LiMn2F9 crystallizes in the triclinic P1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(11), one F(16), one F(2), and one F(3) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one Mn(2)F6 octahedra and corners with three equivalent Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 28-69°. In the second Li site, Li(2) is bonded to one F(14), one F(17), one F(18), and one F(8) atom to form LiF4 tetrahedra that share  a cornercorner with one Mn(4)F6 octahedra and corners with three equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 22-65°. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(12), one F(14), one F(17), one F(4), one F(7), and one F(8) atom to form MnF6 octahedra that share corners with three equivalent Li(2)F4 tetrahedra and  a faceface with one Mn(2)F6 octahedra. In the second Mn site, Mn(2) is bonded to one F(12), one F(15), one F(2), one F(4), one F(6), and one F(7) atom to form MnF6 octahedra that share  a cornercorner with one Li(1)F4 tetrahedra and  a faceface with one Mn(1)F6 octahedra. In the third Mn site, Mn(3) is bonded to one F(10), one F(11), one F(13), one F(16), one F(3), and one F(5) atom to form MnF6 octahedra that share corners with three equivalent Li(1)F4 tetrahedra and  a faceface with one Mn(4)F6 octahedra. In the fourth Mn site, Mn(4) is bonded to one F(1), one F(10), one F(13), one F(18), one F(5), and one F(9) atom to form MnF6 octahedra that share  a cornercorner with one Li(2)F4 tetrahedra and  a faceface with one Mn(3)F6 octahedra. There are eighteen inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one Mn(4) atom. In the second F site, F(2) is bonded in a water-like geometry to one Li(1) and one Mn(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(3) atom. In the fourth F site, F(4) is bonded in an L-shaped geometry to one Mn(1) and one Mn(2) atom. In the fifth F site, F(5) is bonded in an L-shaped geometry to one Mn(3) and one Mn(4) atom. In the sixth F site, F(6) is bonded in a single-bond geometry to one Mn(2) atom. In the seventh F site, F(7) is bonded in an L-shaped geometry to one Mn(1) and one Mn(2) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one Li(2) and one Mn(1) atom. In the ninth F site, F(9) is bonded in a single-bond geometry to one Mn(4) atom. In the tenth F site, F(10) is bonded in an L-shaped geometry to one Mn(3) and one Mn(4) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(3) atom. In the twelfth F site, F(12) is bonded in an L-shaped geometry to one Mn(1) and one Mn(2) atom. In the thirteenth F site, F(13) is bonded in an L-shaped geometry to one Mn(3) and one Mn(4) atom. In the fourteenth F site, F(14) is bonded in a bent 150 degrees geometry to one Li(2) and one Mn(1) atom. In the fifteenth F site, F(15) is bonded in a single-bond geometry to one Mn(2) atom. In the sixteenth F site, F(16) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(3) atom. In the seventeenth F site, F(17) is bonded in a bent 150 degrees geometry to one Li(2) and one Mn(1) atom. In the eighteenth F site, F(18) is bonded in a bent 120 degrees geometry to one Li(2) and one Mn(4) atom.
