NaAu(S2O7)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(7) atoms to form NaO6 octahedra that share corners with two equivalent S(2)O4 tetrahedra and corners with four equivalent S(1)O4 tetrahedra. Au(1) is bonded in a square co-planar geometry to two equivalent O(4) and two equivalent O(6) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form SO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra and  a cornercorner with one S(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 23-47°. In the second S site, S(2) is bonded to one O(2), one O(3), one O(6), and one O(7) atom to form SO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra and  a cornercorner with one S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 19°. There are seven inequivalent O sites. In the first O site, O(6) is bonded in a bent 120 degrees geometry to one Au(1) and one S(2) atom. In the second O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one S(2) atom. In the third O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one S(1) atom. In the fourth O site, O(2) is bonded in a bent 120 degrees geometry to one S(1) and one S(2) atom. In the fifth O site, O(3) is bonded in a single-bond geometry to one S(2) atom. In the sixth O site, O(4) is bonded in a bent 120 degrees geometry to one Au(1) and one S(1) atom. In the seventh O site, O(5) is bonded in a bent 150 degrees geometry to one Na(1) and one S(1) atom.
NaAu(S2O7)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(7) atoms to form NaO6 octahedra that share corners with two equivalent S(2)O4 tetrahedra and corners with four equivalent S(1)O4 tetrahedra. Both Na(1)-O(1) bond lengths are 2.48 Å. Both Na(1)-O(5) bond lengths are 2.48 Å. Both Na(1)-O(7) bond lengths are 2.46 Å. Au(1) is bonded in a square co-planar geometry to two equivalent O(4) and two equivalent O(6) atoms. Both Au(1)-O(4) bond lengths are 2.04 Å. Both Au(1)-O(6) bond lengths are 2.04 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form SO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra and  a cornercorner with one S(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 23-47°. The S(1)-O(1) bond length is 1.44 Å. The S(1)-O(2) bond length is 1.64 Å. The S(1)-O(4) bond length is 1.54 Å. The S(1)-O(5) bond length is 1.44 Å. In the second S site, S(2) is bonded to one O(2), one O(3), one O(6), and one O(7) atom to form SO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra and  a cornercorner with one S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 19°. The S(2)-O(2) bond length is 1.68 Å. The S(2)-O(3) bond length is 1.43 Å. The S(2)-O(6) bond length is 1.54 Å. The S(2)-O(7) bond length is 1.43 Å. There are seven inequivalent O sites. In the first O site, O(6) is bonded in a bent 120 degrees geometry to one Au(1) and one S(2) atom. In the second O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one S(2) atom. In the third O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one S(1) atom. In the fourth O site, O(2) is bonded in a bent 120 degrees geometry to one S(1) and one S(2) atom. In the fifth O site, O(3) is bonded in a single-bond geometry to one S(2) atom. In the sixth O site, O(4) is bonded in a bent 120 degrees geometry to one Au(1) and one S(1) atom. In the seventh O site, O(5) is bonded in a bent 150 degrees geometry to one Na(1) and one S(1) atom.