Li3MnF6 is Ilmenite-like structured and crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form LiF6 octahedra that share edges with three equivalent Mn(1)F6 octahedra. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom. Mn(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form MnF6 octahedra that share edges with three equivalent Li(2)F6 octahedra. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Mn(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Mn(1) atom. In the third F site, F(3) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Mn(1) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Mn(1) atom. In the fifth F site, F(5) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Mn(1) atom. In the sixth F site, F(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Mn(1) atom.
Li3MnF6 is Ilmenite-like structured and crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom. The Li(1)-F(1) bond length is 1.96 Å. The Li(1)-F(2) bond length is 2.44 Å. The Li(1)-F(3) bond length is 2.28 Å. The Li(1)-F(4) bond length is 2.04 Å. The Li(1)-F(5) bond length is 1.90 Å. The Li(1)-F(6) bond length is 2.35 Å. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form LiF6 octahedra that share edges with three equivalent Mn(1)F6 octahedra. The Li(2)-F(1) bond length is 2.10 Å. The Li(2)-F(2) bond length is 2.19 Å. The Li(2)-F(3) bond length is 2.01 Å. The Li(2)-F(4) bond length is 2.14 Å. The Li(2)-F(5) bond length is 2.04 Å. The Li(2)-F(6) bond length is 2.14 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom. The Li(3)-F(1) bond length is 2.33 Å. The Li(3)-F(2) bond length is 1.97 Å. The Li(3)-F(3) bond length is 1.91 Å. The Li(3)-F(4) bond length is 2.44 Å. The Li(3)-F(5) bond length is 2.30 Å. The Li(3)-F(6) bond length is 1.99 Å. Mn(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form MnF6 octahedra that share edges with three equivalent Li(2)F6 octahedra. The Mn(1)-F(1) bond length is 1.92 Å. The Mn(1)-F(2) bond length is 1.88 Å. The Mn(1)-F(3) bond length is 2.07 Å. The Mn(1)-F(4) bond length is 1.89 Å. The Mn(1)-F(5) bond length is 2.07 Å. The Mn(1)-F(6) bond length is 1.92 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Mn(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Mn(1) atom. In the third F site, F(3) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Mn(1) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Mn(1) atom. In the fifth F site, F(5) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Mn(1) atom. In the sixth F site, F(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Mn(1) atom.