Rb3Na(RuO4)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 10-coordinate geometry to one O(2) and nine equivalent O(1) atoms. In the second Rb site, Rb(2) is bonded in a 6-coordinate geometry to six equivalent O(1) atoms. Na(1) is bonded to six equivalent O(1) atoms to form NaO6 octahedra that share corners with six equivalent Ru(1)O4 tetrahedra. Ru(1) is bonded to one O(2) and three equivalent O(1) atoms to form RuO4 tetrahedra that share corners with three equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 16°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Rb(2), three equivalent Rb(1), one Na(1), and one Ru(1) atom. In the second O site, O(2) is bonded in a distorted linear geometry to one Rb(1) and one Ru(1) atom.
Rb3Na(RuO4)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 10-coordinate geometry to one O(2) and nine equivalent O(1) atoms. The Rb(1)-O(2) bond length is 2.76 Å. There are six shorter (3.12 Å) and three longer (3.29 Å) Rb(1)-O(1) bond lengths. In the second Rb site, Rb(2) is bonded in a 6-coordinate geometry to six equivalent O(1) atoms. All Rb(2)-O(1) bond lengths are 3.13 Å. Na(1) is bonded to six equivalent O(1) atoms to form NaO6 octahedra that share corners with six equivalent Ru(1)O4 tetrahedra. All Na(1)-O(1) bond lengths are 2.46 Å. Ru(1) is bonded to one O(2) and three equivalent O(1) atoms to form RuO4 tetrahedra that share corners with three equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 16°. The Ru(1)-O(2) bond length is 1.77 Å. All Ru(1)-O(1) bond lengths are 1.81 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Rb(2), three equivalent Rb(1), one Na(1), and one Ru(1) atom. In the second O site, O(2) is bonded in a distorted linear geometry to one Rb(1) and one Ru(1) atom.