V3Cu5TlO13 crystallizes in the triclinic P-1 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(12), one O(3), one O(4), and one O(6) atom to form VO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one Cu(5)O5 trigonal bipyramid, and corners with three equivalent Cu(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 31-34°. In the second V site, V(2) is bonded to one O(1), one O(10), one O(2), and one O(5) atom to form VO4 tetrahedra that share corners with three equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-69°. In the third V site, V(3) is bonded to one O(11), one O(13), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Cu(1)O6 octahedra,  a cornercorner with one Cu(3)O5 trigonal bipyramid, and corners with three equivalent Cu(5)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 45°. There are five inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(10), one O(11), one O(12), one O(2), and one O(3) atom to form distorted CuO6 octahedra that share  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, and  an edgeedge with one Cu(3)O5 trigonal bipyramid. In the second Cu site, Cu(2) is bonded in a 5-coordinate geometry to one O(10), one O(12), one O(5), one O(7), and one O(9) atom. In the third Cu site, Cu(3) is bonded to one O(12), one O(3), one O(4), one O(7), and one O(8) atom to form CuO5 trigonal bipyramids that share  a cornercorner with one V(3)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra,  an edgeedge with one Cu(1)O6 octahedra, and  an edgeedge with one Cu(5)O5 trigonal bipyramid. In the fourth Cu site, Cu(4) is bonded in a 5-coordinate geometry to one O(10), one O(13), one O(3), one O(5), and one O(7) atom. In the fifth Cu site, Cu(5) is bonded to one O(13), one O(6), one O(7), one O(8), and one O(9) atom to form CuO5 trigonal bipyramids that share  a cornercorner with one V(1)O4 tetrahedra, corners with three equivalent V(3)O4 tetrahedra, and  an edgeedge with one Cu(3)O5 trigonal bipyramid. Tl(1) is bonded in a 3-coordinate geometry to one O(11) and two equivalent O(1) atoms. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to one V(2), one Cu(1), and two equivalent Tl(1) atoms. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one V(2) and one Cu(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one V(1), one Cu(1), one Cu(3), and one Cu(4) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one V(1) and one Cu(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(2), one Cu(2), and one Cu(4) atom. In the sixth O site, O(6) is bonded in a linear geometry to one V(1) and one Cu(5) atom. In the seventh O site, O(7) is bonded to one Cu(2), one Cu(3), one Cu(4), and one Cu(5) atom to form distorted corner-sharing OCu4 trigonal pyramids. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(3), one Cu(3), and one Cu(5) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(3), one Cu(2), and one Cu(5) atom. In the tenth O site, O(10) is bonded to one V(2), one Cu(1), one Cu(2), and one Cu(4) atom to form OVCu3 tetrahedra that share corners with two equivalent O(7)Cu4 trigonal pyramids and  an edgeedge with one O(12)VCu3 tetrahedra. In the eleventh O site, O(11) is bonded in a 2-coordinate geometry to one V(3), one Cu(1), and one Tl(1) atom. In the twelfth O site, O(12) is bonded to one V(1), one Cu(1), one Cu(2), and one Cu(3) atom to form distorted OVCu3 tetrahedra that share corners with two equivalent O(7)Cu4 trigonal pyramids and  an edgeedge with one O(10)VCu3 tetrahedra. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one V(3), one Cu(4), and one Cu(5) atom.
