VCd2BiO6 crystallizes in the orthorhombic Cmc2_1 space group. V(1) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with eight equivalent Cd(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-70°. Cd(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form distorted CdO6 octahedra that share corners with four equivalent Cd(1)O6 octahedra, corners with four equivalent V(1)O4 tetrahedra, and  an edgeedge with one Cd(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-65°. Bi(1) is bonded in a 5-coordinate geometry to one O(3) and four equivalent O(2) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Cd(1) atoms. In the second O site, O(2) is bonded to two equivalent Cd(1) and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OCd2Bi2 tetrahedra. In the third O site, O(3) is bonded in a 4-coordinate geometry to one V(1), two equivalent Cd(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Cd(1) atoms.
VCd2BiO6 crystallizes in the orthorhombic Cmc2_1 space group. V(1) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with eight equivalent Cd(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-70°. The V(1)-O(3) bond length is 1.77 Å. The V(1)-O(4) bond length is 1.72 Å. Both V(1)-O(1) bond lengths are 1.76 Å. Cd(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form distorted CdO6 octahedra that share corners with four equivalent Cd(1)O6 octahedra, corners with four equivalent V(1)O4 tetrahedra, and  an edgeedge with one Cd(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-65°. The Cd(1)-O(3) bond length is 2.42 Å. The Cd(1)-O(4) bond length is 2.36 Å. There is one shorter (2.40 Å) and one longer (2.43 Å) Cd(1)-O(1) bond length. There is one shorter (2.30 Å) and one longer (2.31 Å) Cd(1)-O(2) bond length. Bi(1) is bonded in a 5-coordinate geometry to one O(3) and four equivalent O(2) atoms. The Bi(1)-O(3) bond length is 2.58 Å. There are two shorter (2.26 Å) and two longer (2.28 Å) Bi(1)-O(2) bond lengths. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Cd(1) atoms. In the second O site, O(2) is bonded to two equivalent Cd(1) and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OCd2Bi2 tetrahedra. In the third O site, O(3) is bonded in a 4-coordinate geometry to one V(1), two equivalent Cd(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Cd(1) atoms.