Rb2LiNb2(TeO6)2 crystallizes in the triclinic P1 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 4-coordinate geometry to one O(12), one O(7), one O(8), and one O(9) atom. In the second Rb site, Rb(2) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(2), one O(4), one O(5), and one O(7) atom. Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share  a faceface with one Nb(1)O6 octahedra,  a faceface with one Te(1)O6 octahedra, and  a faceface with one Te(2)O6 octahedra. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(10), one O(11), one O(2), one O(4), one O(5), and one O(8) atom to form distorted NbO6 octahedra that share corners with two equivalent Te(1)O6 octahedra, corners with two equivalent Te(2)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-43°. In the second Nb site, Nb(2) is bonded in a 6-coordinate geometry to one O(12), one O(2), one O(3), one O(6), one O(8), and one O(9) atom. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded to one O(1), one O(10), one O(12), one O(4), one O(6), and one O(7) atom to form TeO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Te(2)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-48°. In the second Te site, Te(2) is bonded to one O(1), one O(11), one O(3), one O(5), one O(7), and one O(9) atom to form distorted TeO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Te(1)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-48°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Rb(2), one Li(1), one Te(1), and one Te(2) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Rb(2), one Li(1), one Nb(1), and one Nb(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Nb(2), and one Te(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Rb(2), one Li(1), one Nb(1), and one Te(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Rb(2), one Li(1), one Nb(1), and one Te(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one Nb(2), and one Te(1) atom. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one Rb(1), one Rb(2), one Te(1), and one Te(2) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to one Rb(1), one Nb(1), and one Nb(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Rb(1), one Nb(2), and one Te(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Nb(1) and one Te(1) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Rb(2), one Nb(1), and one Te(2) atom. In the twelfth O site, O(12) is bonded in a 2-coordinate geometry to one Rb(1), one Nb(2), and one Te(1) atom.
Rb2LiNb2(TeO6)2 crystallizes in the triclinic P1 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 4-coordinate geometry to one O(12), one O(7), one O(8), and one O(9) atom. The Rb(1)-O(12) bond length is 3.17 Å. The Rb(1)-O(7) bond length is 3.17 Å. The Rb(1)-O(8) bond length is 3.32 Å. The Rb(1)-O(9) bond length is 3.01 Å. In the second Rb site, Rb(2) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(2), one O(4), one O(5), and one O(7) atom. The Rb(2)-O(1) bond length is 3.14 Å. The Rb(2)-O(11) bond length is 3.34 Å. The Rb(2)-O(2) bond length is 3.55 Å. The Rb(2)-O(4) bond length is 3.02 Å. The Rb(2)-O(5) bond length is 3.19 Å. The Rb(2)-O(7) bond length is 3.45 Å. Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share  a faceface with one Nb(1)O6 octahedra,  a faceface with one Te(1)O6 octahedra, and  a faceface with one Te(2)O6 octahedra. The Li(1)-O(1) bond length is 2.08 Å. The Li(1)-O(2) bond length is 1.92 Å. The Li(1)-O(3) bond length is 1.94 Å. The Li(1)-O(4) bond length is 2.06 Å. The Li(1)-O(5) bond length is 2.01 Å. The Li(1)-O(6) bond length is 1.97 Å. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(10), one O(11), one O(2), one O(4), one O(5), and one O(8) atom to form distorted NbO6 octahedra that share corners with two equivalent Te(1)O6 octahedra, corners with two equivalent Te(2)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-43°. The Nb(1)-O(10) bond length is 1.97 Å. The Nb(1)-O(11) bond length is 1.97 Å. The Nb(1)-O(2) bond length is 1.86 Å. The Nb(1)-O(4) bond length is 2.14 Å. The Nb(1)-O(5) bond length is 2.09 Å. The Nb(1)-O(8) bond length is 2.20 Å. In the second Nb site, Nb(2) is bonded in a 6-coordinate geometry to one O(12), one O(2), one O(3), one O(6), one O(8), and one O(9) atom. The Nb(2)-O(12) bond length is 2.01 Å. The Nb(2)-O(2) bond length is 2.44 Å. The Nb(2)-O(3) bond length is 1.99 Å. The Nb(2)-O(6) bond length is 2.05 Å. The Nb(2)-O(8) bond length is 1.84 Å. The Nb(2)-O(9) bond length is 2.02 Å. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded to one O(1), one O(10), one O(12), one O(4), one O(6), and one O(7) atom to form TeO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Te(2)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-48°. The Te(1)-O(1) bond length is 1.98 Å. The Te(1)-O(10) bond length is 1.94 Å. The Te(1)-O(12) bond length is 1.94 Å. The Te(1)-O(4) bond length is 1.96 Å. The Te(1)-O(6) bond length is 1.99 Å. The Te(1)-O(7) bond length is 1.97 Å. In the second Te site, Te(2) is bonded to one O(1), one O(11), one O(3), one O(5), one O(7), and one O(9) atom to form distorted TeO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Te(1)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-48°. The Te(2)-O(1) bond length is 2.15 Å. The Te(2)-O(11) bond length is 2.01 Å. The Te(2)-O(3) bond length is 2.13 Å. The Te(2)-O(5) bond length is 2.06 Å. The Te(2)-O(7) bond length is 2.02 Å. The Te(2)-O(9) bond length is 1.97 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Rb(2), one Li(1), one Te(1), and one Te(2) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Rb(2), one Li(1), one Nb(1), and one Nb(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Nb(2), and one Te(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Rb(2), one Li(1), one Nb(1), and one Te(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Rb(2), one Li(1), one Nb(1), and one Te(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one Nb(2), and one Te(1) atom. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one Rb(1), one Rb(2), one Te(1), and one Te(2) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to one Rb(1), one Nb(1), and one Nb(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Rb(1), one Nb(2), and one Te(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Nb(1) and one Te(1) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Rb(2), one Nb(1), and one Te(2) atom. In the twelfth O site, O(12) is bonded in a 2-coordinate geometry to one Rb(1), one Nb(2), and one Te(1) atom.