Na2Mg(Cu2O3)2 crystallizes in the monoclinic Pm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to two equivalent O(3) and four equivalent O(1) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(4) atoms. Mg(1) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(3) atoms. 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), and two equivalent O(4) atoms. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one O(3), one O(4), and two equivalent O(1) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to two equivalent Na(1), one Mg(1), one Cu(1), and two equivalent Cu(2) atoms. In the second O site, O(2) is bonded to two equivalent Na(2) and two equivalent Cu(1) atoms to form distorted ONa2Cu2 tetrahedra that share corners with four equivalent O(4)Na2Cu3 square pyramids, corners with two equivalent O(2)Na2Cu2 tetrahedra, and edges with four equivalent O(4)Na2Cu3 square pyramids. In the third O site, O(3) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent Mg(1), and two equivalent Cu(2) atoms. In the fourth O site, O(4) is bonded to two equivalent Na(2), one Cu(2), and two equivalent Cu(1) atoms to form distorted ONa2Cu3 square pyramids that share corners with six equivalent O(4)Na2Cu3 square pyramids, corners with two equivalent O(2)Na2Cu2 tetrahedra,  an edgeedge with one O(4)Na2Cu3 square pyramid, and edges with two equivalent O(2)Na2Cu2 tetrahedra.
Na2Mg(Cu2O3)2 crystallizes in the monoclinic Pm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to two equivalent O(3) and four equivalent O(1) atoms. There is one shorter (2.11 Å) and one longer (2.26 Å) Na(1)-O(3) bond length. There are two shorter (2.37 Å) and two longer (2.74 Å) Na(1)-O(1) bond lengths. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(4) atoms. There is one shorter (2.25 Å) and one longer (2.35 Å) Na(2)-O(2) bond length. There are two shorter (2.52 Å) and two longer (2.57 Å) Na(2)-O(4) bond lengths. Mg(1) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(3) atoms. Both Mg(1)-O(1) bond lengths are 1.97 Å. There is one shorter (1.98 Å) and one longer (2.08 Å) Mg(1)-O(3) bond length. 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), and two equivalent O(4) atoms. The Cu(1)-O(1) bond length is 1.90 Å. The Cu(1)-O(2) bond length is 1.82 Å. Both Cu(1)-O(4) bond lengths are 2.15 Å. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one O(3), one O(4), and two equivalent O(1) atoms. The Cu(2)-O(3) bond length is 2.02 Å. The Cu(2)-O(4) bond length is 1.86 Å. There is one shorter (2.08 Å) and one longer (2.34 Å) Cu(2)-O(1) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to two equivalent Na(1), one Mg(1), one Cu(1), and two equivalent Cu(2) atoms. In the second O site, O(2) is bonded to two equivalent Na(2) and two equivalent Cu(1) atoms to form distorted ONa2Cu2 tetrahedra that share corners with four equivalent O(4)Na2Cu3 square pyramids, corners with two equivalent O(2)Na2Cu2 tetrahedra, and edges with four equivalent O(4)Na2Cu3 square pyramids. In the third O site, O(3) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent Mg(1), and two equivalent Cu(2) atoms. In the fourth O site, O(4) is bonded to two equivalent Na(2), one Cu(2), and two equivalent Cu(1) atoms to form distorted ONa2Cu3 square pyramids that share corners with six equivalent O(4)Na2Cu3 square pyramids, corners with two equivalent O(2)Na2Cu2 tetrahedra,  an edgeedge with one O(4)Na2Cu3 square pyramid, and edges with two equivalent O(2)Na2Cu2 tetrahedra.