VCr(CuO2)2 crystallizes in the monoclinic C2/m space group. V(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form CrO6 octahedra that share edges with two equivalent Cr(1)O6 octahedra and edges with four equivalent V(1)O6 octahedra. In the second Cr site, Cr(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form CrO6 octahedra that share edges with two equivalent Cr(2)O6 octahedra and edges with four equivalent V(1)O6 octahedra. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a linear geometry to one O(1) and one O(3) atom. In the second Cu site, Cu(2) is bonded in a linear geometry to one O(2) and one O(4) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded to one V(1), two equivalent Cr(2), and one Cu(1) atom to form distorted OVCr2Cu tetrahedra that share  a cornercorner with one O(2)VCr2Cu tetrahedra, corners with two equivalent O(4)V2CrCu tetrahedra, corners with three equivalent O(3)V2CrCu tetrahedra, corners with four equivalent O(1)VCr2Cu tetrahedra,  an edgeedge with one O(1)VCr2Cu tetrahedra, and edges with two equivalent O(3)V2CrCu tetrahedra. In the second O site, O(2) is bonded to one V(1), two equivalent Cr(1), and one Cu(2) atom to form distorted OVCr2Cu tetrahedra that share  a cornercorner with one O(1)VCr2Cu tetrahedra, corners with two equivalent O(3)V2CrCu tetrahedra, corners with three equivalent O(4)V2CrCu tetrahedra, corners with four equivalent O(2)VCr2Cu tetrahedra,  an edgeedge with one O(2)VCr2Cu tetrahedra, and edges with two equivalent O(4)V2CrCu tetrahedra. In the third O site, O(3) is bonded to two equivalent V(1), one Cr(2), and one Cu(1) atom to form distorted OV2CrCu tetrahedra that share corners with two equivalent O(4)V2CrCu tetrahedra, corners with two equivalent O(2)VCr2Cu tetrahedra, corners with three equivalent O(3)V2CrCu tetrahedra, corners with three equivalent O(1)VCr2Cu tetrahedra,  an edgeedge with one O(4)V2CrCu tetrahedra, and edges with two equivalent O(1)VCr2Cu tetrahedra. In the fourth O site, O(4) is bonded to two equivalent V(1), one Cr(1), and one Cu(2) atom to form distorted OV2CrCu tetrahedra that share corners with two equivalent O(3)V2CrCu tetrahedra, corners with two equivalent O(1)VCr2Cu tetrahedra, corners with three equivalent O(4)V2CrCu tetrahedra, corners with three equivalent O(2)VCr2Cu tetrahedra,  an edgeedge with one O(3)V2CrCu tetrahedra, and edges with two equivalent O(2)VCr2Cu tetrahedra.
VCr(CuO2)2 crystallizes in the monoclinic C2/m space group. V(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The V(1)-O(1) bond length is 2.08 Å. The V(1)-O(2) bond length is 2.08 Å. Both V(1)-O(3) bond lengths are 2.05 Å. Both V(1)-O(4) bond lengths are 2.04 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form CrO6 octahedra that share edges with two equivalent Cr(1)O6 octahedra and edges with four equivalent V(1)O6 octahedra. Both Cr(1)-O(4) bond lengths are 2.03 Å. All Cr(1)-O(2) bond lengths are 2.03 Å. In the second Cr site, Cr(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form CrO6 octahedra that share edges with two equivalent Cr(2)O6 octahedra and edges with four equivalent V(1)O6 octahedra. Both Cr(2)-O(3) bond lengths are 2.03 Å. All Cr(2)-O(1) bond lengths are 2.03 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a linear geometry to one O(1) and one O(3) atom. The Cu(1)-O(1) bond length is 1.85 Å. The Cu(1)-O(3) bond length is 1.86 Å. In the second Cu site, Cu(2) is bonded in a linear geometry to one O(2) and one O(4) atom. The Cu(2)-O(2) bond length is 1.84 Å. The Cu(2)-O(4) bond length is 1.85 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one V(1), two equivalent Cr(2), and one Cu(1) atom to form distorted OVCr2Cu tetrahedra that share  a cornercorner with one O(2)VCr2Cu tetrahedra, corners with two equivalent O(4)V2CrCu tetrahedra, corners with three equivalent O(3)V2CrCu tetrahedra, corners with four equivalent O(1)VCr2Cu tetrahedra,  an edgeedge with one O(1)VCr2Cu tetrahedra, and edges with two equivalent O(3)V2CrCu tetrahedra. In the second O site, O(2) is bonded to one V(1), two equivalent Cr(1), and one Cu(2) atom to form distorted OVCr2Cu tetrahedra that share  a cornercorner with one O(1)VCr2Cu tetrahedra, corners with two equivalent O(3)V2CrCu tetrahedra, corners with three equivalent O(4)V2CrCu tetrahedra, corners with four equivalent O(2)VCr2Cu tetrahedra,  an edgeedge with one O(2)VCr2Cu tetrahedra, and edges with two equivalent O(4)V2CrCu tetrahedra. In the third O site, O(3) is bonded to two equivalent V(1), one Cr(2), and one Cu(1) atom to form distorted OV2CrCu tetrahedra that share corners with two equivalent O(4)V2CrCu tetrahedra, corners with two equivalent O(2)VCr2Cu tetrahedra, corners with three equivalent O(3)V2CrCu tetrahedra, corners with three equivalent O(1)VCr2Cu tetrahedra,  an edgeedge with one O(4)V2CrCu tetrahedra, and edges with two equivalent O(1)VCr2Cu tetrahedra. In the fourth O site, O(4) is bonded to two equivalent V(1), one Cr(1), and one Cu(2) atom to form distorted OV2CrCu tetrahedra that share corners with two equivalent O(3)V2CrCu tetrahedra, corners with two equivalent O(1)VCr2Cu tetrahedra, corners with three equivalent O(4)V2CrCu tetrahedra, corners with three equivalent O(2)VCr2Cu tetrahedra,  an edgeedge with one O(3)V2CrCu tetrahedra, and edges with two equivalent O(2)VCr2Cu tetrahedra.