Rb3NaRe2O9 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to three equivalent O(1) and nine equivalent O(2) atoms to form distorted RbO12 cuboctahedra that share corners with three equivalent Rb(2)O12 cuboctahedra, corners with six equivalent Rb(1)O12 cuboctahedra, corners with three equivalent Re(1)O6 octahedra, faces with three equivalent Rb(2)O12 cuboctahedra, faces with four equivalent Rb(1)O12 cuboctahedra, faces with three equivalent Na(1)O6 octahedra, and faces with four equivalent Re(1)O6 octahedra. The corner-sharing octahedral tilt angles are 1°. In the second Rb site, Rb(2) is bonded to six equivalent O(1) and six equivalent O(2) atoms to form distorted RbO12 cuboctahedra that share corners with six equivalent Rb(1)O12 cuboctahedra, corners with six equivalent Rb(2)O12 cuboctahedra, faces with six equivalent Rb(1)O12 cuboctahedra, faces with two equivalent Na(1)O6 octahedra, and faces with six equivalent Re(1)O6 octahedra. Na(1) is bonded to six equivalent O(2) atoms to form NaO6 octahedra that share corners with six equivalent Re(1)O6 octahedra, faces with two equivalent Rb(2)O12 cuboctahedra, and faces with six equivalent Rb(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 7°. Re(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form distorted ReO6 octahedra that share corners with three equivalent Rb(1)O12 cuboctahedra, corners with three equivalent Na(1)O6 octahedra, faces with three equivalent Rb(2)O12 cuboctahedra, faces with four equivalent Rb(1)O12 cuboctahedra, and  a faceface with one Re(1)O6 octahedra. The corner-sharing octahedral tilt angles are 7°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted L-shaped geometry to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Re(1) atoms. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Rb(2), three equivalent Rb(1), one Na(1), and one Re(1) atom.
Rb3NaRe2O9 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to three equivalent O(1) and nine equivalent O(2) atoms to form distorted RbO12 cuboctahedra that share corners with three equivalent Rb(2)O12 cuboctahedra, corners with six equivalent Rb(1)O12 cuboctahedra, corners with three equivalent Re(1)O6 octahedra, faces with three equivalent Rb(2)O12 cuboctahedra, faces with four equivalent Rb(1)O12 cuboctahedra, faces with three equivalent Na(1)O6 octahedra, and faces with four equivalent Re(1)O6 octahedra. The corner-sharing octahedral tilt angles are 1°. All Rb(1)-O(1) bond lengths are 3.05 Å. There are six shorter (3.14 Å) and three longer (3.30 Å) Rb(1)-O(2) bond lengths. In the second Rb site, Rb(2) is bonded to six equivalent O(1) and six equivalent O(2) atoms to form distorted RbO12 cuboctahedra that share corners with six equivalent Rb(1)O12 cuboctahedra, corners with six equivalent Rb(2)O12 cuboctahedra, faces with six equivalent Rb(1)O12 cuboctahedra, faces with two equivalent Na(1)O6 octahedra, and faces with six equivalent Re(1)O6 octahedra. All Rb(2)-O(1) bond lengths are 3.15 Å. All Rb(2)-O(2) bond lengths are 3.05 Å. Na(1) is bonded to six equivalent O(2) atoms to form NaO6 octahedra that share corners with six equivalent Re(1)O6 octahedra, faces with two equivalent Rb(2)O12 cuboctahedra, and faces with six equivalent Rb(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 7°. All Na(1)-O(2) bond lengths are 2.43 Å. Re(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form distorted ReO6 octahedra that share corners with three equivalent Rb(1)O12 cuboctahedra, corners with three equivalent Na(1)O6 octahedra, faces with three equivalent Rb(2)O12 cuboctahedra, faces with four equivalent Rb(1)O12 cuboctahedra, and  a faceface with one Re(1)O6 octahedra. The corner-sharing octahedral tilt angles are 7°. All Re(1)-O(1) bond lengths are 2.05 Å. All Re(1)-O(2) bond lengths are 1.80 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted L-shaped geometry to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Re(1) atoms. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Rb(2), three equivalent Rb(1), one Na(1), and one Re(1) atom.