Fe3Pb8F24 crystallizes in the triclinic P-1 space group. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent F(11), two equivalent F(7), and two equivalent F(8) atoms to form corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles range from 23-29°. In the second Fe site, Fe(2) is bonded to one F(10), one F(4), one F(5), one F(7), one F(8), and one F(9) atom to form corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles range from 23-29°. There are four inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 7-coordinate geometry to one F(1), one F(12), one F(6), two equivalent F(2), and two equivalent F(3) atoms. In the second Pb site, Pb(2) is bonded in a 6-coordinate geometry to one F(1), one F(10), one F(11), one F(12), one F(2), and one F(3) atom. In the third Pb site, Pb(3) is bonded in a 6-coordinate geometry to one F(4), one F(6), two equivalent F(1), and two equivalent F(12) atoms. In the fourth Pb site, Pb(4) is bonded in a 7-coordinate geometry to one F(10), one F(2), one F(3), one F(6), one F(9), and two equivalent F(5) atoms. There are twelve inequivalent F sites. In the first F site, F(12) is bonded to one Pb(1), one Pb(2), and two equivalent Pb(3) atoms to form a mixture of edge and corner-sharing FPb4 tetrahedra. In the second F site, F(1) is bonded to one Pb(1), one Pb(2), and two equivalent Pb(3) atoms to form a mixture of edge and corner-sharing FPb4 tetrahedra. In the third F site, F(2) is bonded to one Pb(2), one Pb(4), and two equivalent Pb(1) atoms to form a mixture of edge and corner-sharing FPb4 tetrahedra. In the fourth F site, F(3) is bonded to one Pb(2), one Pb(4), and two equivalent Pb(1) atoms to form a mixture of edge and corner-sharing FPb4 tetrahedra. In the fifth F site, F(4) is bonded in a distorted bent 120 degrees geometry to one Fe(2) and one Pb(3) atom. In the sixth F site, F(5) is bonded in a 1-coordinate geometry to one Fe(2) and two equivalent Pb(4) atoms. In the seventh F site, F(6) is bonded in a trigonal non-coplanar geometry to one Pb(1), one Pb(3), and one Pb(4) atom. In the eighth F site, F(7) is bonded in a bent 150 degrees geometry to one Fe(1) and one Fe(2) atom. In the ninth F site, F(8) is bonded in a bent 150 degrees geometry to one Fe(1) and one Fe(2) atom. In the tenth F site, F(9) is bonded in a distorted bent 150 degrees geometry to one Fe(2) and one Pb(4) atom. In the eleventh F site, F(10) is bonded in a distorted single-bond geometry to one Fe(2), one Pb(2), and one Pb(4) atom. In the twelfth F site, F(11) is bonded in a distorted single-bond geometry to one Fe(1) and one Pb(2) atom.
Fe3Pb8F24 crystallizes in the triclinic P-1 space group. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent F(11), two equivalent F(7), and two equivalent F(8) atoms to form corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles range from 23-29°. Both Fe(1)-F(11) bond lengths are 1.94 Å. Both Fe(1)-F(7) bond lengths are 2.02 Å. Both Fe(1)-F(8) bond lengths are 2.00 Å. In the second Fe site, Fe(2) is bonded to one F(10), one F(4), one F(5), one F(7), one F(8), and one F(9) atom to form corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles range from 23-29°. The Fe(2)-F(10) bond length is 1.93 Å. The Fe(2)-F(4) bond length is 1.96 Å. The Fe(2)-F(5) bond length is 1.96 Å. The Fe(2)-F(7) bond length is 2.02 Å. The Fe(2)-F(8) bond length is 2.01 Å. The Fe(2)-F(9) bond length is 1.94 Å. There are four inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 7-coordinate geometry to one F(1), one F(12), one F(6), two equivalent F(2), and two equivalent F(3) atoms. The Pb(1)-F(1) bond length is 2.58 Å. The Pb(1)-F(12) bond length is 2.57 Å. The Pb(1)-F(6) bond length is 2.53 Å. There is one shorter (2.50 Å) and one longer (2.67 Å) Pb(1)-F(2) bond length. There is one shorter (2.40 Å) and one longer (2.62 Å) Pb(1)-F(3) bond length. In the second Pb site, Pb(2) is bonded in a 6-coordinate geometry to one F(1), one F(10), one F(11), one F(12), one F(2), and one F(3) atom. The Pb(2)-F(1) bond length is 2.46 Å. The Pb(2)-F(10) bond length is 2.58 Å. The Pb(2)-F(11) bond length is 2.61 Å. The Pb(2)-F(12) bond length is 2.49 Å. The Pb(2)-F(2) bond length is 2.46 Å. The Pb(2)-F(3) bond length is 2.38 Å. In the third Pb site, Pb(3) is bonded in a 6-coordinate geometry to one F(4), one F(6), two equivalent F(1), and two equivalent F(12) atoms. The Pb(3)-F(4) bond length is 2.54 Å. The Pb(3)-F(6) bond length is 2.44 Å. There is one shorter (2.45 Å) and one longer (2.49 Å) Pb(3)-F(1) bond length. There is one shorter (2.42 Å) and one longer (2.62 Å) Pb(3)-F(12) bond length. In the fourth Pb site, Pb(4) is bonded in a 7-coordinate geometry to one F(10), one F(2), one F(3), one F(6), one F(9), and two equivalent F(5) atoms. The Pb(4)-F(10) bond length is 2.66 Å. The Pb(4)-F(2) bond length is 2.48 Å. The Pb(4)-F(3) bond length is 2.63 Å. The Pb(4)-F(6) bond length is 2.34 Å. The Pb(4)-F(9) bond length is 2.45 Å. There is one shorter (2.48 Å) and one longer (2.72 Å) Pb(4)-F(5) bond length. There are twelve inequivalent F sites. In the first F site, F(12) is bonded to one Pb(1), one Pb(2), and two equivalent Pb(3) atoms to form a mixture of edge and corner-sharing FPb4 tetrahedra. In the second F site, F(1) is bonded to one Pb(1), one Pb(2), and two equivalent Pb(3) atoms to form a mixture of edge and corner-sharing FPb4 tetrahedra. In the third F site, F(2) is bonded to one Pb(2), one Pb(4), and two equivalent Pb(1) atoms to form a mixture of edge and corner-sharing FPb4 tetrahedra. In the fourth F site, F(3) is bonded to one Pb(2), one Pb(4), and two equivalent Pb(1) atoms to form a mixture of edge and corner-sharing FPb4 tetrahedra. In the fifth F site, F(4) is bonded in a distorted bent 120 degrees geometry to one Fe(2) and one Pb(3) atom. In the sixth F site, F(5) is bonded in a 1-coordinate geometry to one Fe(2) and two equivalent Pb(4) atoms. In the seventh F site, F(6) is bonded in a trigonal non-coplanar geometry to one Pb(1), one Pb(3), and one Pb(4) atom. In the eighth F site, F(7) is bonded in a bent 150 degrees geometry to one Fe(1) and one Fe(2) atom. In the ninth F site, F(8) is bonded in a bent 150 degrees geometry to one Fe(1) and one Fe(2) atom. In the tenth F site, F(9) is bonded in a distorted bent 150 degrees geometry to one Fe(2) and one Pb(4) atom. In the eleventh F site, F(10) is bonded in a distorted single-bond geometry to one Fe(2), one Pb(2), and one Pb(4) atom. In the twelfth F site, F(11) is bonded in a distorted single-bond geometry to one Fe(1) and one Pb(2) atom.