Li3MnF6 is Ilmenite-like structured and crystallizes in the triclinic P1 space group. There are nine inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(11), one F(12), one F(5), one F(6), one F(7), and one F(9) atom to form LiF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Li(5)F6 octahedra,  an edgeedge with one Li(8)F6 octahedra, and  an edgeedge with one Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. In the second Li site, Li(2) is bonded to one F(1), one F(11), one F(13), one F(2), one F(4), and one F(7) atom to form LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(6)F6 octahedra, corners with two equivalent Li(7)F6 octahedra, corners with two equivalent Mn(3)F6 octahedra,  an edgeedge with one Mn(1)F6 octahedra,  an edgeedge with one Mn(2)F6 octahedra, and faces with two equivalent Li(5)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-54°. In the third Li site, Li(3) is bonded to one F(10), one F(12), one F(14), one F(15), one F(8), and one F(9) atom to form LiF6 octahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra,  an edgeedge with one Li(6)F6 octahedra,  an edgeedge with one Li(7)F6 octahedra, and  an edgeedge with one Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 37-48°. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one F(10), one F(12), one F(14), one F(15), one F(8), and one F(9) atom. In the fifth Li site, Li(5) is bonded to one F(1), one F(11), one F(13), one F(2), one F(4), and one F(7) atom to form distorted LiF6 octahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra,  an edgeedge with one Li(6)F6 octahedra,  an edgeedge with one Li(7)F6 octahedra,  an edgeedge with one Mn(3)F6 octahedra, and faces with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 40-48°. In the sixth Li site, Li(6) is bonded to one F(10), one F(13), one F(16), one F(18), one F(4), and one F(8) atom to form LiF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Li(5)F6 octahedra,  an edgeedge with one Li(8)F6 octahedra, and  an edgeedge with one Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-56°. In the seventh Li site, Li(7) is bonded to one F(1), one F(14), one F(15), one F(17), one F(2), and one F(3) atom to form LiF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Li(5)F6 octahedra,  an edgeedge with one Li(8)F6 octahedra, and  an edgeedge with one Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-52°. In the eighth Li site, Li(8) is bonded to one F(16), one F(17), one F(18), one F(3), one F(5), and one F(6) atom to form LiF6 octahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra,  an edgeedge with one Li(6)F6 octahedra,  an edgeedge with one Li(7)F6 octahedra, and  an edgeedge with one Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 38-47°. In the ninth Li site, Li(9) is bonded in a 6-coordinate geometry to one F(16), one F(17), one F(18), one F(3), one F(5), and one F(6) atom. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(2), one F(3), one F(4), one F(5), one F(8), and one F(9) atom to form MnF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(5)F6 octahedra, corners with two equivalent Li(6)F6 octahedra, corners with two equivalent Li(7)F6 octahedra, corners with two equivalent Li(8)F6 octahedra, and  an edgeedge with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 37-55°. In the second Mn site, Mn(2) is bonded to one F(11), one F(12), one F(13), one F(14), one F(16), and one F(17) atom to form MnF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(5)F6 octahedra, corners with two equivalent Li(6)F6 octahedra, corners with two equivalent Li(7)F6 octahedra, corners with two equivalent Li(8)F6 octahedra, and  an edgeedge with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 38-56°. In the third Mn site, Mn(3) is bonded to one F(1), one F(10), one F(15), one F(18), one F(6), and one F(7) atom to form MnF6 octahedra that share corners with two equivalent Li(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Li(5)F6 octahedra,  an edgeedge with one Li(6)F6 octahedra,  an edgeedge with one Li(7)F6 octahedra, and  an edgeedge with one Li(8)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. There are eighteen inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(5), one Li(7), and one Mn(3) atom. