Pb5(VO4)3Cl crystallizes in the hexagonal P6_3/m space group. V(1) is bonded in a tetrahedral geometry to one O(2), one O(3), and two equivalent O(1) atoms. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 6-coordinate geometry to three equivalent O(2) and three equivalent O(3) atoms. In the second Pb site, Pb(2) is bonded in a 5-coordinate geometry to one O(2), four equivalent O(1), and two equivalent Cl(1) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one V(1) and two equivalent Pb(2) atoms. In the second O site, O(2) is bonded in a 1-coordinate geometry to one V(1), one Pb(2), and two equivalent Pb(1) atoms. In the third O site, O(3) is bonded in a distorted single-bond geometry to one V(1) and two equivalent Pb(1) atoms. Cl(1) is bonded to six equivalent Pb(2) atoms to form face-sharing ClPb6 octahedra.
Pb5(VO4)3Cl crystallizes in the hexagonal P6_3/m space group. V(1) is bonded in a tetrahedral geometry to one O(2), one O(3), and two equivalent O(1) atoms. The V(1)-O(2) bond length is 1.77 Å. The V(1)-O(3) bond length is 1.75 Å. Both V(1)-O(1) bond lengths are 1.74 Å. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 6-coordinate geometry to three equivalent O(2) and three equivalent O(3) atoms. All Pb(1)-O(2) bond lengths are 2.75 Å. All Pb(1)-O(3) bond lengths are 2.52 Å. In the second Pb site, Pb(2) is bonded in a 5-coordinate geometry to one O(2), four equivalent O(1), and two equivalent Cl(1) atoms. The Pb(2)-O(2) bond length is 2.37 Å. There are two shorter (2.61 Å) and two longer (2.67 Å) Pb(2)-O(1) bond lengths. Both Pb(2)-Cl(1) bond lengths are 3.23 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one V(1) and two equivalent Pb(2) atoms. In the second O site, O(2) is bonded in a 1-coordinate geometry to one V(1), one Pb(2), and two equivalent Pb(1) atoms. In the third O site, O(3) is bonded in a distorted single-bond geometry to one V(1) and two equivalent Pb(1) atoms. Cl(1) is bonded to six equivalent Pb(2) atoms to form face-sharing ClPb6 octahedra.