Li3AlF6 crystallizes in the orthorhombic Pna2_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(2), one F(3), one F(5), and two equivalent F(6) atoms. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(3), one F(5), and two equivalent F(4) atoms. In the third Li site, Li(3) is bonded to one F(1), one F(2), one F(3), one F(5), and two equivalent F(6) atoms to form distorted LiF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Al(1)F6 octahedra, and edges with two equivalent Al(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. Al(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 AlF6 octahedra that share corners with two equivalent Li(3)F6 octahedra and edges with two equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. There are six inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Al(1) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), and one Al(1) atom to form a mixture of edge and corner-sharing FLi3Al trigonal pyramids. In the third F site, F(3) is bonded to one Li(1), one Li(2), one Li(3), and one Al(1) atom to form a mixture of distorted edge and corner-sharing FLi3Al trigonal pyramids. In the fourth F site, F(4) is bonded in a trigonal planar geometry to two equivalent Li(2) and one Al(1) atom. In the fifth F site, F(5) is bonded to one Li(1), one Li(2), one Li(3), and one Al(1) atom to form a mixture of distorted edge and corner-sharing FLi3Al trigonal pyramids. In the sixth F site, F(6) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(3), and one Al(1) atom.
Li3AlF6 crystallizes in the orthorhombic Pna2_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(2), one F(3), one F(5), and two equivalent F(6) atoms. The Li(1)-F(1) bond length is 1.85 Å. The Li(1)-F(2) bond length is 2.07 Å. The Li(1)-F(3) bond length is 1.87 Å. The Li(1)-F(5) bond length is 2.03 Å. There is one shorter (2.07 Å) and one longer (2.38 Å) Li(1)-F(6) bond length. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(3), one F(5), and two equivalent F(4) atoms. The Li(2)-F(1) bond length is 2.39 Å. The Li(2)-F(2) bond length is 1.96 Å. The Li(2)-F(3) bond length is 2.09 Å. The Li(2)-F(5) bond length is 2.11 Å. There is one shorter (1.85 Å) and one longer (1.91 Å) Li(2)-F(4) bond length. In the third Li site, Li(3) is bonded to one F(1), one F(2), one F(3), one F(5), and two equivalent F(6) atoms to form distorted LiF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Al(1)F6 octahedra, and edges with two equivalent Al(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. The Li(3)-F(1) bond length is 1.97 Å. The Li(3)-F(2) bond length is 1.91 Å. The Li(3)-F(3) bond length is 2.17 Å. The Li(3)-F(5) bond length is 1.89 Å. There is one shorter (2.03 Å) and one longer (2.05 Å) Li(3)-F(6) bond length. Al(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 AlF6 octahedra that share corners with two equivalent Li(3)F6 octahedra and edges with two equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. The Al(1)-F(1) bond length is 1.80 Å. The Al(1)-F(2) bond length is 1.82 Å. The Al(1)-F(3) bond length is 1.80 Å. The Al(1)-F(4) bond length is 1.79 Å. The Al(1)-F(5) bond length is 1.81 Å. The Al(1)-F(6) bond length is 1.84 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Al(1) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), and one Al(1) atom to form a mixture of edge and corner-sharing FLi3Al trigonal pyramids. In the third F site, F(3) is bonded to one Li(1), one Li(2), one Li(3), and one Al(1) atom to form a mixture of distorted edge and corner-sharing FLi3Al trigonal pyramids. In the fourth F site, F(4) is bonded in a trigonal planar geometry to two equivalent Li(2) and one Al(1) atom. In the fifth F site, F(5) is bonded to one Li(1), one Li(2), one Li(3), and one Al(1) atom to form a mixture of distorted edge and corner-sharing FLi3Al trigonal pyramids. In the sixth F site, F(6) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(3), and one Al(1) atom.