Na5CuCO5 crystallizes in the orthorhombic Pmm2 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), and two equivalent O(1) atoms. In the second Na site, Na(2) is bonded in a see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. In the third Na site, Na(3) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(3) atoms. Cu(1) is bonded in a linear geometry to two equivalent O(1) atoms. C(1) is bonded in a trigonal planar geometry to one O(3) and two equivalent O(2) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Cu(1) atom to form corner-sharing ONa5Cu octahedra. The corner-sharing octahedral tilt angles range from 1-11°. In the second O site, O(2) is bonded in a 1-coordinate geometry to one Na(1), two equivalent Na(2), and one C(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Na(3), and one C(1) atom.
Na5CuCO5 crystallizes in the orthorhombic Pmm2 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), and two equivalent O(1) atoms. The Na(1)-O(2) bond length is 2.39 Å. The Na(1)-O(3) bond length is 2.31 Å. Both Na(1)-O(1) bond lengths are 2.28 Å. In the second Na site, Na(2) is bonded in a see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. There is one shorter (2.44 Å) and one longer (2.46 Å) Na(2)-O(1) bond length. Both Na(2)-O(2) bond lengths are 2.53 Å. In the third Na site, Na(3) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(3) atoms. Both Na(3)-O(1) bond lengths are 2.39 Å. Both Na(3)-O(3) bond lengths are 2.41 Å. Cu(1) is bonded in a linear geometry to two equivalent O(1) atoms. Both Cu(1)-O(1) bond lengths are 1.81 Å. C(1) is bonded in a trigonal planar geometry to one O(3) and two equivalent O(2) atoms. The C(1)-O(3) bond length is 1.31 Å. Both C(1)-O(2) bond lengths are 1.30 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Cu(1) atom to form corner-sharing ONa5Cu octahedra. The corner-sharing octahedral tilt angles range from 1-11°. In the second O site, O(2) is bonded in a 1-coordinate geometry to one Na(1), two equivalent Na(2), and one C(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Na(3), and one C(1) atom.