Pb5Al3F19 crystallizes in the triclinic P-1 space group. There are three inequivalent Al sites. In the first Al site, Al(1) is bonded to one F(15), one F(17), one F(20), one F(6), one F(7), and one F(8) atom 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(11), one F(12), one F(16), one F(18), one F(3), and one F(5) atom. In the third Al site, Al(3) is bonded in an octahedral geometry to one F(13), one F(14), one F(19), one F(2), one F(4), and one F(9) atom. There are five inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 6-coordinate geometry to one F(1), one F(10), two equivalent F(11), and two equivalent F(4) atoms. In the second Pb site, Pb(2) is bonded in a 4-coordinate geometry to one F(10), one F(12), one F(16), and one F(5) atom. In the third Pb site, Pb(3) is bonded in a 6-coordinate geometry to one F(10), one F(18), one F(3), one F(5), one F(6), and one F(7) atom. In the fourth Pb site, Pb(4) is bonded in a 6-coordinate geometry to one F(1), one F(13), one F(14), one F(17), one F(8), and one F(9) atom. In the fifth Pb site, Pb(5) is bonded in a 4-coordinate geometry to one F(1), one F(19), one F(2), and one F(9) atom. There are twenty inequivalent F sites. In the first F site, F(1) is bonded in a trigonal non-coplanar geometry to one Pb(1), one Pb(4), and one Pb(5) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to one Al(3) and one Pb(5) atom. In the third F site, F(3) is bonded in a distorted single-bond geometry to one Al(2) and one Pb(3) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to one Al(3) and two equivalent Pb(1) atoms. In the fifth F site, F(5) is bonded in a distorted single-bond geometry to one Al(2), one Pb(2), and one Pb(3) atom. In the sixth F site, F(6) is bonded in a single-bond geometry to one Al(1) and one Pb(3) atom. In the seventh F site, F(7) is bonded in a single-bond geometry to one Al(1) and one Pb(3) atom. In the eighth F site, F(8) is bonded in a distorted single-bond geometry to one Al(1) and one Pb(4) atom. In the ninth F site, F(9) is bonded in a distorted single-bond geometry to one Al(3), one Pb(4), and one Pb(5) atom. In the tenth F site, F(10) is bonded in a 3-coordinate geometry to one Pb(1), one Pb(2), and one Pb(3) atom. In the eleventh F site, F(11) is bonded in a distorted single-bond geometry to one Al(2) and two equivalent Pb(1) atoms. In the twelfth F site, F(12) is bonded in a distorted single-bond geometry to one Al(2) and one Pb(2) atom. In the thirteenth F site, F(13) is bonded in a single-bond geometry to one Al(3) and one Pb(4) atom. In the fourteenth F site, F(14) is bonded in a distorted single-bond geometry to one Al(3) and one Pb(4) atom. In the fifteenth F site, F(15) is bonded in a linear geometry to two equivalent Al(1) atoms. In the sixteenth F site, F(16) is bonded in a distorted single-bond geometry to one Al(2) and one Pb(2) atom. In the seventeenth F site, F(17) is bonded in a single-bond geometry to one Al(1) and one Pb(4) atom. In the eighteenth F site, F(18) is bonded in a distorted single-bond geometry to one Al(2) and one Pb(3) atom. In the nineteenth F site, F(19) is bonded in a distorted bent 150 degrees geometry to one Al(3) and one Pb(5) atom. In the twentieth F site, F(20) is bonded in a linear geometry to two equivalent Al(1) atoms.
