Li3Mn4F19 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(17), one F(5), one F(6), and two equivalent F(3) atoms to form LiF5 trigonal bipyramids that share  a cornercorner with one Mn(2)F6 octahedra, corners with three equivalent Mn(1)F6 octahedra,  a cornercorner with one Mn(3)F5 trigonal bipyramid, and  an edgeedge with one Li(1)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 17-47°. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(1), one F(12), one F(2), one F(8), and one F(9) atom. In the third Li site, Li(3) is bonded to one F(10), one F(13), one F(14), one F(15), one F(18), and one F(7) atom to form distorted LiF6 octahedra that share  a cornercorner with one Mn(4)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra,  a cornercorner with one Mn(3)F5 trigonal bipyramid, and  an edgeedge with one Mn(3)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 11-37°. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(11), one F(16), one F(17), one F(2), one F(3), and one F(9) atom to form MnF6 octahedra that share  a cornercorner with one Mn(4)F6 octahedra,  a cornercorner with one Mn(3)F5 trigonal bipyramid, and corners with three equivalent Li(1)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 18°. In the second Mn site, Mn(2) is bonded to one F(10), one F(12), one F(13), one F(6), and two equivalent F(8) atoms to form MnF6 octahedra that share corners with two equivalent Li(3)F6 octahedra,  a cornercorner with one Li(1)F5 trigonal bipyramid, and  an edgeedge with one Mn(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 11-14°. In the third Mn site, Mn(3) is bonded to one F(11), one F(14), one F(18), one F(5), and one F(7) atom to form distorted MnF5 trigonal bipyramids that share  a cornercorner with one Li(3)F6 octahedra,  a cornercorner with one Mn(1)F6 octahedra,  a cornercorner with one Li(1)F5 trigonal bipyramid, and  an edgeedge with one Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 9-21°. In the fourth Mn site, Mn(4) is bonded to one F(1), one F(15), one F(16), one F(4), and two equivalent F(19) atoms to form MnF6 octahedra that share  a cornercorner with one Li(3)F6 octahedra,  a cornercorner with one Mn(1)F6 octahedra, and  an edgeedge with one Mn(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 18-37°. There are nineteen inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Li(2) and one Mn(4) atom. In the second F site, F(2) is bonded in a distorted L-shaped geometry to one Li(2) and one Mn(1) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one Mn(1) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to one Mn(4) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(3) atom. In the sixth F site, F(6) is bonded in a linear geometry to one Li(1) and one Mn(2) atom. In the seventh F site, F(7) is bonded in a water-like geometry to one Li(3) and one Mn(3) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Mn(2) atoms. In the ninth F site, F(9) is bonded in a water-like geometry to one Li(2) and one Mn(1) atom. In the tenth F site, F(10) is bonded in a linear geometry to one Li(3) and one Mn(2) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to one Mn(1) and one Mn(3) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one Li(2) and one Mn(2) atom. In the thirteenth F site, F(13) is bonded in a linear geometry to one Li(3) and one Mn(2) atom. In the fourteenth F site, F(14) is bonded in a linear geometry to one Li(3) and one Mn(3) atom. In the fifteenth F site, F(15) is bonded in a bent 150 degrees geometry to one Li(3) and one Mn(4) atom. In the sixteenth F site, F(16) is bonded in a bent 150 degrees geometry to one Mn(1) and one Mn(4) atom. In the seventeenth F site, F(17) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(1) atom. In the eighteenth F site, F(18) is bonded in a water-like geometry to one Li(3) and one Mn(3) atom. In the nineteenth F site, F(19) is bonded in a water-like geometry to two equivalent Mn(4) atoms.