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(5), one Li(7), and one Mn(1) atom. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(7), one Li(8), one Li(9), and one Mn(1) atom. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(5), one Li(6), and one Mn(1) atom. In the fifth F site, F(5) is bonded to one Li(1), one Li(8), one Li(9), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing FLi3Mn trigonal pyramids. In the sixth F site, F(6) is bonded to one Li(1), one Li(8), one Li(9), and one Mn(3) atom to form a mixture of corner and edge-sharing FLi3Mn trigonal pyramids. In the seventh F site, F(7) is bonded to one Li(1), one Li(2), one Li(5), and one Mn(3) atom to form a mixture of distorted corner and edge-sharing FLi3Mn trigonal pyramids. In the eighth F site, F(8) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Li(6), and one Mn(1) atom. In the ninth F site, F(9) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Li(4), and one Mn(1) atom. In the tenth F site, F(10) is bonded to one Li(3), one Li(4), one Li(6), and one Mn(3) atom to form a mixture of distorted corner and edge-sharing FLi3Mn trigonal pyramids. In the eleventh F site, F(11) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(5), and one Mn(2) atom. In the twelfth F site, F(12) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Li(4), and one Mn(2) atom. In the thirteenth F site, F(13) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(5), one Li(6), and one Mn(2) atom. In the fourteenth F site, F(14) is bonded to one Li(3), one Li(4), one Li(7), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing FLi3Mn trigonal pyramids. In the fifteenth F site, F(15) is bonded to one Li(3), one Li(4), one Li(7), and one Mn(3) atom to form a mixture of corner and edge-sharing FLi3Mn trigonal pyramids. In the sixteenth F site, F(16) is bonded in a distorted rectangular see-saw-like geometry to one Li(6), one Li(8), one Li(9), and one Mn(2) atom. In the seventeenth F site, F(17) is bonded in a distorted rectangular see-saw-like geometry to one Li(7), one Li(8), one Li(9), and one Mn(2) atom. In the eighteenth F site, F(18) is bonded in a distorted rectangular see-saw-like geometry to one Li(6), one Li(8), one Li(9), and one Mn(3) atom.
Li3MnF6 is Ilmenite-like structured and crystallizes in the triclinic P1 space group. There are nine inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(11), one F(12), one F(5), one F(6), one F(7), and one F(9) atom to form LiF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Li(5)F6 octahedra,  an edgeedge with one Li(8)F6 octahedra, and  an edgeedge with one Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. The Li(1)-F(11) bond length is 2.34 Å. The Li(1)-F(12) bond length is 2.07 Å. The Li(1)-F(5) bond length is 2.04 Å. The Li(1)-F(6) bond length is 2.00 Å. The Li(1)-F(7) bond length is 2.17 Å. The Li(1)-F(9) bond length is 2.11 Å. In the second Li site, Li(2) is bonded to one F(1), one F(11), one F(13), one F(2), one F(4), and one F(7) atom to form LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(6)F6 octahedra, corners with two equivalent Li(7)F6 octahedra, corners with two equivalent Mn(3)F6 octahedra,  an edgeedge with one Mn(1)F6 octahedra,  an edgeedge with one Mn(2)F6 octahedra, and faces with two equivalent Li(5)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-54°. The Li(2)-F(1) bond length is 2.03 Å. The Li(2)-F(11) bond length is 2.04 Å. The Li(2)-F(13) bond length is 2.10 Å. The Li(2)-F(2) bond length is 2.03 Å. The Li(2)-F(4) bond length is 2.06 Å. The Li(2)-F(7) bond length is 2.04 Å. In the third Li site, Li(3) is bonded