NaCu3O4 crystallizes in the orthorhombic Cmmm space group. Na(1) is bonded in a body-centered cubic geometry to eight equivalent O(1) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to four equivalent O(1) atoms. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to four equivalent O(1) atoms. O(1) is bonded to two equivalent Na(1), one Cu(2), and two equivalent Cu(1) atoms to form a mixture of distorted edge, corner, and face-sharing ONa2Cu3 trigonal bipyramids.
NaCu3O4 crystallizes in the orthorhombic Cmmm space group. Na(1) is bonded in a body-centered cubic geometry to eight equivalent O(1) atoms. All Na(1)-O(1) bond lengths are 2.65 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to four equivalent O(1) atoms. There are two shorter (1.88 Å) and two longer (1.90 Å) Cu(1)-O(1) bond lengths. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to four equivalent O(1) atoms. All Cu(2)-O(1) bond lengths are 1.92 Å. O(1) is bonded to two equivalent Na(1), one Cu(2), and two equivalent Cu(1) atoms to form a mixture of distorted edge, corner, and face-sharing ONa2Cu3 trigonal bipyramids.