V5FePbO11 crystallizes in the orthorhombic Cmc2_1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(6), two equivalent O(3), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent V(4)O5 trigonal bipyramids, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-58°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent V(4)O5 trigonal bipyramids, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-59°. In the third V site, V(3) is bonded to one O(4), one O(7), two equivalent O(5), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with three equivalent V(4)O5 trigonal bipyramids, and  a faceface with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-52°. In the fourth V site, V(4) is bonded to one O(1), one O(6), one O(7), and two equivalent O(8) atoms to form VO5 trigonal bipyramids that share corners with two equivalent V(1)O6 octahedra, corners with three equivalent V(3)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-58°. Fe(1) is bonded to one O(2), one O(7), two equivalent O(3), and two equivalent O(8) atoms to form distorted FeO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with three equivalent V(4)O5 trigonal bipyramids, and  a faceface with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-59°. Pb(1) is bonded in a 3-coordinate geometry to one O(2) and two equivalent O(3) atoms. There are eight inequivalent O sites. In the first O site, O(4) is bonded in a distorted trigonal planar geometry to one V(3) and two equivalent V(2) atoms. In the second O site, O(5) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the third O site, O(6) is bonded in a rectangular see-saw-like geometry to one V(1), one V(4), and two equivalent V(2) atoms. In the fourth O site, O(7) is bonded in a 3-coordinate geometry to one V(3), one V(4), and one Fe(1) atom. In the fifth O site, O(8) is bonded in a 3-coordinate geometry to one V(3), one V(4), and one Fe(1) atom. In the sixth O site, O(1) is bonded in a rectangular see-saw-like geometry to one V(1), one V(4), and two equivalent V(2) atoms. In the seventh O site, O(2) is bonded to two equivalent V(2), one Fe(1), and one Pb(1) atom to form a mixture of distorted corner and edge-sharing OV2FePb tetrahedra. In the eighth O site, O(3) is bonded to one V(1), one V(2), one Fe(1), and one Pb(1) atom to form a mixture of distorted corner and edge-sharing OV2FePb tetrahedra.
V5FePbO11 crystallizes in the orthorhombic Cmc2_1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(6), two equivalent O(3), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent V(4)O5 trigonal bipyramids, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-58°. The V(1)-O(1) bond length is 2.05 Å. The V(1)-O(6) bond length is 2.04 Å. Both V(1)-O(3) bond lengths are 1.95 Å. Both V(1)-O(5) bond lengths are 1.92 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent V(4)O5 trigonal bipyramids, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-59°. The V(2)-O(1) bond length is 2.05 Å. The V(2)-O(2) bond length is 1.96 Å. The V(2)-O(3) bond length is 2.01 Å. The V(2)-O(4) bond length is 1.94 Å. The V(2)-O(5) bond length is 1.99 Å. The V(2)-O(6) bond length is 2.12 Å. In the third V site, V(3) is bonded to one O(4), one O(7), two equivalent O(5), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with three equivalent V(4)O5 trigonal bipyramids, and  a faceface with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-52°. The V(3)-O(4) bond length is 2.02 Å. The V(3)-O(7) bond length is 2.13 Å. Both V(3)-O(5) bond lengths are 2.02 Å. Both V(3)-O(8) bond lengths are 2.05 Å. In the fourth V site, V(4) is bonded to one O(1), one O(6), one O(7), and two equivalent O(8) atoms to form VO5 trigonal bipyramids that share corners with two equivalent V(1)O6 octahedra, corners with three equivalent V(3)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-58°. The V(4)-O(1) bond length is 2.31 Å. The V(4)-O(6) bond length is 2.04 Å. The V(4)-O(7) bond length is 1.76 Å. Both V(4)-O(8) bond lengths are 1.85 Å. Fe(1) is bonded to one O(2), one O(7), two equivalent O(3), and two equivalent O(8) atoms to form distorted FeO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with three equivalent V(4)O5 trigonal bipyramids, and  a faceface with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-59°. The Fe(1)-O(2) bond length is 2.10 Å. The Fe(1)-O(7) bond length is 2.31 Å. Both Fe(1)-O(3) bond lengths are 2.05 Å. Both Fe(1)-O(8) bond lengths are 2.16 Å. Pb(1) is bonded in a 3-coordinate geometry to one O(2) and two equivalent O(3) atoms. The Pb(1)-O(2) bond length is 2.50 Å. Both Pb(1)-O(3) bond lengths are 2.46 Å. There are eight inequivalent O sites. In the first O site, O(4) is bonded in a distorted trigonal planar geometry to one V(3) and two equivalent V(2) atoms. In the second O site, O(5) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the third O site, O(6) is bonded in a rectangular see-saw-like geometry to one V(1), one V(4), and two equivalent V(2) atoms. In the fourth O site, O(7) is bonded in a 3-coordinate geometry to one V(3), one V(4), and one Fe(1) atom. In the fifth O site, O(8) is bonded in a 3-coordinate geometry to one V(3), one V(4), and one Fe(1) atom. In the sixth O site, O(1) is bonded in a rectangular see-saw-like geometry to one V(1), one V(4), and two equivalent V(2) atoms. In the seventh O site, O(2) is bonded to two equivalent V(2), one Fe(1), and one Pb(1) atom to form a mixture of distorted corner and edge-sharing OV2FePb tetrahedra. In the eighth O site, O(3) is bonded to one V(1), one V(2), one Fe(1), and one Pb(1) atom to form a mixture of distorted corner and edge-sharing OV2FePb tetrahedra.