to one F(10), one F(12), one F(14), one F(15), one F(8), and one F(9) atom to form LiF6 octahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra,  an edgeedge with one Li(6)F6 octahedra,  an edgeedge with one Li(7)F6 octahedra, and  an edgeedge with one Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 37-48°. The Li(3)-F(10) bond length is 2.14 Å. The Li(3)-F(12) bond length is 1.97 Å. The Li(3)-F(14) bond length is 1.97 Å. The Li(3)-F(15) bond length is 1.96 Å. The Li(3)-F(8) bond length is 2.20 Å. The Li(3)-F(9) bond length is 1.98 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one F(10), one F(12), one F(14), one F(15), one F(8), and one F(9) atom. The Li(4)-F(10) bond length is 2.03 Å. The Li(4)-F(12) bond length is 2.32 Å. The Li(4)-F(14) bond length is 1.92 Å. The Li(4)-F(15) bond length is 1.89 Å. The Li(4)-F(8) bond length is 2.03 Å. The Li(4)-F(9) bond length is 2.22 Å. In the fifth Li site, Li(5) is bonded to one F(1), one F(11), one F(13), one F(2), one F(4), and one F(7) atom to form distorted LiF6 octahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra,  an edgeedge with one Li(6)F6 octahedra,  an edgeedge with one Li(7)F6 octahedra,  an edgeedge with one Mn(3)F6 octahedra, and faces with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 40-48°. The Li(5)-F(1) bond length is 2.02 Å. The Li(5)-F(11) bond length is 2.26 Å. The Li(5)-F(13) bond length is 1.87 Å. The Li(5)-F(2) bond length is 2.14 Å. The Li(5)-F(4) bond length is 1.86 Å. The Li(5)-F(7) bond length is 2.04 Å. In the sixth Li site, Li(6) is bonded to one F(10), one F(13), one F(16), one F(18), one F(4), and one F(8) atom to form LiF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Li(5)F6 octahedra,  an edgeedge with one Li(8)F6 octahedra, and  an edgeedge with one Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-56°. The Li(6)-F(10) bond length is 2.10 Å. The Li(6)-F(13) bond length is 1.99 Å. The Li(6)-F(16) bond length is 2.23 Å. The Li(6)-F(18) bond length is 2.09 Å. The Li(6)-F(4) bond length is 1.96 Å. The Li(6)-F(8) bond length is 2.36 Å. In the seventh Li site, Li(7) is bonded to one F(1), one F(14), one F(15), one F(17), one F(2), and one F(3) atom to form LiF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Li(5)F6 octahedra,  an edgeedge with one Li(8)F6 octahedra, and  an edgeedge with one Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-52°. The Li(7)-F(1) bond length is 2.16 Å. The Li(7)-F(14) bond length is 2.05 Å. The Li(7)-F(15) bond length is 2.00 Å. The Li(7)-F(17) bond length is 2.13 Å. The Li(7)-F(2) bond length is 2.24 Å. The Li(7)-F(3) bond length is 2.12 Å. In the eighth Li site, Li(8) is bonded to one F(16), one F(17), one F(18), one F(3), one F(5), and one F(6) atom to form LiF6 octahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra,  an edgeedge with one Li(6)F6 octahedra,  an edgeedge with one Li(7)F6 octahedra, and  an edgeedge with one Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 38-47°. The Li(8)-F(16) bond length is 2.10 Å. The Li(8)-F(17) bond length is 2.01 Å. The Li(8)-F(18) bond length is 2.13 Å. The Li(8)-F(3) bond length is 2.00 Å. The Li(8)-F(5) bond length is 1.96 Å. The Li(8)-F(6) bond length is 1.97 Å. In the ninth Li site, Li(9) is bonded in a 6-coordinate geometry to one F(16), one F(17), one F(18), one F(3), one F(5), and one F(6) atom. The Li(9)-F(16) bond length is 2.02 Å. The Li(9)-F(17) bond length is 2.26 Å. The Li(9)-F(18) bond length is 1.99 Å. The Li(9)-F(3) bond length is 2.40 Å. The Li(9)-F(5) bond length is 1.92 Å. The Li(9)-F(6) bond length is 1.87 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(2), one F(3), one F(4), one F(5), one F(8), and one F(9) atom to form MnF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(5)F6 octahedra, corners with two equivalent Li(6)F6 octahedra, corners with two equivalent Li(7)F6 octahedra, corners with two equivalent Li(8)F6 octahedra, and  an edgeedge