V3Pb5F19 crystallizes in the tetragonal I4cm space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in an octahedral geometry to one F(1), one F(3), two equivalent F(2), and two equivalent F(7) atoms. In the second V site, V(2) is bonded to two equivalent F(5) and four equivalent F(6) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedra are not tilted. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 5-coordinate geometry to one F(2), one F(3), one F(4), one F(6), and one F(7) atom. In the second Pb site, Pb(2) is bonded in a 6-coordinate geometry to two equivalent F(4) and four equivalent F(1) atoms. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one V(1) and two equivalent Pb(2) atoms. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to one V(1) and one Pb(1) atom. In the third F site, F(3) is bonded in a distorted single-bond geometry to one V(1) and two equivalent Pb(1) atoms. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Pb(2) and two equivalent Pb(1) atoms. In the fifth F site, F(5) is bonded in a linear geometry to two equivalent V(2) atoms. In the sixth F site, F(6) is bonded in a single-bond geometry to one V(2) and one Pb(1) atom. In the seventh F site, F(7) is bonded in a distorted bent 150 degrees geometry to one V(1) and one Pb(1) atom.
V3Pb5F19 crystallizes in the tetragonal I4cm space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in an octahedral geometry to one F(1), one F(3), two equivalent F(2), and two equivalent F(7) atoms. The V(1)-F(1) bond length is 1.98 Å. The V(1)-F(3) bond length is 1.95 Å. Both V(1)-F(2) bond lengths are 1.99 Å. Both V(1)-F(7) bond lengths are 2.00 Å. In the second V site, V(2) is bonded to two equivalent F(5) and four equivalent F(6) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedra are not tilted. There is one shorter (1.93 Å) and one longer (1.95 Å) V(2)-F(5) bond length. All V(2)-F(6) bond lengths are 1.97 Å. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 5-coordinate geometry to one F(2), one F(3), one F(4), one F(6), and one F(7) atom. The Pb(1)-F(2) bond length is 2.47 Å. The Pb(1)-F(3) bond length is 2.65 Å. The Pb(1)-F(4) bond length is 2.41 Å. The Pb(1)-F(6) bond length is 2.69 Å. The Pb(1)-F(7) bond length is 2.39 Å. In the second Pb site, Pb(2) is bonded in a 6-coordinate geometry to two equivalent F(4) and four equivalent F(1) atoms. Both Pb(2)-F(4) bond lengths are 2.54 Å. There are two shorter (2.45 Å) and two longer (2.49 Å) Pb(2)-F(1) bond lengths. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one V(1) and two equivalent Pb(2) atoms. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to one V(1) and one Pb(1) atom. In the third F site, F(3) is bonded in a distorted single-bond geometry to one V(1) and two equivalent Pb(1) atoms. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Pb(2) and two equivalent Pb(1) atoms. In the fifth F site, F(5) is bonded in a linear geometry to two equivalent V(2) atoms. In the sixth F site, F(6) is bonded in a single-bond geometry to one V(2) and one Pb(1) atom. In the seventh F site, F(7) is bonded in a distorted bent 150 degrees geometry to one V(1) and one Pb(1) atom.