V4PbBi6O20 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(6), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Pb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 70°. In the second V site, V(2) is bonded to one O(1), one O(10), one O(5), and one O(7) atom to form VO4 tetrahedra that share  an edgeedge with one Pb(1)O6 octahedra. Pb(1) is bonded to two equivalent O(1), two equivalent O(10), and two equivalent O(9) atoms to form distorted PbO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra and edges with two equivalent V(2)O4 tetrahedra. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(5), one O(6), one O(7), one O(8), and two equivalent O(4) atoms. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to one O(10), one O(2), one O(4), one O(5), one O(6), one O(9), and two equivalent O(3) atoms. In the third Bi site, Bi(3) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(7) atom. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one V(2), one Pb(1), and one Bi(3) atom. In the second O site, O(2) is bonded in a 1-coordinate geometry to one V(1), one Bi(2), and one Bi(3) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Bi(3) and two equivalent Bi(2) atoms. In the fourth O site, O(4) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(1) atoms to form distorted edge-sharing OBi4 tetrahedra. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one V(2), one Bi(1), and one Bi(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one V(1), one Bi(1), and one Bi(2) atom. In the seventh O site, O(7) is bonded in a 1-coordinate geometry to one V(2), one Bi(1), and one Bi(3) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one V(1) and one Bi(1) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one V(1), one Pb(1), and one Bi(2) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one V(2), one Pb(1), and one Bi(2) atom.
V4PbBi6O20 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(6), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Pb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 70°. The V(1)-O(2) bond length is 1.75 Å. The V(1)-O(6) bond length is 1.75 Å. The V(1)-O(8) bond length is 1.73 Å. The V(1)-O(9) bond length is 1.76 Å. In the second V site, V(2) is bonded to one O(1), one O(10), one O(5), and one O(7) atom to form VO4 tetrahedra that share  an edgeedge with one Pb(1)O6 octahedra. The V(2)-O(1) bond length is 1.74 Å. The V(2)-O(10) bond length is 1.73 Å. The V(2)-O(5) bond length is 1.76 Å. The V(2)-O(7) bond length is 1.74 Å. Pb(1) is bonded to two equivalent O(1), two equivalent O(10), and two equivalent O(9) atoms to form distorted PbO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra and edges with two equivalent V(2)O4 tetrahedra. Both Pb(1)-O(1) bond lengths are 2.64 Å. Both Pb(1)-O(10) bond lengths are 2.67 Å. Both Pb(1)-O(9) bond lengths are 2.54 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(5), one O(6), one O(7), one O(8), and two equivalent O(4) atoms. The Bi(1)-O(5) bond length is 2.31 Å. The Bi(1)-O(6) bond length is 2.40 Å. The Bi(1)-O(7) bond length is 2.79 Å. The Bi(1)-O(8) bond length is 2.50 Å. There is one shorter (2.19 Å) and one longer (2.33 Å) Bi(1)-O(4) bond length. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to one O(10), one O(2), one O(4), one O(5), one O(6), one O(9), and two equivalent O(3) atoms. The Bi(2)-O(10) bond length is 2.42 Å. The Bi(2)-O(2) bond length is 2.76 Å. The Bi(2)-O(4) bond length is 2.66 Å. The Bi(2)-O(5) bond length is 2.81 Å. The Bi(2)-O(6) bond length is 2.71 Å. The Bi(2)-O(9) bond length is 2.39 Å. There is one shorter (2.25 Å) and one longer (2.34 Å) Bi(2)-O(3) bond length. In the third Bi site, Bi(3) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(7) atom. The Bi(3)-O(1) bond length is 2.44 Å. The Bi(3)-O(2) bond length is 2.38 Å. The Bi(3)-O(3) bond length is 2.14 Å. The Bi(3)-O(4) bond length is 2.34 Å. The Bi(3)-O(7) bond length is 2.32 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one V(2), one Pb(1), and one Bi(3) atom. In the second O site, O(2) is bonded in a 1-coordinate geometry to one V(1), one Bi(2), and one Bi(3) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Bi(3) and two equivalent Bi(2) atoms. In the fourth O site, O(4) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(1) atoms to form distorted edge-sharing OBi4 tetrahedra. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one V(2), one Bi(1), and one Bi(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one V(1), one Bi(1), and one Bi(2) atom. In the seventh O site, O(7) is bonded in a 1-coordinate geometry to one V(2), one Bi(1), and one Bi(3) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one V(1) and one Bi(1) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one V(1), one Pb(1), and one Bi(2) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one V(2), one Pb(1), and one Bi(2) atom.