Rb2Li2SiO4 crystallizes in the triclinic P-1 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one O(2), two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. In the second Rb site, Rb(2) is bonded in a 6-coordinate geometry to two equivalent O(1) and four equivalent O(3) atoms. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(4), and two equivalent O(2) atoms. In the second Li site, Li(2) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent Si(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. Si(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra and  an edgeedge with one Li(2)O4 tetrahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), one Li(1), one Li(2), and one Si(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Rb(1), one Li(2), two equivalent Li(1), and one Si(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to two equivalent Rb(1), four equivalent Rb(2), and one Si(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Rb(1), one Li(1), two equivalent Li(2), and one Si(1) atom.
Rb2Li2SiO4 crystallizes in the triclinic P-1 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one O(2), two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. The Rb(1)-O(2) bond length is 2.92 Å. There is one shorter (3.20 Å) and one longer (3.26 Å) Rb(1)-O(1) bond length. There is one shorter (3.18 Å) and one longer (3.20 Å) Rb(1)-O(3) bond length. There is one shorter (3.10 Å) and one longer (3.11 Å) Rb(1)-O(4) bond length. In the second Rb site, Rb(2) is bonded in a 6-coordinate geometry to two equivalent O(1) and four equivalent O(3) atoms. There is one shorter (2.84 Å) and one longer (3.10 Å) Rb(2)-O(1) bond length. There are a spread of Rb(2)-O(3) bond distances ranging from 2.79-3.36 Å. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(4), and two equivalent O(2) atoms. The Li(1)-O(1) bond length is 1.89 Å. The Li(1)-O(4) bond length is 2.16 Å. Both Li(1)-O(2) bond lengths are 1.97 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent Si(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The Li(2)-O(1) bond length is 2.01 Å. The Li(2)-O(2) bond length is 2.00 Å. There is one shorter (1.95 Å) and one longer (2.01 Å) Li(2)-O(4) bond length. Si(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra and  an edgeedge with one Li(2)O4 tetrahedra. The Si(1)-O(1) bond length is 1.66 Å. The Si(1)-O(2) bond length is 1.69 Å. The Si(1)-O(3) bond length is 1.64 Å. The Si(1)-O(4) bond length is 1.68 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), one Li(1), one Li(2), and one Si(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Rb(1), one Li(2), two equivalent Li(1), and one Si(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to two equivalent Rb(1), four equivalent Rb(2), and one Si(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Rb(1), one Li(1), two equivalent Li(2), and one Si(1) atom.