Na2Ba2U(S2O)2 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent S(1), three equivalent S(2), and one O(1) atom. Ba(1) is bonded to two equivalent S(2), three equivalent S(1), and two equivalent O(1) atoms to form distorted BaS5O2 pentagonal bipyramids that share  a cornercorner with one U(1)S4O2 octahedra, corners with two equivalent Ba(1)S5O2 pentagonal bipyramids, edges with three equivalent U(1)S4O2 octahedra, and edges with four equivalent Ba(1)S5O2 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 17°. U(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent O(1) atoms to form distorted US4O2 octahedra that share corners with two equivalent Ba(1)S5O2 pentagonal bipyramids and edges with six equivalent Ba(1)S5O2 pentagonal bipyramids. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Na(1), three equivalent Ba(1), and one U(1) atom to form SBa3Na2U octahedra that share corners with two equivalent S(2)Ba2Na3U octahedra, corners with three equivalent S(1)Ba3Na2U octahedra, corners with four equivalent O(1)Ba2NaU tetrahedra, edges with three equivalent S(1)Ba3Na2U octahedra, edges with six equivalent S(2)Ba2Na3U octahedra, and edges with three equivalent O(1)Ba2NaU tetrahedra. The corner-sharing octahedral tilt angles range from 0-22°. In the second S site, S(2) is bonded to three equivalent Na(1), two equivalent Ba(1), and one U(1) atom to form distorted SBa2Na3U octahedra that share corners with two equivalent S(1)Ba3Na2U octahedra, corners with three equivalent S(2)Ba2Na3U octahedra, corners with five equivalent O(1)Ba2NaU tetrahedra, edges with three equivalent S(2)Ba2Na3U octahedra, edges with six equivalent S(1)Ba3Na2U octahedra, and edges with two equivalent O(1)Ba2NaU tetrahedra. The corner-sharing octahedral tilt angles range from 0-22°. O(1) is bonded to one Na(1), two equivalent Ba(1), and one U(1) atom to form distorted OBa2NaU tetrahedra that share corners with four equivalent S(1)Ba3Na2U octahedra, corners with five equivalent S(2)Ba2Na3U octahedra,  a cornercorner with one O(1)Ba2NaU tetrahedra, edges with two equivalent S(2)Ba2Na3U octahedra, edges with three equivalent S(1)Ba3Na2U octahedra, and  an edgeedge with one O(1)Ba2NaU tetrahedra. The corner-sharing octahedral tilt angles range from 17-90°.
Na2Ba2U(S2O)2 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent S(1), three equivalent S(2), and one O(1) atom. There is one shorter (2.83 Å) and one longer (2.93 Å) Na(1)-S(1) bond length. There are a spread of Na(1)-S(2) bond distances ranging from 3.00-3.30 Å. The Na(1)-O(1) bond length is 2.43 Å. Ba(1) is bonded to two equivalent S(2), three equivalent S(1), and two equivalent O(1) atoms to form distorted BaS5O2 pentagonal bipyramids that share  a cornercorner with one U(1)S4O2 octahedra, corners with two equivalent Ba(1)S5O2 pentagonal bipyramids, edges with three equivalent U(1)S4O2 octahedra, and edges with four equivalent Ba(1)S5O2 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 17°. There is one shorter (3.22 Å) and one longer (3.25 Å) Ba(1)-S(2) bond length. There are a spread of Ba(1)-S(1) bond distances ranging from 3.20-3.25 Å. There is one shorter (2.81 Å) and one longer (2.82 Å) Ba(1)-O(1) bond length. U(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent O(1) atoms to form distorted US4O2 octahedra that share corners with two equivalent Ba(1)S5O2 pentagonal bipyramids and edges with six equivalent Ba(1)S5O2 pentagonal bipyramids. Both U(1)-S(1) bond lengths are 2.67 Å. Both U(1)-S(2) bond lengths are 2.68 Å. Both U(1)-O(1) bond lengths are 1.92 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Na(1), three equivalent Ba(1), and one U(1) atom to form SBa3Na2U octahedra that share corners with two equivalent S(2)Ba2Na3U octahedra, corners with three equivalent S(1)Ba3Na2U octahedra, corners with four equivalent O(1)Ba2NaU tetrahedra, edges with three equivalent S(1)Ba3Na2U octahedra, edges with six equivalent S(2)Ba2Na3U octahedra, and edges with three equivalent O(1)Ba2NaU tetrahedra. The corner-sharing octahedral tilt angles range from 0-22°. In the second S site, S(2) is bonded to three equivalent Na(1), two equivalent Ba(1), and one U(1) atom to form distorted SBa2Na3U octahedra that share corners with two equivalent S(1)Ba3Na2U octahedra, corners with three equivalent S(2)Ba2Na3U octahedra, corners with five equivalent O(1)Ba2NaU tetrahedra, edges with three equivalent S(2)Ba2Na3U octahedra, edges with six equivalent S(1)Ba3Na2U octahedra, and edges with two equivalent O(1)Ba2NaU tetrahedra. The corner-sharing octahedral tilt angles range from 0-22°. O(1) is bonded to one Na(1), two equivalent Ba(1), and one U(1) atom to form distorted OBa2NaU tetrahedra that share corners with four equivalent S(1)Ba3Na2U octahedra, corners with five equivalent S(2)Ba2Na3U octahedra,  a cornercorner with one O(1)Ba2NaU tetrahedra, edges with two equivalent S(2)Ba2Na3U octahedra, edges with three equivalent S(1)Ba3Na2U octahedra, and  an edgeedge with one O(1)Ba2NaU tetrahedra. The corner-sharing octahedral tilt angles range from 17-90°.