V3Cu4CdTlO13 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(6), one O(7), and two equivalent O(8) atoms to form VO4 tetrahedra that share corners with three equivalent Cd(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-76°. In the second V site, V(2) is bonded to one O(3), one O(9), and two equivalent O(10) atoms to form VO4 tetrahedra that share  a cornercorner with one Cd(1)O6 octahedra,  a cornercorner with one Cu(2)O5 trigonal bipyramid, and corners with three equivalent Cu(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 51°. In the third V site, V(3) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form VO4 tetrahedra that share corners with two equivalent Cd(1)O6 octahedra,  a cornercorner with one Cu(3)O5 trigonal bipyramid, and corners with three equivalent Cu(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 36°. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted rectangular see-saw-like geometry to one O(10), one O(4), one O(5), and one O(7) atom. In the second Cu site, Cu(2) is bonded to one O(2), one O(3), one O(5), and two equivalent O(4) atoms to form CuO5 trigonal bipyramids that share  a cornercorner with one V(2)O4 tetrahedra, corners with three equivalent V(3)O4 tetrahedra,  an edgeedge with one Cd(1)O6 octahedra, and  an edgeedge with one Cu(3)O5 trigonal bipyramid. In the third Cu site, Cu(3) is bonded to one O(1), one O(3), one O(5), and two equivalent O(10) atoms to form distorted CuO5 trigonal bipyramids that share  a cornercorner with one V(3)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, and  an edgeedge with one Cu(2)O5 trigonal bipyramid. Cd(1) is bonded to one O(7), one O(9), two equivalent O(4), and two equivalent O(8) atoms to form CdO6 octahedra that share  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, and  an edgeedge with one Cu(2)O5 trigonal bipyramid. Tl(1) is bonded in a 5-coordinate geometry to one O(9) and four equivalent O(8) atoms. There are ten inequivalent O sites. In the first O site, O(7) is bonded to one V(1), two equivalent Cu(1), and one Cd(1) atom to form distorted corner-sharing OVCdCu2 trigonal pyramids. In the second O site, O(8) is bonded in a 2-coordinate geometry to one V(1), one Cd(1), and two equivalent Tl(1) atoms. In the third O site, O(9) is bonded in a distorted bent 120 degrees geometry to one V(2), one Cd(1), and one Tl(1) atom. In the fourth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(2), one Cu(1), and one Cu(3) atom. In the fifth O site, O(1) is bonded in a linear geometry to one V(3) and one Cu(3) atom. In the sixth O site, O(2) is bonded in a distorted bent 120 degrees geometry to one V(3) and one Cu(2) atom. In the seventh O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one Cu(2), and one Cu(3) atom. In the eighth O site, O(4) is bonded in a 4-coordinate geometry to one V(3), one Cu(1), one Cu(2), and one Cd(1) atom. In the ninth O site, O(5) is bonded to one Cu(2), one Cu(3), and two equivalent Cu(1) atoms to form distorted corner-sharing OCu4 trigonal pyramids. In the tenth O site, O(6) is bonded in a distorted single-bond geometry to one V(1) atom.
