PbBiVO5 crystallizes in the triclinic P1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(6), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Bi(1)O5 square pyramid and corners with two equivalent Bi(2)O5 square pyramids. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Bi(2)O5 square pyramid and corners with two equivalent Bi(1)O5 square pyramids. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(4), one O(5), and one O(7) atom. In the second Pb site, Pb(2) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(5), one O(6), and one O(9) atom. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(2), one O(3), one O(5), and one O(6) atom to form distorted BiO5 square pyramids that share  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and  an edgeedge with one Bi(2)O5 square pyramid. In the second Bi site, Bi(2) is bonded to one O(1), one O(10), one O(4), one O(5), and one O(9) atom to form distorted BiO5 square pyramids that share  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O5 square pyramid. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Pb(1), one Pb(2), one Bi(1), and one Bi(2) atom to form edge-sharing OBi2Pb2 tetrahedra. In the second O site, O(2) is bonded in a 1-coordinate geometry to one V(2), one Pb(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(2), one Pb(2), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one V(2), one Pb(1), and one Bi(2) atom. In the fifth O site, O(5) is bonded to one Pb(1), one Pb(2), one Bi(1), and one Bi(2) atom to form edge-sharing OBi2Pb2 tetrahedra. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one V(1), one Pb(2), and one Bi(1) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one V(1) and one Pb(1) atom. In the eighth O site, O(8) is bonded in a single-bond geometry to one V(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one V(1), one Pb(2), and one Bi(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one V(1), one Pb(1), and one Bi(2) atom.
PbBiVO5 crystallizes in the triclinic P1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(6), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Bi(1)O5 square pyramid and corners with two equivalent Bi(2)O5 square pyramids. The V(1)-O(10) bond length is 1.76 Å. The V(1)-O(6) bond length is 1.77 Å. The V(1)-O(7) bond length is 1.71 Å. The V(1)-O(9) bond length is 1.77 Å. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Bi(2)O5 square pyramid and corners with two equivalent Bi(1)O5 square pyramids. The V(2)-O(2) bond length is 1.76 Å. The V(2)-O(3) bond length is 1.76 Å. The V(2)-O(4) bond length is 1.77 Å. The V(2)-O(8) bond length is 1.71 Å. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(4), one O(5), and one O(7) atom. The Pb(1)-O(1) bond length is 2.47 Å. The Pb(1)-O(10) bond length is 2.70 Å. The Pb(1)-O(2) bond length is 2.74 Å. The Pb(1)-O(4) bond length is 2.55 Å. The Pb(1)-O(5) bond length is 2.56 Å. The Pb(1)-O(7) bond length is 2.83 Å. In the second Pb site, Pb(2) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(5), one O(6), and one O(9) atom. The Pb(2)-O(1) bond length is 2.55 Å. The Pb(2)-O(3) bond length is 2.69 Å. The Pb(2)-O(5) bond length is 2.47 Å. The Pb(2)-O(6) bond length is 2.56 Å. The Pb(2)-O(9) bond length is 2.65 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(2), one O(3), one O(5), and one O(6) atom to form distorted BiO5 square pyramids that share  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and  an edgeedge with one Bi(2)O5 square pyramid. The Bi(1)-O(1) bond length is 2.30 Å. The Bi(1)-O(2) bond length is 2.36 Å. The Bi(1)-O(3) bond length is 2.33 Å. The Bi(1)-O(5) bond length is 2.17 Å. The Bi(1)-O(6) bond length is 2.41 Å. In the second Bi site, Bi(2) is bonded to one O(1), one O(10), one O(4), one O(5), and one O(9) atom to form distorted BiO5 square pyramids that share  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O5 square pyramid. The Bi(2)-O(1) bond length is 2.17 Å. The Bi(2)-O(10) bond length is 2.33 Å. The Bi(2)-O(4) bond length is 2.39 Å. The Bi(2)-O(5) bond length is 2.30 Å. The Bi(2)-O(9) bond length is 2.38 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Pb(1), one Pb(2), one Bi(1), and one Bi(2) atom to form edge-sharing OBi2Pb2 tetrahedra. In the second O site, O(2) is bonded in a 1-coordinate geometry to one V(2), one Pb(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(2), one Pb(2), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one V(2), one Pb(1), and one Bi(2) atom. In the fifth O site, O(5) is bonded to one Pb(1), one Pb(2), one Bi(1), and one Bi(2) atom to form edge-sharing OBi2Pb2 tetrahedra. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one V(1), one Pb(2), and one Bi(1) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one V(1) and one Pb(1) atom. In the eighth O site, O(8) is bonded in a single-bond geometry to one V(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one V(1), one Pb(2), and one Bi(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one V(1), one Pb(1), and one Bi(2) atom.