Pb5F8 crystallizes in the monoclinic Cm space group. There are ten inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 7-coordinate geometry to one F(12), one F(2), one F(7), two equivalent F(16), and two equivalent F(6) atoms. In the second Pb site, Pb(2) is bonded in a 4-coordinate geometry to two equivalent F(1) and two equivalent F(7) atoms. In the third Pb site, Pb(3) is bonded in a 6-coordinate geometry to one F(1), one F(14), one F(4), one F(9), and two equivalent F(11) atoms. In the fourth Pb site, Pb(4) is bonded in a 7-coordinate geometry to one F(13), one F(16), one F(5), two equivalent F(2), and two equivalent F(4) atoms. In the fifth Pb site, Pb(5) is bonded in a 7-coordinate geometry to one F(10), one F(15), one F(5), two equivalent F(14), and two equivalent F(3) atoms. In the sixth Pb site, Pb(6) is bonded in a 4-coordinate geometry to one F(13), one F(16), one F(3), and one F(8) atom. In the seventh Pb site, Pb(7) is bonded in a 7-coordinate geometry to one F(14), one F(6), one F(9), two equivalent F(10), and two equivalent F(12) atoms. In the eighth Pb site, Pb(8) is bonded in a 6-coordinate geometry to one F(2), one F(3), one F(7), one F(8), and two equivalent F(5) atoms. In the ninth Pb site, Pb(9) is bonded in a 6-coordinate geometry to one F(11), one F(12), two equivalent F(8), and two equivalent F(9) atoms. In the tenth Pb site, Pb(10) is bonded in a 4-coordinate geometry to one F(1), one F(10), one F(15), and one F(4) atom. There are sixteen inequivalent F sites. In the first F site, F(1) is bonded to one Pb(10), one Pb(3), and two equivalent Pb(2) atoms to form a mixture of distorted corner and edge-sharing FPb4 tetrahedra. In the second F site, F(2) is bonded to one Pb(1), one Pb(8), and two equivalent Pb(4) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra. In the third F site, F(3) is bonded to one Pb(6), one Pb(8), and two equivalent Pb(5) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra. In the fourth F site, F(4) is bonded to one Pb(10), one Pb(3), and two equivalent Pb(4) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra. In the fifth F site, F(5) is bonded to one Pb(4), one Pb(5), and two equivalent Pb(8) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra. In the sixth F site, F(6) is bonded in a trigonal non-coplanar geometry to one Pb(7) and two equivalent Pb(1) atoms. In the seventh F site, F(7) is bonded to one Pb(1), one Pb(8), and two equivalent Pb(2) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra. In the eighth F site, F(8) is bonded to one Pb(6), one Pb(8), and two equivalent Pb(9) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra. In the ninth F site, F(9) is bonded to one Pb(3), one Pb(7), and two equivalent Pb(9) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra. In the tenth F site, F(10) is bonded to one Pb(10), one Pb(5), and two equivalent Pb(7) atoms to form a mixture of distorted corner and edge-sharing FPb4 tetrahedra. In the eleventh F site, F(11) is bonded in a distorted trigonal non-coplanar geometry to one Pb(9) and two equivalent Pb(3) atoms. In the twelfth F site, F(12) is bonded to one Pb(1), one Pb(9), and two equivalent Pb(7) atoms to form a mixture of distorted corner and edge-sharing FPb4 tetrahedra. In the thirteenth F site, F(13) is bonded in a distorted water-like geometry to one Pb(4) and one Pb(6) atom. In the fourteenth F site, F(14) is bonded to one Pb(3), one Pb(7), and two equivalent Pb(5) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra. In the fifteenth F site, F(15) is bonded in a bent 120 degrees geometry to one Pb(10) and one Pb(5) atom. In the sixteenth F site, F(16) is bonded to one Pb(4), one Pb(6), and two equivalent Pb(1) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra.
