Na5CuS4(NO6)2 crystallizes in the tetragonal P-4 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(3), one O(6), two equivalent O(4), and two equivalent O(5) atoms. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one S(1), one O(1), one O(2), one O(3), one O(4), and one O(5) atom. In the third Na site, Na(3) is bonded in a distorted octahedral geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to four equivalent S(1) atoms to form edge-sharing CuS4 tetrahedra. In the second Cu site, Cu(2) is bonded to four equivalent S(1) atoms to form edge-sharing CuS4 tetrahedra. N(1) is bonded in a trigonal planar geometry to one O(4), one O(5), and one O(6) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one Na(2), one Cu(1), one Cu(2), and one S(2) atom. In the second S site, S(2) is bonded in a trigonal non-coplanar geometry to one S(1), one O(1), one O(2), and one O(3) atom. There are six inequivalent O sites. In the first O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), and one S(2) atom to form distorted corner-sharing ONa3S tetrahedra. In the second O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one N(1) atom. In the third O site, O(5) is bonded in a distorted see-saw-like geometry to one Na(2), two equivalent Na(1), and one N(1) atom. In the fourth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Na(3), and one N(1) atom. In the fifth O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one S(2) atom. In the sixth O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one Na(3), and one S(2) atom.
Na5CuS4(NO6)2 crystallizes in the tetragonal P-4 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(3), one O(6), two equivalent O(4), and two equivalent O(5) atoms. The Na(1)-O(1) bond length is 2.54 Å. The Na(1)-O(3) bond length is 2.44 Å. The Na(1)-O(6) bond length is 2.63 Å. There is one shorter (2.54 Å) and one longer (2.60 Å) Na(1)-O(4) bond length. There is one shorter (2.54 Å) and one longer (2.69 Å) Na(1)-O(5) bond length. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one S(1), one O(1), one O(2), one O(3), one O(4), and one O(5) atom. The Na(2)-S(1) bond length is 3.22 Å. The Na(2)-O(1) bond length is 2.30 Å. The Na(2)-O(2) bond length is 2.34 Å. The Na(2)-O(3) bond length is 2.43 Å. The Na(2)-O(4) bond length is 2.69 Å. The Na(2)-O(5) bond length is 2.53 Å. In the third Na site, Na(3) is bonded in a distorted octahedral geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms. Both Na(3)-O(2) bond lengths are 2.34 Å. Both Na(3)-O(3) bond lengths are 2.38 Å. Both Na(3)-O(6) bond lengths are 2.51 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to four equivalent S(1) atoms to form edge-sharing CuS4 tetrahedra. All Cu(1)-S(1) bond lengths are 2.35 Å. In the second Cu site, Cu(2) is bonded to four equivalent S(1) atoms to form edge-sharing CuS4 tetrahedra. All Cu(2)-S(1) bond lengths are 2.35 Å. N(1) is bonded in a trigonal planar geometry to one O(4), one O(5), and one O(6) atom. The N(1)-O(4) bond length is 1.27 Å. The N(1)-O(5) bond length is 1.27 Å. The N(1)-O(6) bond length is 1.26 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one Na(2), one Cu(1), one Cu(2), and one S(2) atom. The S(1)-S(2) bond length is 2.08 Å. In the second S site, S(2) is bonded in a trigonal non-coplanar geometry to one S(1), one O(1), one O(2), and one O(3) atom. The S(2)-O(1) bond length is 1.47 Å. The S(2)-O(2) bond length is 1.48 Å. The S(2)-O(3) bond length is 1.49 Å. There are six inequivalent O sites. In the first O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), and one S(2) atom to form distorted corner-sharing ONa3S tetrahedra. In the second O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one N(1) atom. In the third O site, O(5) is bonded in a distorted see-saw-like geometry to one Na(2), two equivalent Na(1), and one N(1) atom. In the fourth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Na(3), and one N(1) atom. In the fifth O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one S(2) atom. In the sixth O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one Na(3), and one S(2) atom.