LiMn2F9 crystallizes in the triclinic P1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(11), one F(16), one F(2), and one F(3) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one Mn(2)F6 octahedra and corners with three equivalent Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 28-69°. The Li(1)-F(11) bond length is 1.96 Å. The Li(1)-F(16) bond length is 1.93 Å. The Li(1)-F(2) bond length is 1.96 Å. The Li(1)-F(3) bond length is 1.91 Å. In the second Li site, Li(2) is bonded to one F(14), one F(17), one F(18), and one F(8) atom to form LiF4 tetrahedra that share  a cornercorner with one Mn(4)F6 octahedra and corners with three equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 22-65°. The Li(2)-F(14) bond length is 1.93 Å. The Li(2)-F(17) bond length is 1.92 Å. The Li(2)-F(18) bond length is 1.96 Å. The Li(2)-F(8) bond length is 1.96 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(12), one F(14), one F(17), one F(4), one F(7), and one F(8) atom to form MnF6 octahedra that share corners with three equivalent Li(2)F4 tetrahedra and  a faceface with one Mn(2)F6 octahedra. The Mn(1)-F(12) bond length is 1.93 Å. The Mn(1)-F(14) bond length is 1.79 Å. The Mn(1)-F(17) bond length is 1.79 Å. The Mn(1)-F(4) bond length is 1.93 Å. The Mn(1)-F(7) bond length is 1.92 Å. The Mn(1)-F(8) bond length is 1.79 Å. In the second Mn site, Mn(2) is bonded to one F(12), one F(15), one F(2), one F(4), one F(6), and one F(7) atom to form MnF6 octahedra that share  a cornercorner with one Li(1)F4 tetrahedra and  a faceface with one Mn(1)F6 octahedra. The Mn(2)-F(12) bond length is 2.00 Å. The Mn(2)-F(15) bond length is 1.75 Å. The Mn(2)-F(2) bond length is 1.79 Å. The Mn(2)-F(4) bond length is 2.01 Å. The Mn(2)-F(6) bond length is 1.76 Å. The Mn(2)-F(7) bond length is 1.95 Å. In the third Mn site, Mn(3) is bonded to one F(10), one F(11), one F(13), one F(16), one F(3), and one F(5) atom to form MnF6 octahedra that share corners with three equivalent Li(1)F4 tetrahedra and  a faceface with one Mn(4)F6 octahedra. The Mn(3)-F(10) bond length is 1.92 Å. The Mn(3)-F(11) bond length is 1.79 Å. The Mn(3)-F(13) bond length is 1.93 Å. The Mn(3)-F(16) bond length is 1.79 Å. The Mn(3)-F(3) bond length is 1.79 Å. The Mn(3)-F(5) bond length is 1.93 Å. In the fourth Mn site, Mn(4) is bonded to one F(1), one F(10), one F(13), one F(18), one F(5), and one F(9) atom to form MnF6 octahedra that share  a cornercorner with one Li(2)F4 tetrahedra and  a faceface with one Mn(3)F6 octahedra. The Mn(4)-F(1) bond length is 1.75 Å. The Mn(4)-F(10) bond length is 1.95 Å. The Mn(4)-F(13) bond length is 2.00 Å. The Mn(4)-F(18) bond length is 1.79 Å. The Mn(4)-F(5) bond length is 2.01 Å. The Mn(4)-F(9) bond length is 1.76 Å. There are eighteen inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one Mn(4) atom. In the second F site, F(2) is bonded in a water-like geometry to one Li(1) and one Mn(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(3) atom. In the fourth F site, F(4) is bonded in an L-shaped geometry to one Mn(1) and one Mn(2) atom. In the fifth F site, F(5) is bonded in an L-shaped geometry to one Mn(3) and one Mn(4) atom. In the sixth F site, F(6) is bonded in a single-bond geometry to one Mn(2) atom. In the seventh F site, F(7) is bonded in an L-shaped geometry to one Mn(1) and one Mn(2) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one Li(2) and one Mn(1) atom. In the ninth F site, F(9) is bonded in a single-bond geometry to one Mn(4) atom. In the tenth F site, F(10) is bonded in an L-shaped geometry to one Mn(3) and one Mn(4) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(3) atom. In the twelfth F site, F(12) is bonded in an L-shaped geometry to one Mn(1) and one Mn(2) atom. In the thirteenth F site, F(13) is bonded in an L-shaped geometry to one Mn(3) and one Mn(4) atom. In the fourteenth F site, F(14) is bonded in a bent 150 degrees geometry to one Li(2) and one Mn(1) atom. In the fifteenth F site, F(15) is bonded in a single-bond geometry to one Mn(2) atom. In the sixteenth F site, F(16) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(3) atom. In the seventeenth F site, F(17) is bonded in a bent 150 degrees geometry to one Li(2) and one Mn(1) atom. In the eighteenth F site, F(18) is bonded in a bent 120 degrees geometry to one Li(2) and one Mn(4) atom.