with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 37-55°. The Mn(1)-F(2) bond length is 1.94 Å. The Mn(1)-F(3) bond length is 1.91 Å. The Mn(1)-F(4) bond length is 2.13 Å. The Mn(1)-F(5) bond length is 2.14 Å. The Mn(1)-F(8) bond length is 1.90 Å. The Mn(1)-F(9) bond length is 1.93 Å. In the second Mn site, Mn(2) is bonded to one F(11), one F(12), one F(13), one F(14), one F(16), and one F(17) atom to form MnF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(5)F6 octahedra, corners with two equivalent Li(6)F6 octahedra, corners with two equivalent Li(7)F6 octahedra, corners with two equivalent Li(8)F6 octahedra, and  an edgeedge with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 38-56°. The Mn(2)-F(11) bond length is 1.90 Å. The Mn(2)-F(12) bond length is 1.94 Å. The Mn(2)-F(13) bond length is 2.12 Å. The Mn(2)-F(14) bond length is 2.15 Å. The Mn(2)-F(16) bond length is 1.94 Å. The Mn(2)-F(17) bond length is 1.91 Å. In the third Mn site, Mn(3) is bonded to one F(1), one F(10), one F(15), one F(18), one F(6), and one F(7) atom to form MnF6 octahedra that share corners with two equivalent Li(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Li(5)F6 octahedra,  an edgeedge with one Li(6)F6 octahedra,  an edgeedge with one Li(7)F6 octahedra, and  an edgeedge with one Li(8)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. The Mn(3)-F(1) bond length is 1.90 Å. The Mn(3)-F(10) bond length is 1.90 Å. The Mn(3)-F(15) bond length is 2.08 Å. The Mn(3)-F(18) bond length is 1.91 Å. The Mn(3)-F(6) bond length is 2.08 Å. The Mn(3)-F(7) bond length is 1.90 Å. There are eighteen inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(5), one Li(7), and one Mn(3) atom. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(5), one Li(7), and one Mn(1) atom. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(7), one Li(8), one Li(9), and one Mn(1) atom. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(5), one Li(6), and one Mn(1) atom. In the fifth F site, F(5) is bonded to one Li(1), one Li(8), one Li(9), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing FLi3Mn trigonal pyramids. In the sixth F site, F(6) is bonded to one Li(1), one Li(8), one Li(9), and one Mn(3) atom to form a mixture of corner and edge-sharing FLi3Mn trigonal pyramids. In the seventh F site, F(7) is bonded to one Li(1), one Li(2), one Li(5), and one Mn(3) atom to form a mixture of distorted corner and edge-sharing FLi3Mn trigonal pyramids. In the eighth F site, F(8) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Li(6), and one Mn(1) atom. In the ninth F site, F(9) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Li(4), and one Mn(1) atom. In the tenth F site, F(10) is bonded to one Li(3), one Li(4), one Li(6), and one Mn(3) atom to form a mixture of distorted corner and edge-sharing FLi3Mn trigonal pyramids. In the eleventh F site, F(11) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(5), and one Mn(2) atom. In the twelfth F site, F(12) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Li(4), and one Mn(2) atom. In the thirteenth F site, F(13) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(5), one Li(6), and one Mn(2) atom. In the fourteenth F site, F(14) is bonded to one Li(3), one Li(4), one Li(7), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing FLi3Mn trigonal pyramids. In the fifteenth F site, F(15) is bonded to one Li(3), one Li(4), one Li(7), and one Mn(3) atom to form a mixture of corner and edge-sharing FLi3Mn trigonal pyramids. In the sixteenth F site, F(16) is bonded in a distorted rectangular see-saw-like geometry to one Li(6), one Li(8), one Li(9), and one Mn(2) atom. In the seventeenth F site, F(17) is bonded in a distorted rectangular see-saw-like geometry to one Li(7), one Li(8), one Li(9), and one Mn(2) atom. In the eighteenth F site, F(18) is bonded in a distorted rectangular see-saw-like geometry to one Li(6), one Li(8), one Li(9), and one Mn(3) atom.