RbNa3Li12Ti4O16 crystallizes in the tetragonal I4/m space group. Rb(1) is bonded in a body-centered cubic geometry to eight equivalent O(2) atoms. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a body-centered cubic geometry to eight equivalent O(2) atoms. In the second Na site, Na(2) is bonded in a body-centered cubic geometry to four equivalent O(1) and four equivalent O(3) atoms. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with four equivalent Ti(1)O4 tetrahedra, corners with four equivalent Li(2)O4 trigonal pyramids, and edges with two equivalent Li(2)O4 trigonal pyramids. In the second Li site, Li(2) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Ti(1)O4 tetrahedra, corners with four equivalent Li(2)O4 trigonal pyramids,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Ti(1)O4 tetrahedra. Ti(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form TiO4 tetrahedra that share corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 trigonal pyramids, and edges with two equivalent Li(2)O4 trigonal pyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Na(2), one Li(1), two equivalent Li(2), and one Ti(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Rb(1), one Na(1), one Li(1), two equivalent Li(2), and one Ti(1) atom. In the third O site, O(3) is bonded to two equivalent Na(2), one Li(1), two equivalent Li(2), and one Ti(1) atom to form a mixture of distorted corner and edge-sharing ONa2Li3Ti octahedra. The corner-sharing octahedral tilt angles are 67°.
RbNa3Li12Ti4O16 crystallizes in the tetragonal I4/m space group. Rb(1) is bonded in a body-centered cubic geometry to eight equivalent O(2) atoms. All Rb(1)-O(2) bond lengths are 2.88 Å. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a body-centered cubic geometry to eight equivalent O(2) atoms. All Na(1)-O(2) bond lengths are 2.76 Å. In the second Na site, Na(2) is bonded in a body-centered cubic geometry to four equivalent O(1) and four equivalent O(3) atoms. All Na(2)-O(1) bond lengths are 2.76 Å. All Na(2)-O(3) bond lengths are 2.61 Å. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with four equivalent Ti(1)O4 tetrahedra, corners with four equivalent Li(2)O4 trigonal pyramids, and edges with two equivalent Li(2)O4 trigonal pyramids. The Li(1)-O(1) bond length is 1.99 Å. The Li(1)-O(3) bond length is 1.93 Å. Both Li(1)-O(2) bond lengths are 2.01 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Ti(1)O4 tetrahedra, corners with four equivalent Li(2)O4 trigonal pyramids,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Ti(1)O4 tetrahedra. The Li(2)-O(1) bond length is 1.91 Å. The Li(2)-O(3) bond length is 2.02 Å. There is one shorter (1.90 Å) and one longer (2.09 Å) Li(2)-O(2) bond length. Ti(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form TiO4 tetrahedra that share corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 trigonal pyramids, and edges with two equivalent Li(2)O4 trigonal pyramids. The Ti(1)-O(1) bond length is 1.82 Å. The Ti(1)-O(3) bond length is 1.82 Å. Both Ti(1)-O(2) bond lengths are 1.82 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Na(2), one Li(1), two equivalent Li(2), and one Ti(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Rb(1), one Na(1), one Li(1), two equivalent Li(2), and one Ti(1) atom. In the third O site, O(3) is bonded to two equivalent Na(2), one Li(1), two equivalent Li(2), and one Ti(1) atom to form a mixture of distorted corner and edge-sharing ONa2Li3Ti octahedra. The corner-sharing octahedral tilt angles are 67°.