VCuBi2O7 crystallizes in the triclinic P-1 space group. V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form VO4 tetrahedra that share corners with two equivalent Bi(1)O6 pentagonal pyramids. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to two equivalent O(5) and two equivalent O(6) atoms. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent O(6) and two equivalent O(7) atoms. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(3), one O(4), one O(5), one O(6), and two equivalent O(7) atoms to form distorted BiO6 pentagonal pyramids that share corners with two equivalent V(1)O4 tetrahedra and  an edgeedge with one Bi(1)O6 pentagonal pyramid. In the second Bi site, Bi(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(7), and two equivalent O(5) atoms. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one V(1) and one Bi(2) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one V(1) and one Bi(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(1), one Bi(1), and one Bi(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one Bi(1), and one Bi(2) atom. In the fifth O site, O(5) is bonded to one Cu(1), one Bi(1), and two equivalent Bi(2) atoms to form a mixture of distorted edge and corner-sharing OCuBi3 tetrahedra. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Cu(1), one Cu(2), and one Bi(1) atom. In the seventh O site, O(7) is bonded to one Cu(2), one Bi(2), and two equivalent Bi(1) atoms to form a mixture of distorted edge and corner-sharing OCuBi3 tetrahedra.
VCuBi2O7 crystallizes in the triclinic P-1 space group. V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form VO4 tetrahedra that share corners with two equivalent Bi(1)O6 pentagonal pyramids. The V(1)-O(1) bond length is 1.72 Å. The V(1)-O(2) bond length is 1.72 Å. The V(1)-O(3) bond length is 1.79 Å. The V(1)-O(4) bond length is 1.77 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to two equivalent O(5) and two equivalent O(6) atoms. Both Cu(1)-O(5) bond lengths are 1.86 Å. Both Cu(1)-O(6) bond lengths are 1.89 Å. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent O(6) and two equivalent O(7) atoms. Both Cu(2)-O(6) bond lengths are 1.89 Å. Both Cu(2)-O(7) bond lengths are 1.90 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(3), one O(4), one O(5), one O(6), and two equivalent O(7) atoms to form distorted BiO6 pentagonal pyramids that share corners with two equivalent V(1)O4 tetrahedra and  an edgeedge with one Bi(1)O6 pentagonal pyramid. The Bi(1)-O(3) bond length is 2.52 Å. The Bi(1)-O(4) bond length is 2.52 Å. The Bi(1)-O(5) bond length is 2.34 Å. The Bi(1)-O(6) bond length is 2.33 Å. There is one shorter (2.34 Å) and one longer (2.35 Å) Bi(1)-O(7) bond length. In the second Bi site, Bi(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(7), and two equivalent O(5) atoms. The Bi(2)-O(1) bond length is 2.65 Å. The Bi(2)-O(2) bond length is 2.57 Å. The Bi(2)-O(3) bond length is 2.32 Å. The Bi(2)-O(4) bond length is 2.35 Å. The Bi(2)-O(7) bond length is 2.42 Å. There is one shorter (2.33 Å) and one longer (2.43 Å) Bi(2)-O(5) bond length. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one V(1) and one Bi(2) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one V(1) and one Bi(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(1), one Bi(1), and one Bi(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one Bi(1), and one Bi(2) atom. In the fifth O site, O(5) is bonded to one Cu(1), one Bi(1), and two equivalent Bi(2) atoms to form a mixture of distorted edge and corner-sharing OCuBi3 tetrahedra. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Cu(1), one Cu(2), and one Bi(1) atom. In the seventh O site, O(7) is bonded to one Cu(2), one Bi(2), and two equivalent Bi(1) atoms to form a mixture of distorted edge and corner-sharing OCuBi3 tetrahedra.