Bi4Cu3V2O14 crystallizes in the triclinic P-1 space group. V(1) is bonded in a tetrahedral geometry to one O(3), one O(4), one O(5), and one O(6) atom. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(5), and two equivalent O(7) atoms. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(6), and two equivalent O(7) atoms. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Cu(1), one Cu(2), one Bi(1), and one Bi(2) atom to form distorted OCu2Bi2 tetrahedra that share  a cornercorner with one O(1)Cu2Bi2 tetrahedra,  a cornercorner with one O(2)Cu2Bi2 tetrahedra, corners with two equivalent O(7)Bi4 tetrahedra,  an edgeedge with one O(7)Bi4 tetrahedra, and edges with two equivalent O(2)Cu2Bi2 tetrahedra. In the second O site, O(2) is bonded to one Cu(1), one Cu(2), one Bi(1), and one Bi(2) atom to form OCu2Bi2 tetrahedra that share  a cornercorner with one O(1)Cu2Bi2 tetrahedra,  a cornercorner with one O(2)Cu2Bi2 tetrahedra, corners with two equivalent O(7)Bi4 tetrahedra,  an edgeedge with one O(7)Bi4 tetrahedra, and edges with two equivalent O(1)Cu2Bi2 tetrahedra. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(1) and one Cu(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one V(1) and one Cu(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one V(1) and one Bi(1) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one V(1) and one Bi(2) atom. In the seventh O site, O(7) is bonded to two equivalent Bi(1) and two equivalent Bi(2) atoms to form OBi4 tetrahedra that share corners with two equivalent O(1)Cu2Bi2 tetrahedra, corners with two equivalent O(2)Cu2Bi2 tetrahedra,  an edgeedge with one O(1)Cu2Bi2 tetrahedra,  an edgeedge with one O(2)Cu2Bi2 tetrahedra, and edges with two equivalent O(7)Bi4 tetrahedra.
Bi4Cu3V2O14 crystallizes in the triclinic P-1 space group. V(1) is bonded in a tetrahedral geometry to one O(3), one O(4), one O(5), and one O(6) atom. The V(1)-O(3) bond length is 1.72 Å. The V(1)-O(4) bond length is 1.75 Å. The V(1)-O(5) bond length is 1.74 Å. The V(1)-O(6) bond length is 1.77 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Cu(1)-O(1) bond length is 1.95 Å. The Cu(1)-O(2) bond length is 1.95 Å. The Cu(1)-O(3) bond length is 1.94 Å. The Cu(1)-O(4) bond length is 1.94 Å. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Cu(2)-O(1) bond lengths are 1.95 Å. Both Cu(2)-O(2) bond lengths are 1.96 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(5), and two equivalent O(7) atoms. The Bi(1)-O(1) bond length is 2.31 Å. The Bi(1)-O(2) bond length is 2.30 Å. The Bi(1)-O(5) bond length is 2.71 Å. There is one shorter (2.28 Å) and one longer (2.34 Å) Bi(1)-O(7) bond length. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(6), and two equivalent O(7) atoms. The Bi(2)-O(1) bond length is 2.47 Å. The Bi(2)-O(2) bond length is 2.32 Å. The Bi(2)-O(6) bond length is 2.50 Å. Both Bi(2)-O(7) bond lengths are 2.29 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Cu(1), one Cu(2), one Bi(1), and one Bi(2) atom to form distorted OCu2Bi2 tetrahedra that share  a cornercorner with one O(1)Cu2Bi2 tetrahedra,  a cornercorner with one O(2)Cu2Bi2 tetrahedra, corners with two equivalent O(7)Bi4 tetrahedra,  an edgeedge with one O(7)Bi4 tetrahedra, and edges with two equivalent O(2)Cu2Bi2 tetrahedra. In the second O site, O(2) is bonded to one Cu(1), one Cu(2), one Bi(1), and one Bi(2) atom to form OCu2Bi2 tetrahedra that share  a cornercorner with one O(1)Cu2Bi2 tetrahedra,  a cornercorner with one O(2)Cu2Bi2 tetrahedra, corners with two equivalent O(7)Bi4 tetrahedra,  an edgeedge with one O(7)Bi4 tetrahedra, and edges with two equivalent O(1)Cu2Bi2 tetrahedra. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(1) and one Cu(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one V(1) and one Cu(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one V(1) and one Bi(1) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one V(1) and one Bi(2) atom. In the seventh O site, O(7) is bonded to two equivalent Bi(1) and two equivalent Bi(2) atoms to form OBi4 tetrahedra that share corners with two equivalent O(1)Cu2Bi2 tetrahedra, corners with two equivalent O(2)Cu2Bi2 tetrahedra,  an edgeedge with one O(1)Cu2Bi2 tetrahedra,  an edgeedge with one O(2)Cu2Bi2 tetrahedra, and edges with two equivalent O(7)Bi4 tetrahedra.