Li3MnF6 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one F(2), one F(3), one F(4), and two equivalent F(1) atoms. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one F(2), one F(3), and one F(6) atom. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one F(2), two equivalent F(5), and two equivalent F(6) atoms. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a distorted octahedral geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. In the second Mn site, Mn(2) is bonded in an octahedral geometry to two equivalent F(4), two equivalent F(5), and two equivalent F(6) atoms. There are six inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one Mn(1) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), and one Mn(1) atom to form distorted corner-sharing FLi3Mn trigonal pyramids. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one Mn(1) atom. In the fourth F site, F(4) is bonded in a 2-coordinate geometry to one Li(1) and one Mn(2) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to two equivalent Li(3) and one Mn(2) atom. In the sixth F site, F(6) is bonded to one Li(2), two equivalent Li(3), and one Mn(2) atom to form distorted corner-sharing FLi3Mn trigonal pyramids.
Li3MnF6 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one F(2), one F(3), one F(4), and two equivalent F(1) atoms. The Li(1)-F(2) bond length is 1.93 Å. The Li(1)-F(3) bond length is 1.93 Å. The Li(1)-F(4) bond length is 1.92 Å. There is one shorter (2.14 Å) and one longer (2.31 Å) Li(1)-F(1) bond length. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one F(2), one F(3), and one F(6) atom. The Li(2)-F(2) bond length is 1.96 Å. The Li(2)-F(3) bond length is 2.03 Å. The Li(2)-F(6) bond length is 1.92 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one F(2), two equivalent F(5), and two equivalent F(6) atoms. The Li(3)-F(2) bond length is 1.90 Å. There is one shorter (2.03 Å) and one longer (2.16 Å) Li(3)-F(5) bond length. There is one shorter (1.91 Å) and one longer (2.28 Å) Li(3)-F(6) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a distorted octahedral geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. Both Mn(1)-F(1) bond lengths are 1.89 Å. Both Mn(1)-F(2) bond lengths are 2.26 Å. Both Mn(1)-F(3) bond lengths are 1.90 Å. In the second Mn site, Mn(2) is bonded in an octahedral geometry to two equivalent F(4), two equivalent F(5), and two equivalent F(6) atoms. Both Mn(2)-F(4) bond lengths are 1.89 Å. Both Mn(2)-F(5) bond lengths are 1.87 Å. Both Mn(2)-F(6) bond lengths are 2.15 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one Mn(1) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), and one Mn(1) atom to form distorted corner-sharing FLi3Mn trigonal pyramids. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one Mn(1) atom. In the fourth F site, F(4) is bonded in a 2-coordinate geometry to one Li(1) and one Mn(2) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to two equivalent Li(3) and one Mn(2) atom. In the sixth F site, F(6) is bonded to one Li(2), two equivalent Li(3), and one Mn(2) atom to form distorted corner-sharing FLi3Mn trigonal pyramids.