Na2BaV2CuO8 crystallizes in the monoclinic C2/c space group. Na(1) is bonded to one O(1), one O(2), one O(3), and two equivalent O(4) atoms to form NaO5 trigonal bipyramids that share corners with five equivalent V(1)O4 tetrahedra and  an edgeedge with one Na(1)O5 trigonal bipyramid. Ba(1) is bonded in a 10-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(4), and four equivalent O(3) atoms. 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 five equivalent Na(1)O5 trigonal bipyramids. Cu(1) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. There are four inequivalent O sites. In the first O site, O(3) is bonded in a 2-coordinate geometry to one Na(1), two equivalent Ba(1), and one V(1) atom. In the second O site, O(4) is bonded in a 1-coordinate geometry to two equivalent Na(1), one Ba(1), and one V(1) atom. In the third O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Ba(1), one V(1), and one Cu(1) atom. In the fourth O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Ba(1), one V(1), and one Cu(1) atom.
Na2BaV2CuO8 crystallizes in the monoclinic C2/c space group. Na(1) is bonded to one O(1), one O(2), one O(3), and two equivalent O(4) atoms to form NaO5 trigonal bipyramids that share corners with five equivalent V(1)O4 tetrahedra and  an edgeedge with one Na(1)O5 trigonal bipyramid. The Na(1)-O(1) bond length is 2.49 Å. The Na(1)-O(2) bond length is 2.50 Å. The Na(1)-O(3) bond length is 2.34 Å. There is one shorter (2.40 Å) and one longer (2.53 Å) Na(1)-O(4) bond length. Ba(1) is bonded in a 10-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(4), and four equivalent O(3) atoms. Both Ba(1)-O(1) bond lengths are 2.77 Å. Both Ba(1)-O(2) bond lengths are 2.82 Å. Both Ba(1)-O(4) bond lengths are 2.95 Å. There are two shorter (2.96 Å) and two longer (3.06 Å) Ba(1)-O(3) bond lengths. 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 five equivalent Na(1)O5 trigonal bipyramids. The V(1)-O(1) bond length is 1.79 Å. The V(1)-O(2) bond length is 1.76 Å. The V(1)-O(3) bond length is 1.72 Å. The V(1)-O(4) bond length is 1.72 Å. Cu(1) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Cu(1)-O(1) bond lengths are 1.97 Å. Both Cu(1)-O(2) bond lengths are 2.00 Å. There are four inequivalent O sites. In the first O site, O(3) is bonded in a 2-coordinate geometry to one Na(1), two equivalent Ba(1), and one V(1) atom. In the second O site, O(4) is bonded in a 1-coordinate geometry to two equivalent Na(1), one Ba(1), and one V(1) atom. In the third O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Ba(1), one V(1), and one Cu(1) atom. In the fourth O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Ba(1), one V(1), and one Cu(1) atom.