Rb3Na(WO4)2 crystallizes in the trigonal P-3m1 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a distorted hexagonal planar geometry to six equivalent O(1) atoms. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to one O(2) and nine equivalent O(1) atoms. Na(1) is bonded to six equivalent O(1) atoms to form NaO6 octahedra that share corners with six equivalent W(1)O4 tetrahedra. W(1) is bonded to one O(2) and three equivalent O(1) atoms to form WO4 tetrahedra that share corners with three equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 18°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Rb(1), three equivalent Rb(2), one Na(1), and one W(1) atom. In the second O site, O(2) is bonded in a linear geometry to one Rb(2) and one W(1) atom.
Rb3Na(WO4)2 crystallizes in the trigonal P-3m1 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a distorted hexagonal planar geometry to six equivalent O(1) atoms. All Rb(1)-O(1) bond lengths are 3.14 Å. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to one O(2) and nine equivalent O(1) atoms. The Rb(2)-O(2) bond length is 2.65 Å. There are six shorter (3.19 Å) and three longer (3.38 Å) Rb(2)-O(1) bond lengths. Na(1) is bonded to six equivalent O(1) atoms to form NaO6 octahedra that share corners with six equivalent W(1)O4 tetrahedra. All Na(1)-O(1) bond lengths are 2.51 Å. W(1) is bonded to one O(2) and three equivalent O(1) atoms to form WO4 tetrahedra that share corners with three equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 18°. The W(1)-O(2) bond length is 1.81 Å. All W(1)-O(1) bond lengths are 1.82 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Rb(1), three equivalent Rb(2), one Na(1), and one W(1) atom. In the second O site, O(2) is bonded in a linear geometry to one Rb(2) and one W(1) atom.