V3Cu4CdTlO13 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(6), one O(7), and two equivalent O(8) atoms to form VO4 tetrahedra that share corners with three equivalent Cd(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-76°. The V(1)-O(6) bond length is 1.69 Å. The V(1)-O(7) bond length is 1.94 Å. Both V(1)-O(8) bond lengths are 1.73 Å. In the second V site, V(2) is bonded to one O(3), one O(9), and two equivalent O(10) atoms to form VO4 tetrahedra that share  a cornercorner with one Cd(1)O6 octahedra,  a cornercorner with one Cu(2)O5 trigonal bipyramid, and corners with three equivalent Cu(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 51°. The V(2)-O(3) bond length is 1.77 Å. The V(2)-O(9) bond length is 1.70 Å. Both V(2)-O(10) bond lengths are 1.78 Å. In the third V site, V(3) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form VO4 tetrahedra that share corners with two equivalent Cd(1)O6 octahedra,  a cornercorner with one Cu(3)O5 trigonal bipyramid, and corners with three equivalent Cu(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 36°. The V(3)-O(1) bond length is 1.70 Å. The V(3)-O(2) bond length is 1.74 Å. Both V(3)-O(4) bond lengths are 1.82 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted rectangular see-saw-like geometry to one O(10), one O(4), one O(5), and one O(7) atom. The Cu(1)-O(10) bond length is 1.94 Å. The Cu(1)-O(4) bond length is 1.98 Å. The Cu(1)-O(5) bond length is 1.94 Å. The Cu(1)-O(7) bond length is 1.98 Å. In the second Cu site, Cu(2) is bonded to one O(2), one O(3), one O(5), and two equivalent O(4) atoms to form CuO5 trigonal bipyramids that share  a cornercorner with one V(2)O4 tetrahedra, corners with three equivalent V(3)O4 tetrahedra,  an edgeedge with one Cd(1)O6 octahedra, and  an edgeedge with one Cu(3)O5 trigonal bipyramid. The Cu(2)-O(2) bond length is 1.95 Å. The Cu(2)-O(3) bond length is 1.98 Å. The Cu(2)-O(5) bond length is 2.01 Å. Both Cu(2)-O(4) bond lengths are 2.24 Å. In the third Cu site, Cu(3) is bonded to one O(1), one O(3), one O(5), and two equivalent O(10) atoms to form distorted CuO5 trigonal bipyramids that share  a cornercorner with one V(3)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, and  an edgeedge with one Cu(2)O5 trigonal bipyramid. The Cu(3)-O(1) bond length is 1.92 Å. The Cu(3)-O(3) bond length is 2.07 Å. The Cu(3)-O(5) bond length is 2.04 Å. Both Cu(3)-O(10) bond lengths are 2.05 Å. Cd(1) is bonded to one O(7), one O(9), two equivalent O(4), and two equivalent O(8) atoms to form CdO6 octahedra that share  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, and  an edgeedge with one Cu(2)O5 trigonal bipyramid. The Cd(1)-O(7) bond length is 2.31 Å. The Cd(1)-O(9) bond length is 2.24 Å. Both Cd(1)-O(4) bond lengths are 2.51 Å. Both Cd(1)-O(8) bond lengths are 2.25 Å. Tl(1) is bonded in a 5-coordinate geometry to one O(9) and four equivalent O(8) atoms. The Tl(1)-O(9) bond length is 2.90 Å. There are two shorter (2.82 Å) and two longer (2.88 Å) Tl(1)-O(8) bond lengths. There are ten inequivalent O sites. In the first O site, O(7) is bonded to one V(1), two equivalent Cu(1), and one Cd(1) atom to form distorted corner-sharing OVCdCu2 trigonal pyramids. In the second O site, O(8) is bonded in a 2-coordinate geometry to one V(1), one Cd(1), and two equivalent Tl(1) atoms. In the third O site, O(9) is bonded in a distorted bent 120 degrees geometry to one V(2), one Cd(1), and one Tl(1) atom. In the fourth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(2), one Cu(1), and one Cu(3) atom. In the fifth O site, O(1) is bonded in a linear geometry to one V(3) and one Cu(3) atom. In the sixth O site, O(2) is bonded in a distorted bent 120 degrees geometry to one V(3) and one Cu(2) atom. In the seventh O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one Cu(2), and one Cu(3) atom. In the eighth O site, O(4) is bonded in a 4-coordinate geometry to one V(3), one Cu(1), one Cu(2), and one Cd(1) atom. In the ninth O site, O(5) is bonded to one Cu(2), one Cu(3), and two equivalent Cu(1) atoms to form distorted corner-sharing OCu4 trigonal pyramids. In the tenth O site, O(6) is bonded in a distorted single-bond geometry to one V(1) atom.