bond length is 1.97 Å. The Mn(2)-O(9) bond length is 1.97 Å. The Mn(2)-F(1) bond length is 2.27 Å. The Mn(2)-F(2) bond length is 2.23 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(10), one O(3), one O(5), one O(7), and one F(1) atom to form MnO5F octahedra that share  a cornercorner with one Li(3)O3F tetrahedra,  a cornercorner with one Li(4)O3F tetrahedra, corners with two equivalent Li(2)O3F tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Mn(4)O5F octahedra, edges with two equivalent Mn(1)O5F octahedra, and edges with two equivalent Mn(6)O6 octahedra. The Mn(3)-O(1) bond length is 1.85 Å. The Mn(3)-O(10) bond length is 1.96 Å. The Mn(3)-O(3) bond length is 1.95 Å. The Mn(3)-O(5) bond length is 1.95 Å. The Mn(3)-O(7) bond length is 1.94 Å. The Mn(3)-F(1) bond length is 2.09 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(11), one O(13), one O(2), one O(5), and one F(3) atom to form MnO5F octahedra that share corners with three equivalent Li(4)O3F tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Mn(7)O4F2 octahedra,  an edgeedge with one Mn(8)O4F2 octahedra,  an edgeedge with one Mn(1)O5F octahedra,  an edgeedge with one Mn(3)O5F octahedra,  an edgeedge with one Mn(5)O6 octahedra, and  an edgeedge with one Mn(6)O6 octahedra. The Mn(4)-O(1) bond length is 2.17 Å. The Mn(4)-O(11) bond length is 1.96 Å. The Mn(4)-O(13) bond length is 1.98 Å. The Mn(4)-O(2) bond length is 2.00 Å. The Mn(4)-O(5) bond length is 1.97 Å. The Mn(4)-F(3) bond length is 2.29 Å. In the fifth Mn site, Mn(5) is bonded to one O(11), one O(12), one O(13), one O(4), one O(6), and one O(8) atom to form MnO6 octahedra that share  a cornercorner with one Li(2)O3F tetrahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(3)O3F tetrahedra, corners with two equivalent Li(4)O3F tetrahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Mn(4)O5F octahedra, edges with two equivalent Mn(7)O4F2 octahedra, and edges with two equivalent Mn(8)O4F2 octahedra. The Mn(5)-O(11) bond length is 2.02 Å. The Mn(5)-O(12) bond length is 2.24 Å. The Mn(5)-O(13) bond length is 1.97 Å. The Mn(5)-O(4) bond length is 2.02 Å. The Mn(5)-O(6) bond length is 1.98 Å. The Mn(5)-O(8) bond length is 2.24 Å. In the sixth Mn site, Mn(6) is bonded to one O(10), one O(2), one O(3), one O(5), one O(7), and one O(9) atom to form MnO6 octahedra that share  a cornercorner with one Li(3)O3F tetrahedra,  a cornercorner with one Li(4)O3F tetrahedra, corners with two equivalent Li(2)O3F tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Mn(4)O5F octahedra, edges with two equivalent Mn(1)O5F octahedra, and edges with two equivalent Mn(3)O5F octahedra. The Mn(6)-O(10) bond length is 2.10 Å. The Mn(6)-O(2) bond length is 1.95 Å. The Mn(6)-O(3) bond length is 2.17 Å. The Mn(6)-O(5) bond length is 2.09 Å. The Mn(6)-O(7) bond length is 2.17 Å. The Mn(6)-O(9) bond length is 1.97 Å. In the seventh Mn site, Mn(7) is bonded to one O(11), one O(12), one O(4), one O(8), one F(2), and one F(3) atom to form MnO4F2 octahedra that share  a cornercorner with one Li(2)O3F tetrahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(3)O3F tetrahedra, corners with two equivalent Li(4)O3F tetrahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Mn(4)O5F octahedra, edges with two equivalent Mn(8)O4F2 octahedra, and edges with two equivalent Mn(5)O6 octahedra. The Mn(7)-O(11) bond length is 2.00 Å. The Mn(7)-O(12) bond length is 1.94 Å. The Mn(7)-O(4) bond length is 2.00 Å. The Mn(7)-O(8) bond length is 1.94 Å. The Mn(7)-F(2) bond length is 2.24 Å. The Mn(7)-F(3) bond length is 2.22 Å. In the eighth Mn site, Mn(8) is bonded to one O(12), one O(13), one O(6), one O(8), one F(2), and one F(3) atom to form MnO4F2 octahedra that share  a cornercorner with one Li(2)O3F tetrahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(3)O3F tetrahedra, corners with two equivalent Li(4)O3F tetrahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Mn(4)O5F octahedra, edges with two equivalent Mn(7)O4F2 octahedra, and edges with two equivalent Mn(5)O6 octahedra. The Mn(8)-O(12) bond length is 1.93 Å. The Mn(8)-O(13) bond length is 1.98 Å. The Mn(8)-O(6) bond length is 2.00 Å. The Mn(8)-O(8) bond length is 1.94 Å. The Mn(8)-F(2) bond length is 2.25 Å. The Mn(8)-F(3) bond length is 2.23 Å. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom. In the second O site, O(2) is bonded to one Li(1), one Mn(1), one Mn(4), and one Mn(6) atom to form distorted corner-sharing OLiMn3 tetrahedra. In the third O site, O(3) is bonded to one Li(4), one Mn(1), one Mn(3), and one Mn(6) atom to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra. In the fourth O site, O(4) is bonded to one Li(3), one Mn(2), one Mn(5), and one Mn(7) atom to form a mixture of corner and edge-sharing OLiMn3 tetrahedra. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(3), one Mn(4), and one Mn(6) atom. In the sixth O site, O(6) is bonded to one Li(3), one Mn(2), one Mn(5), and one Mn(8) atom to form a mixture of corner and edge-sharing OLiMn3 tetrahedra. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Mn(1), one Mn(3), and one Mn(6) atom. In the eighth O site, O(8) is bonded to one Li(2), one Mn(5), one Mn(7), and one Mn(8) atom to form a mixture of distorted corner and edge-sharing OLiMn3 trigonal pyramids. In the ninth O site, O(9) is bonded to one Li(2), one Mn(1), one Mn(2), and one Mn(6) atom to form a mixture of corner and edge-sharing OLiMn3 tetrahedra. In the tenth O site, O(10) is bonded to one Li(2), one Mn(2), one Mn(3), and one Mn(6) atom to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra. In the eleventh O site, O(11) is bonded to one Li(4), one Mn(4), one Mn(5), and one Mn(7) atom to form a mixture of corner and edge-sharing OLiMn3 tetrahedra. In the twelfth O site, O(12) is bonded to one Li(1), one Mn(5), one Mn(7), and one Mn(8) atom to form a mixture of distorted corner and edge-sharing OLiMn3 trigonal pyramids. In the thirteenth O site, O(13) is bonded to one Li(4), one Mn(4), one Mn(5), and one Mn(8) atom to form a mixture of corner and edge-sharing OLiMn3 tetrahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(2), one Mn(1), one Mn(2), and one Mn(3) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(3), one Mn(2), one Mn(7), and one Mn(8) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(4), one Mn(4), one Mn(7), and one Mn(8) atom.