Pb5F8 crystallizes in the monoclinic Cm space group. There are ten inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 7-coordinate geometry to one F(12), one F(2), one F(7), two equivalent F(16), and two equivalent F(6) atoms. The Pb(1)-F(12) bond length is 2.54 Å. The Pb(1)-F(2) bond length is 2.58 Å. The Pb(1)-F(7) bond length is 2.41 Å. Both Pb(1)-F(16) bond lengths are 2.60 Å. Both Pb(1)-F(6) bond lengths are 2.48 Å. In the second Pb site, Pb(2) is bonded in a 4-coordinate geometry to two equivalent F(1) and two equivalent F(7) atoms. Both Pb(2)-F(1) bond lengths are 2.57 Å. Both Pb(2)-F(7) bond lengths are 2.63 Å. In the third Pb site, Pb(3) is bonded in a 6-coordinate geometry to one F(1), one F(14), one F(4), one F(9), and two equivalent F(11) atoms. The Pb(3)-F(1) bond length is 2.43 Å. The Pb(3)-F(14) bond length is 2.55 Å. The Pb(3)-F(4) bond length is 2.56 Å. The Pb(3)-F(9) bond length is 2.49 Å. Both Pb(3)-F(11) bond lengths are 2.49 Å. In the fourth Pb site, Pb(4) is bonded in a 7-coordinate geometry to one F(13), one F(16), one F(5), two equivalent F(2), and two equivalent F(4) atoms. The Pb(4)-F(13) bond length is 2.49 Å. The Pb(4)-F(16) bond length is 2.41 Å. The Pb(4)-F(5) bond length is 2.59 Å. Both Pb(4)-F(2) bond lengths are 2.59 Å. Both Pb(4)-F(4) bond lengths are 2.57 Å. In the fifth Pb site, Pb(5) is bonded in a 7-coordinate geometry to one F(10), one F(15), one F(5), two equivalent F(14), and two equivalent F(3) atoms. The Pb(5)-F(10) bond length is 2.72 Å. The Pb(5)-F(15) bond length is 2.33 Å. The Pb(5)-F(5) bond length is 2.52 Å. Both Pb(5)-F(14) bond lengths are 2.60 Å. Both Pb(5)-F(3) bond lengths are 2.56 Å. In the sixth Pb site, Pb(6) is bonded in a 4-coordinate geometry to one F(13), one F(16), one F(3), and one F(8) atom. The Pb(6)-F(13) bond length is 2.44 Å. The Pb(6)-F(16) bond length is 2.55 Å. The Pb(6)-F(3) bond length is 2.54 Å. The Pb(6)-F(8) bond length is 2.65 Å. In the seventh Pb site, Pb(7) is bonded in a 7-coordinate geometry to one F(14), one F(6), one F(9), two equivalent F(10), and two equivalent F(12) atoms. The Pb(7)-F(14) bond length is 2.63 Å. The Pb(7)-F(6) bond length is 2.53 Å. The Pb(7)-F(9) bond length is 2.59 Å. Both Pb(7)-F(10) bond lengths are 2.55 Å. Both Pb(7)-F(12) bond lengths are 2.55 Å. In the eighth Pb site, Pb(8) is bonded in a 6-coordinate geometry to one F(2), one F(3), one F(7), one F(8), and two equivalent F(5) atoms. The Pb(8)-F(2) bond length is 2.60 Å. The Pb(8)-F(3) bond length is 2.72 Å. The Pb(8)-F(7) bond length is 2.60 Å. The Pb(8)-F(8) bond length is 2.55 Å. Both Pb(8)-F(5) bond lengths are 2.71 Å. In the ninth Pb site, Pb(9) is bonded in a 6-coordinate geometry to one F(11), one F(12), two equivalent F(8), and two equivalent F(9) atoms. The Pb(9)-F(11) bond length is 2.49 Å. The Pb(9)-F(12) bond length is 2.77 Å. Both Pb(9)-F(8) bond lengths are 2.51 Å. Both Pb(9)-F(9) bond lengths are 2.65 Å. In the tenth Pb site, Pb(10) is bonded in a 4-coordinate geometry to one F(1), one F(10), one F(15), and one F(4) atom. The Pb(10)-F(1) bond length is 2.70 Å. The Pb(10)-F(10) bond length is 2.50 Å. The Pb(10)-F(15) bond length is 2.49 Å. The Pb(10)-F(4) bond length is 2.65 Å. There are sixteen inequivalent F sites. In the first F site, F(1) is bonded to one Pb(10), one Pb(3), and two equivalent Pb(2) atoms to form a mixture of distorted corner and edge-sharing FPb4 tetrahedra. In the second F site, F(2) is bonded to one Pb(1), one Pb(8), and two equivalent Pb(4) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra. In the third F site, F(3) is bonded to one Pb(6), one Pb(8), and two equivalent Pb(5) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra. In the fourth F site, F(4) is bonded to one Pb(10), one Pb(3), and two equivalent Pb(4) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra. In the fifth F site, F(5) is bonded to one Pb(4), one Pb(5), and two equivalent Pb(8) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra. In the sixth F site, F(6) is bonded in a trigonal non-coplanar geometry to one Pb(7) and two equivalent Pb(1) atoms. In the seventh F site, F(7) is bonded to one Pb(1), one Pb(8), and two equivalent Pb(2) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra. In the eighth F site, F(8) is bonded to one Pb(6), one Pb(8), and two equivalent Pb(9) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra. In the ninth F site, F(9) is bonded to one Pb(3), one Pb(7), and two equivalent Pb(9) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra. In the tenth F site, F(10) is bonded to one Pb(10), one Pb(5), and two equivalent Pb(7) atoms to form a mixture of distorted corner and edge-sharing FPb4 tetrahedra. In the eleventh F site, F(11) is bonded in a distorted trigonal non-coplanar geometry to one Pb(9) and two equivalent Pb(3) atoms. In the twelfth F site, F(12) is bonded to one Pb(1), one Pb(9), and two equivalent Pb(7) atoms to form a mixture of distorted corner and edge-sharing FPb4 tetrahedra. In the thirteenth F site, F(13) is bonded in a distorted water-like geometry to one Pb(4) and one Pb(6) atom. In the fourteenth F site, F(14) is bonded to one Pb(3), one Pb(7), and two equivalent Pb(5) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra. In the fifteenth F site, F(15) is bonded in a bent 120 degrees geometry to one Pb(10) and one Pb(5) atom. In the sixteenth F site, F(16) is bonded to one Pb(4), one Pb(6), and two equivalent Pb(1) atoms to form a mixture of corner and edge-sharing FPb4 tetrahedra.