PbV2O6 crystallizes in the orthorhombic C222 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(2)O4 tetrahedra, and  a cornercorner with one Pb(1)O4 trigonal pyramid. In the second V site, V(2) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form VO4 tetrahedra that share corners with two equivalent V(1)O4 tetrahedra and corners with two equivalent Pb(1)O4 trigonal pyramids. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted PbO4 trigonal pyramids that share corners with two equivalent V(1)O4 tetrahedra and corners with two equivalent V(2)O4 tetrahedra. In the second Pb site, Pb(2) is bonded in a 4-coordinate geometry to four equivalent O(5) atoms. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one V(2) and one Pb(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one V(1) and one Pb(1) atom. In the third O site, O(3) is bonded in a water-like geometry to one V(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the fifth O site, O(5) is bonded in a distorted water-like geometry to one V(1) and one Pb(2) atom.
PbV2O6 crystallizes in the orthorhombic C222 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(2)O4 tetrahedra, and  a cornercorner with one Pb(1)O4 trigonal pyramid. The V(1)-O(2) bond length is 1.67 Å. The V(1)-O(3) bond length is 1.86 Å. The V(1)-O(4) bond length is 1.80 Å. The V(1)-O(5) bond length is 1.71 Å. In the second V site, V(2) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form VO4 tetrahedra that share corners with two equivalent V(1)O4 tetrahedra and corners with two equivalent Pb(1)O4 trigonal pyramids. Both V(2)-O(1) bond lengths are 1.69 Å. Both V(2)-O(3) bond lengths are 1.85 Å. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted PbO4 trigonal pyramids that share corners with two equivalent V(1)O4 tetrahedra and corners with two equivalent V(2)O4 tetrahedra. Both Pb(1)-O(1) bond lengths are 2.37 Å. Both Pb(1)-O(2) bond lengths are 2.52 Å. In the second Pb site, Pb(2) is bonded in a 4-coordinate geometry to four equivalent O(5) atoms. All Pb(2)-O(5) bond lengths are 2.52 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one V(2) and one Pb(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one V(1) and one Pb(1) atom. In the third O site, O(3) is bonded in a water-like geometry to one V(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the fifth O site, O(5) is bonded in a distorted water-like geometry to one V(1) and one Pb(2) atom.