Li3PF6 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 linear geometry to two equivalent F(2) atoms. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted LiF6 octahedra that share faces with two equivalent P(1)F6 octahedra. In the third Li site, Li(3) is bonded in a square co-planar geometry to two equivalent F(1) and two equivalent F(3) atoms. P(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form PF6 octahedra that share faces with two equivalent Li(2)F6 octahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one P(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one P(1) atom. In the third F site, F(3) is bonded in a T-shaped geometry to one Li(2), one Li(3), and one P(1) atom.
Li3PF6 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 linear geometry to two equivalent F(2) atoms. Both Li(1)-F(2) bond lengths are 1.81 Å. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted LiF6 octahedra that share faces with two equivalent P(1)F6 octahedra. Both Li(2)-F(1) bond lengths are 1.95 Å. Both Li(2)-F(2) bond lengths are 2.27 Å. Both Li(2)-F(3) bond lengths are 1.91 Å. In the third Li site, Li(3) is bonded in a square co-planar geometry to two equivalent F(1) and two equivalent F(3) atoms. Both Li(3)-F(1) bond lengths are 2.00 Å. Both Li(3)-F(3) bond lengths are 2.06 Å. P(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form PF6 octahedra that share faces with two equivalent Li(2)F6 octahedra. Both P(1)-F(1) bond lengths are 2.00 Å. Both P(1)-F(2) bond lengths are 1.98 Å. Both P(1)-F(3) bond lengths are 1.98 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one P(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one P(1) atom. In the third F site, F(3) is bonded in a T-shaped geometry to one Li(2), one Li(3), and one P(1) atom.