Li3MnF6 is Ilmenite-like structured and crystallizes in the triclinic P-1 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(6), two equivalent F(2), and two equivalent F(5) atoms. In the second Li site, Li(2) is bonded to one F(2), one F(3), two equivalent F(4), and two equivalent F(6) atoms to form distorted LiF6 pentagonal pyramids that share  a cornercorner with one Mn(1)F6 octahedra,  a cornercorner with one Mn(2)F6 octahedra,  an edgeedge with one Mn(1)F6 octahedra,  an edgeedge with one Mn(2)F6 octahedra, and edges with two equivalent Li(2)F6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 38-44°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one F(4), one F(5), two equivalent F(1), and two equivalent F(3) atoms. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent F(3), two equivalent F(5), and two equivalent F(6) atoms to form MnF6 octahedra that share corners with two equivalent Li(2)F6 pentagonal pyramids and edges with two equivalent Li(2)F6 pentagonal pyramids. In the second Mn site, Mn(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(4) atoms to form MnF6 octahedra that share corners with two equivalent Li(2)F6 pentagonal pyramids and edges with two equivalent Li(2)F6 pentagonal pyramids. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Li(3), and one Mn(2) atom. In the second F site, F(2) is bonded to one Li(2), two equivalent Li(1), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing FLi3Mn trigonal pyramids. In the third F site, F(3) is bonded in a distorted see-saw-like geometry to one Li(2), two equivalent Li(3), and one Mn(1) atom. In the fourth F site, F(4) is bonded to one Li(3), two equivalent Li(2), and one Mn(2) atom to form a mixture of corner and edge-sharing FLi3Mn trigonal pyramids. In the fifth F site, F(5) is bonded to one Li(3), two equivalent Li(1), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing FLi3Mn tetrahedra. In the sixth F site, F(6) is bonded to one Li(1), two equivalent Li(2), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing FLi3Mn tetrahedra.
Li3MnF6 is Ilmenite-like structured and crystallizes in the triclinic P-1 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(6), two equivalent F(2), and two equivalent F(5) atoms. The Li(1)-F(1) bond length is 2.46 Å. The Li(1)-F(6) bond length is 2.22 Å. There is one shorter (1.95 Å) and one longer (2.13 Å) Li(1)-F(2) bond length. There is one shorter (1.98 Å) and one longer (2.16 Å) Li(1)-F(5) bond length. In the second Li site, Li(2) is bonded to one F(2), one F(3), two equivalent F(4), and two equivalent F(6) atoms to form distorted LiF6 pentagonal pyramids that share  a cornercorner with one Mn(1)F6 octahedra,  a cornercorner with one Mn(2)F6 octahedra,  an edgeedge with one Mn(1)F6 octahedra,  an edgeedge with one Mn(2)F6 octahedra, and edges with two equivalent Li(2)F6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 38-44°. The Li(2)-F(2) bond length is 2.23 Å. The Li(2)-F(3) bond length is 2.04 Å. There is one shorter (1.96 Å) and one longer (2.11 Å) Li(2)-F(4) bond length. There is one shorter (2.06 Å) and one longer (2.34 Å) Li(2)-F(6) bond length. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one F(4), one F(5), two equivalent F(1), and two equivalent F(3) atoms. The Li(3)-F(4) bond length is 2.14 Å. The Li(3)-F(5) bond length is 2.07 Å. There is one shorter (2.01 Å) and one longer (2.27 Å) Li(3)-F(1) bond length. There is one shorter (2.01 Å) and one longer (2.14 Å) Li(3)-F(3) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent F(3), two equivalent F(5), and two equivalent F(6) atoms to form MnF6 octahedra that share corners with two equivalent Li(2)F6 pentagonal pyramids and edges with two equivalent Li(2)F6 pentagonal pyramids. Both Mn(1)-F(3) bond lengths are 2.00 Å. Both Mn(1)-F(5) bond lengths are 2.02 Å. Both Mn(1)-F(6) bond lengths are 1.88 Å. In the second Mn site, Mn(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(4) atoms to form MnF6 octahedra that share corners with two equivalent Li(2)F6 pentagonal pyramids and edges with two equivalent Li(2)F6 pentagonal pyramids. Both Mn(2)-F(1) bond lengths are 1.86 Å. Both Mn(2)-F(2) bond lengths are 2.00 Å. Both Mn(2)-F(4) bond lengths are 2.00 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Li(3), and one Mn(2) atom. In the second F site, F(2) is bonded to one Li(2), two equivalent Li(1), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing FLi3Mn trigonal pyramids. In the third F site, F(3) is bonded in a distorted see-saw-like geometry to one Li(2), two equivalent Li(3), and one Mn(1) atom. In the fourth F site, F(4) is bonded to one Li(3), two equivalent Li(2), and one Mn(2) atom to form a mixture of corner and edge-sharing FLi3Mn trigonal pyramids. In the fifth F site, F(5) is bonded to one Li(3), two equivalent Li(1), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing FLi3Mn tetrahedra. In the sixth F site, F(6) is bonded to one Li(1), two equivalent Li(2), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing FLi3Mn tetrahedra.