Pb5Al3F19 crystallizes in the tetragonal I4/m space group. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one F(7), one F(8), and four equivalent F(4) atoms to form corner-sharing AlF6 octahedra. The corner-sharing octahedra are not tilted. In the second Al site, Al(2) is bonded in an octahedral geometry to one F(2), one F(3), two equivalent F(1), and two equivalent F(6) atoms. There are three inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 6-coordinate geometry to one F(3), one F(5), two equivalent F(4), and two equivalent F(6) atoms. In the second Pb site, Pb(2) is bonded in a 4-coordinate geometry to one F(3), one F(5), and two equivalent F(1) atoms. In the third Pb site, Pb(3) is bonded in a 4-coordinate geometry to four equivalent F(2) atoms. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Al(2) and one Pb(2) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to one Al(2) and two equivalent Pb(3) atoms. In the third F site, F(3) is bonded in a distorted single-bond geometry to one Al(2), one Pb(1), and one Pb(2) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to one Al(1) and one Pb(1) atom. In the fifth F site, F(8) is bonded in a linear geometry to two equivalent Al(1) atoms. In the sixth F site, F(5) is bonded in a 1-coordinate geometry to one Pb(1) and one Pb(2) atom. In the seventh F site, F(6) is bonded in a distorted single-bond geometry to one Al(2) and one Pb(1) atom. In the eighth F site, F(7) is bonded in a linear geometry to two equivalent Al(1) atoms.
Pb5Al3F19 crystallizes in the tetragonal I4/m space group. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one F(7), one F(8), and four equivalent F(4) atoms to form corner-sharing AlF6 octahedra. The corner-sharing octahedra are not tilted. The Al(1)-F(7) bond length is 1.81 Å. The Al(1)-F(8) bond length is 1.85 Å. All Al(1)-F(4) bond lengths are 1.82 Å. In the second Al site, Al(2) is bonded in an octahedral geometry to one F(2), one F(3), two equivalent F(1), and two equivalent F(6) atoms. The Al(2)-F(2) bond length is 1.85 Å. The Al(2)-F(3) bond length is 1.82 Å. Both Al(2)-F(1) bond lengths are 1.82 Å. Both Al(2)-F(6) bond lengths are 1.84 Å. There are three inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 6-coordinate geometry to one F(3), one F(5), two equivalent F(4), and two equivalent F(6) atoms. The Pb(1)-F(3) bond length is 2.54 Å. The Pb(1)-F(5) bond length is 2.65 Å. Both Pb(1)-F(4) bond lengths are 2.65 Å. Both Pb(1)-F(6) bond lengths are 2.54 Å. In the second Pb site, Pb(2) is bonded in a 4-coordinate geometry to one F(3), one F(5), and two equivalent F(1) atoms. The Pb(2)-F(3) bond length is 2.59 Å. The Pb(2)-F(5) bond length is 2.33 Å. Both Pb(2)-F(1) bond lengths are 2.53 Å. In the third Pb site, Pb(3) is bonded in a 4-coordinate geometry to four equivalent F(2) atoms. All Pb(3)-F(2) bond lengths are 2.53 Å. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Al(2) and one Pb(2) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to one Al(2) and two equivalent Pb(3) atoms. In the third F site, F(3) is bonded in a distorted single-bond geometry to one Al(2), one Pb(1), and one Pb(2) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to one Al(1) and one Pb(1) atom. In the fifth F site, F(8) is bonded in a linear geometry to two equivalent Al(1) atoms. In the sixth F site, F(5) is bonded in a 1-coordinate geometry to one Pb(1) and one Pb(2) atom. In the seventh F site, F(6) is bonded in a distorted single-bond geometry to one Al(2) and one Pb(1) atom. In the eighth F site, F(7) is bonded in a linear geometry to two equivalent Al(1) atoms.