Pb5Al3F19 crystallizes in the triclinic P-1 space group. There are three inequivalent Al sites. In the first Al site, Al(1) is bonded to one F(15), one F(17), one F(20), one F(6), one F(7), and one F(8) atom to form corner-sharing AlF6 octahedra. The corner-sharing octahedra are not tilted. The Al(1)-F(15) bond length is 1.81 Å. The Al(1)-F(17) bond length is 1.82 Å. The Al(1)-F(20) bond length is 1.85 Å. The Al(1)-F(6) bond length is 1.82 Å. The Al(1)-F(7) bond length is 1.82 Å. The Al(1)-F(8) bond length is 1.81 Å. In the second Al site, Al(2) is bonded in an octahedral geometry to one F(11), one F(12), one F(16), one F(18), one F(3), and one F(5) atom. The Al(2)-F(11) bond length is 1.86 Å. The Al(2)-F(12) bond length is 1.82 Å. The Al(2)-F(16) bond length is 1.83 Å. The Al(2)-F(18) bond length is 1.86 Å. The Al(2)-F(3) bond length is 1.82 Å. The Al(2)-F(5) bond length is 1.83 Å. In the third Al site, Al(3) is bonded in an octahedral geometry to one F(13), one F(14), one F(19), one F(2), one F(4), and one F(9) atom. The Al(3)-F(13) bond length is 1.86 Å. The Al(3)-F(14) bond length is 1.83 Å. The Al(3)-F(19) bond length is 1.82 Å. The Al(3)-F(2) bond length is 1.83 Å. The Al(3)-F(4) bond length is 1.85 Å. The Al(3)-F(9) bond length is 1.82 Å. There are five inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 6-coordinate geometry to one F(1), one F(10), two equivalent F(11), and two equivalent F(4) atoms. The Pb(1)-F(1) bond length is 2.52 Å. The Pb(1)-F(10) bond length is 2.70 Å. There is one shorter (2.52 Å) and one longer (2.58 Å) Pb(1)-F(11) bond length. There is one shorter (2.53 Å) and one longer (2.65 Å) Pb(1)-F(4) bond length. In the second Pb site, Pb(2) is bonded in a 4-coordinate geometry to one F(10), one F(12), one F(16), and one F(5) atom. The Pb(2)-F(10) bond length is 2.31 Å. The Pb(2)-F(12) bond length is 2.55 Å. The Pb(2)-F(16) bond length is 2.53 Å. The Pb(2)-F(5) bond length is 2.61 Å. In the third Pb site, Pb(3) is bonded in a 6-coordinate geometry to one F(10), one F(18), one F(3), one F(5), one F(6), and one F(7) atom. The Pb(3)-F(10) bond length is 2.58 Å. The Pb(3)-F(18) bond length is 2.61 Å. The Pb(3)-F(3) bond length is 2.50 Å. The Pb(3)-F(5) bond length is 2.54 Å. The Pb(3)-F(6) bond length is 2.66 Å. The Pb(3)-F(7) bond length is 2.67 Å. In the fourth Pb site, Pb(4) is bonded in a 6-coordinate geometry to one F(1), one F(13), one F(14), one F(17), one F(8), and one F(9) atom. The Pb(4)-F(1) bond length is 2.58 Å. The Pb(4)-F(13) bond length is 2.67 Å. The Pb(4)-F(14) bond length is 2.46 Å. The Pb(4)-F(17) bond length is 2.71 Å. The Pb(4)-F(8) bond length is 2.59 Å. The Pb(4)-F(9) bond length is 2.57 Å. In the fifth Pb site, Pb(5) is bonded in a 4-coordinate geometry to one F(1), one F(19), one F(2), and one F(9) atom. The Pb(5)-F(1) bond length is 2.32 Å. The Pb(5)-F(19) bond length is 2.51 Å. The Pb(5)-F(2) bond length is 2.61 Å. The Pb(5)-F(9) bond length is 2.60 Å. There are twenty inequivalent F sites. In the first F site, F(1) is bonded in a trigonal non-coplanar geometry to one Pb(1), one Pb(4), and one Pb(5) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to one Al(3) and one Pb(5) atom. In the third F site, F(3) is bonded in a distorted single-bond geometry to one Al(2) and one Pb(3) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to one Al(3) and two equivalent Pb(1) atoms. In the fifth F site, F(5) is bonded in a distorted single-bond geometry to one Al(2), one Pb(2), and one Pb(3) atom. In the sixth F site, F(6) is bonded in a single-bond geometry to one Al(1) and one Pb(3) atom. In the seventh F site, F(7) is bonded in a single-bond geometry to one Al(1) and one Pb(3) atom. In the eighth F site, F(8) is bonded in a distorted single-bond geometry to one Al(1) and one Pb(4) atom. In the ninth F site, F(9) is bonded in a distorted single-bond geometry to one Al(3), one Pb(4), and one Pb(5) atom. In the tenth F site, F(10) is bonded in a 3-coordinate geometry to one Pb(1), one Pb(2), and one Pb(3) atom. In the eleventh F site, F(11) is bonded in a distorted single-bond geometry to one Al(2) and two equivalent Pb(1) atoms. In the twelfth F site, F(12) is bonded in a distorted single-bond geometry to one Al(2) and one Pb(2) atom. In the thirteenth F site, F(13) is bonded in a single-bond geometry to one Al(3) and one Pb(4) atom. In the fourteenth F site, F(14) is bonded in a distorted single-bond geometry to one Al(3) and one Pb(4) atom. In the fifteenth F site, F(15) is bonded in a linear geometry to two equivalent Al(1) atoms. In the sixteenth F site, F(16) is bonded in a distorted single-bond geometry to one Al(2) and one Pb(2) atom. In the seventeenth F site, F(17) is bonded in a single-bond geometry to one Al(1) and one Pb(4) atom. In the eighteenth F site, F(18) is bonded in a distorted single-bond geometry to one Al(2) and one Pb(3) atom. In the nineteenth F site, F(19) is bonded in a distorted bent 150 degrees geometry to one Al(3) and one Pb(5) atom. In the twentieth F site, F(20) is bonded in a linear geometry to two equivalent Al(1) atoms.