VPbPO6 crystallizes in the monoclinic P2_1/c space group. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form distorted VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and  an edgeedge with one V(1)O6 octahedra. Pb(1) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(5), and two equivalent O(6) atoms. P(1) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-61°. There are six inequivalent O sites. In the first O site, O(6) is bonded in a distorted single-bond geometry to two equivalent Pb(1) and one P(1) atom. In the second O site, O(1) is bonded in a 2-coordinate geometry to one V(1), one Pb(1), and one P(1) atom. In the third O site, O(2) is bonded in a bent 120 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(3) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(1) atom. In the fifth O site, O(4) is bonded in a distorted single-bond geometry to one V(1) and one Pb(1) atom. In the sixth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent V(1) and one Pb(1) atom.
VPbPO6 crystallizes in the monoclinic P2_1/c space group. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form distorted VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and  an edgeedge with one V(1)O6 octahedra. The V(1)-O(1) bond length is 2.00 Å. The V(1)-O(2) bond length is 1.98 Å. The V(1)-O(3) bond length is 2.13 Å. The V(1)-O(4) bond length is 1.67 Å. There is one shorter (1.73 Å) and one longer (2.12 Å) V(1)-O(5) bond length. Pb(1) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(5), and two equivalent O(6) atoms. The Pb(1)-O(1) bond length is 2.68 Å. The Pb(1)-O(4) bond length is 2.52 Å. The Pb(1)-O(5) bond length is 2.66 Å. There is one shorter (2.43 Å) and one longer (2.61 Å) Pb(1)-O(6) bond length. P(1) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-61°. The P(1)-O(1) bond length is 1.58 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.54 Å. There are six inequivalent O sites. In the first O site, O(6) is bonded in a distorted single-bond geometry to two equivalent Pb(1) and one P(1) atom. In the second O site, O(1) is bonded in a 2-coordinate geometry to one V(1), one Pb(1), and one P(1) atom. In the third O site, O(2) is bonded in a bent 120 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(3) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(1) atom. In the fifth O site, O(4) is bonded in a distorted single-bond geometry to one V(1) and one Pb(1) atom. In the sixth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent V(1) and one Pb(1) atom.