Li3Mn4F19 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(17), one F(5), one F(6), and two equivalent F(3) atoms to form LiF5 trigonal bipyramids that share  a cornercorner with one Mn(2)F6 octahedra, corners with three equivalent Mn(1)F6 octahedra,  a cornercorner with one Mn(3)F5 trigonal bipyramid, and  an edgeedge with one Li(1)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 17-47°. The Li(1)-F(17) bond length is 1.96 Å. The Li(1)-F(5) bond length is 1.96 Å. The Li(1)-F(6) bond length is 1.97 Å. There is one shorter (2.12 Å) and one longer (2.16 Å) Li(1)-F(3) bond length. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(1), one F(12), one F(2), one F(8), and one F(9) atom. The Li(2)-F(1) bond length is 2.02 Å. The Li(2)-F(12) bond length is 1.91 Å. The Li(2)-F(2) bond length is 2.42 Å. The Li(2)-F(8) bond length is 2.39 Å. The Li(2)-F(9) bond length is 1.97 Å. In the third Li site, Li(3) is bonded to one F(10), one F(13), one F(14), one F(15), one F(18), and one F(7) atom to form distorted LiF6 octahedra that share  a cornercorner with one Mn(4)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra,  a cornercorner with one Mn(3)F5 trigonal bipyramid, and  an edgeedge with one Mn(3)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 11-37°. The Li(3)-F(10) bond length is 1.95 Å. The Li(3)-F(13) bond length is 2.10 Å. The Li(3)-F(14) bond length is 2.06 Å. The Li(3)-F(15) bond length is 2.11 Å. The Li(3)-F(18) bond length is 2.09 Å. The Li(3)-F(7) bond length is 2.18 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(11), one F(16), one F(17), one F(2), one F(3), and one F(9) atom to form MnF6 octahedra that share  a cornercorner with one Mn(4)F6 octahedra,  a cornercorner with one Mn(3)F5 trigonal bipyramid, and corners with three equivalent Li(1)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 18°. The Mn(1)-F(11) bond length is 1.91 Å. The Mn(1)-F(16) bond length is 1.95 Å. The Mn(1)-F(17) bond length is 1.79 Å. The Mn(1)-F(2) bond length is 1.78 Å. The Mn(1)-F(3) bond length is 1.87 Å. The Mn(1)-F(9) bond length is 1.79 Å. In the second Mn site, Mn(2) is bonded to one F(10), one F(12), one F(13), one F(6), and two equivalent F(8) atoms to form MnF6 octahedra that share corners with two equivalent Li(3)F6 octahedra,  a cornercorner with one Li(1)F5 trigonal bipyramid, and  an edgeedge with one Mn(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 11-14°. The Mn(2)-F(10) bond length is 1.80 Å. The Mn(2)-F(12) bond length is 1.83 Å. The Mn(2)-F(13) bond length is 1.80 Å. The Mn(2)-F(6) bond length is 1.79 Å. There is one shorter (1.95 Å) and one longer (1.99 Å) Mn(2)-F(8) bond length. In the third Mn site, Mn(3) is bonded to one F(11), one F(14), one F(18), one F(5), and one F(7) atom to form distorted MnF5 trigonal bipyramids that share  a cornercorner with one Li(3)F6 octahedra,  a cornercorner with one Mn(1)F6 octahedra,  a cornercorner with one Li(1)F5 trigonal bipyramid, and  an edgeedge with one Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 9-21°. The Mn(3)-F(11) bond length is 1.93 Å. The Mn(3)-F(14) bond length is 1.79 Å. The Mn(3)-F(18) bond length is 1.78 Å. The Mn(3)-F(5) bond length is 1.80 Å. The Mn(3)-F(7) bond length is 1.79 Å. In the fourth Mn site, Mn(4) is bonded to one F(1), one F(15), one F(16), one F(4), and two equivalent F(19) atoms to form MnF6 octahedra that share  a cornercorner with one Li(3)F6 octahedra,  a cornercorner with one Mn(1)F6 octahedra, and  an edgeedge with one Mn(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 18-37°. The Mn(4)-F(1) bond length is 1.79 Å. The Mn(4)-F(15) bond length is 1.80 Å. The Mn(4)-F(16) bond length is 1.89 Å. The Mn(4)-F(4) bond length is 1.80 Å. There is one shorter (1.92 Å) and one longer (2.03 Å) Mn(4)-F(19) bond length. There are nineteen inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Li(2) and one Mn(4) atom. In the second F site, F(2) is bonded in a distorted L-shaped geometry to one Li(2) and one Mn(1) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one Mn(1) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to one Mn(4) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(3) atom. In the sixth F site, F(6) is bonded in a linear geometry to one Li(1) and one Mn(2) atom. In the seventh F site, F(7) is bonded in a water-like geometry to one Li(3) and one Mn(3) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Mn(2) atoms. In the ninth F site, F(9) is bonded in a water-like geometry to one Li(2) and one Mn(1) atom. In the tenth F site, F(10) is bonded in a linear geometry to one Li(3) and one Mn(2) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to one Mn(1) and one Mn(3) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one Li(2) and one Mn(2) atom. In the thirteenth F site, F(13) is bonded in a linear geometry to one Li(3) and one Mn(2) atom. In the fourteenth F site, F(14) is bonded in a linear geometry to one Li(3) and one Mn(3) atom. In the fifteenth F site, F(15) is bonded in a bent 150 degrees geometry to one Li(3) and one Mn(4) atom. In the sixteenth F site, F(16) is bonded in a bent 150 degrees geometry to one Mn(1) and one Mn(4) atom. In the seventeenth F site, F(17) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(1) atom. In the eighteenth F site, F(18) is bonded in a water-like geometry to one Li(3) and one Mn(3) atom. In the nineteenth F site, F(19) is bonded in a water-like geometry to two equivalent Mn(4) atoms.