Li2Cu3F9 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one F(1), one F(6), and two equivalent F(2) atoms. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one F(1), one F(2), one F(3), and one F(7) atom. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(5), one F(6), and two equivalent F(3) atoms. In the second Cu site, Cu(2) is bonded in a distorted hexagonal planar geometry to one F(8), one F(9), two equivalent F(4), and two equivalent F(5) atoms. In the third Cu site, Cu(3) is bonded in a 4-coordinate geometry to one F(6), one F(7), one F(8), and one F(9) atom. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one Cu(1) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Cu(1) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(2) and two equivalent Cu(1) atoms. In the fourth F site, F(4) is bonded in a distorted bent 120 degrees geometry to two equivalent Cu(2) atoms. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Cu(1) and two equivalent Cu(2) atoms. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Li(1), one Cu(1), and one Cu(3) atom. In the seventh F site, F(7) is bonded in a 2-coordinate geometry to one Li(2) and one Cu(3) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one Cu(2) and one Cu(3) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one Cu(2) and one Cu(3) atom.
Li2Cu3F9 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one F(1), one F(6), and two equivalent F(2) atoms. The Li(1)-F(1) bond length is 2.21 Å. The Li(1)-F(6) bond length is 2.04 Å. There is one shorter (2.10 Å) and one longer (2.20 Å) Li(1)-F(2) bond length. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one F(1), one F(2), one F(3), and one F(7) atom. The Li(2)-F(1) bond length is 2.02 Å. The Li(2)-F(2) bond length is 2.26 Å. The Li(2)-F(3) bond length is 2.44 Å. The Li(2)-F(7) bond length is 1.88 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(5), one F(6), and two equivalent F(3) atoms. The Cu(1)-F(1) bond length is 2.24 Å. The Cu(1)-F(2) bond length is 2.29 Å. The Cu(1)-F(5) bond length is 1.89 Å. The Cu(1)-F(6) bond length is 2.15 Å. There is one shorter (2.24 Å) and one longer (2.27 Å) Cu(1)-F(3) bond length. In the second Cu site, Cu(2) is bonded in a distorted hexagonal planar geometry to one F(8), one F(9), two equivalent F(4), and two equivalent F(5) atoms. The Cu(2)-F(8) bond length is 2.23 Å. The Cu(2)-F(9) bond length is 2.10 Å. There is one shorter (2.05 Å) and one longer (2.23 Å) Cu(2)-F(4) bond length. There is one shorter (2.09 Å) and one longer (2.25 Å) Cu(2)-F(5) bond length. In the third Cu site, Cu(3) is bonded in a 4-coordinate geometry to one F(6), one F(7), one F(8), and one F(9) atom. The Cu(3)-F(6) bond length is 1.45 Å. The Cu(3)-F(7) bond length is 1.48 Å. The Cu(3)-F(8) bond length is 2.06 Å. The Cu(3)-F(9) bond length is 2.03 Å. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one Cu(1) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Cu(1) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(2) and two equivalent Cu(1) atoms. In the fourth F site, F(4) is bonded in a distorted bent 120 degrees geometry to two equivalent Cu(2) atoms. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Cu(1) and two equivalent Cu(2) atoms. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Li(1), one Cu(1), and one Cu(3) atom. In the seventh F site, F(7) is bonded in a 2-coordinate geometry to one Li(2) and one Cu(3) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one Cu(2) and one Cu(3) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one Cu(2) and one Cu(3) atom.