V3Cu5TlO13 crystallizes in the triclinic P-1 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(12), one O(3), one O(4), and one O(6) atom to form VO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one Cu(5)O5 trigonal bipyramid, and corners with three equivalent Cu(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 31-34°. The V(1)-O(12) bond length is 1.84 Å. The V(1)-O(3) bond length is 1.78 Å. The V(1)-O(4) bond length is 1.75 Å. The V(1)-O(6) bond length is 1.69 Å. In the second V site, V(2) is bonded to one O(1), one O(10), one O(2), and one O(5) atom to form VO4 tetrahedra that share corners with three equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-69°. The V(2)-O(1) bond length is 1.70 Å. The V(2)-O(10) bond length is 1.96 Å. The V(2)-O(2) bond length is 1.75 Å. The V(2)-O(5) bond length is 1.70 Å. In the third V site, V(3) is bonded to one O(11), one O(13), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Cu(1)O6 octahedra,  a cornercorner with one Cu(3)O5 trigonal bipyramid, and corners with three equivalent Cu(5)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 45°. The V(3)-O(11) bond length is 1.72 Å. The V(3)-O(13) bond length is 1.79 Å. The V(3)-O(8) bond length is 1.77 Å. The V(3)-O(9) bond length is 1.75 Å. There are five inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(10), one O(11), one O(12), one O(2), and one O(3) atom to form distorted CuO6 octahedra that share  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, and  an edgeedge with one Cu(3)O5 trigonal bipyramid. The Cu(1)-O(1) bond length is 2.35 Å. The Cu(1)-O(10) bond length is 2.01 Å. The Cu(1)-O(11) bond length is 1.95 Å. The Cu(1)-O(12) bond length is 2.14 Å. The Cu(1)-O(2) bond length is 1.98 Å. The Cu(1)-O(3) bond length is 2.57 Å. In the second Cu site, Cu(2) is bonded in a 5-coordinate geometry to one O(10), one O(12), one O(5), one O(7), and one O(9) atom. The Cu(2)-O(10) bond length is 1.99 Å. The Cu(2)-O(12) bond length is 2.04 Å. The Cu(2)-O(5) bond length is 2.30 Å. The Cu(2)-O(7) bond length is 1.98 Å. The Cu(2)-O(9) bond length is 1.97 Å. In the third Cu site, Cu(3) is bonded to one O(12), one O(3), one O(4), one O(7), and one O(8) atom to form CuO5 trigonal bipyramids that share  a cornercorner with one V(3)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra,  an edgeedge with one Cu(1)O6 octahedra, and  an edgeedge with one Cu(5)O5 trigonal bipyramid. The Cu(3)-O(12) bond length is 2.14 Å. The Cu(3)-O(3) bond length is 2.24 Å. The Cu(3)-O(4) bond length is 1.93 Å. The Cu(3)-O(7) bond length is 1.99 Å. The Cu(3)-O(8) bond length is 1.96 Å. In the fourth Cu site, Cu(4) is bonded in a 5-coordinate geometry to one O(10), one O(13), one O(3), one O(5), and one O(7) atom. The Cu(4)-O(10) bond length is 2.00 Å. The Cu(4)-O(13) bond length is 1.97 Å. The Cu(4)-O(3) bond length is 1.96 Å. The Cu(4)-O(5) bond length is 2.28 Å. The Cu(4)-O(7) bond length is 1.94 Å. In the fifth Cu site, Cu(5) is bonded to one O(13), one O(6), one O(7), one O(8), and one O(9) atom to form CuO5 trigonal bipyramids that share  a cornercorner with one V(1)O4 tetrahedra, corners with three equivalent V(3)O4 tetrahedra, and  an edgeedge with one Cu(3)O5 trigonal bipyramid. The Cu(5)-O(13) bond length is 2.06 Å. The Cu(5)-O(6) bond length is 1.88 Å. The Cu(5)-O(7) bond length is 1.96 Å. The Cu(5)-O(8) bond length is 2.01 Å. The Cu(5)-O(9) bond length is 2.14 Å. Tl(1) is bonded in a 3-coordinate geometry to one O(11) and two equivalent O(1) atoms. The Tl(1)-O(11) bond length is 2.83 Å. There is one shorter (2.79 Å) and one longer (2.83 Å) Tl(1)-O(1) bond length. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to one V(2), one Cu(1), and two equivalent Tl(1) atoms. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one V(2) and one Cu(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one V(1), one Cu(1), one Cu(3), and one Cu(4) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one V(1) and one Cu(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(2), one Cu(2), and one Cu(4) atom. In the sixth O site, O(6) is bonded in a linear geometry to one V(1) and one Cu(5) atom. In the seventh O site, O(7) is bonded to one Cu(2), one Cu(3), one Cu(4), and one Cu(5) atom to form distorted corner-sharing OCu4 trigonal pyramids. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(3), one Cu(3), and one Cu(5) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(3), one Cu(2), and one Cu(5) atom. In the tenth O site, O(10) is bonded to one V(2), one Cu(1), one Cu(2), and one Cu(4) atom to form OVCu3 tetrahedra that share corners with two equivalent O(7)Cu4 trigonal pyramids and  an edgeedge with one O(12)VCu3 tetrahedra. In the eleventh O site, O(11) is bonded in a 2-coordinate geometry to one V(3), one Cu(1), and one Tl(1) atom. In the twelfth O site, O(12) is bonded to one V(1), one Cu(1), one Cu(2), and one Cu(3) atom to form distorted OVCu3 tetrahedra that share corners with two equivalent O(7)Cu4 trigonal pyramids and  an edgeedge with one O(10)VCu3 tetrahedra. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one V(3), one Cu(4), and one Cu(5) atom.