Rb3LiTbV2O8 crystallizes in the triclinic P1 space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one Li(1), one O(1), one O(2), one O(4), one O(8), and two equivalent O(6) atoms. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to one O(2), one O(4), one O(8), two equivalent O(3), two equivalent O(5), and two equivalent O(7) atoms. In the third Rb site, Rb(3) is bonded in a 3-coordinate geometry to one O(1) and two equivalent O(2) atoms. Li(1) is bonded in a distorted trigonal non-coplanar geometry to one Rb(1), one O(4), one O(5), and one O(8) atom. Tb(1) is bonded in a 6-coordinate geometry to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded in a tetrahedral geometry to one O(1), one O(3), one O(5), and one O(7) atom. In the second V site, V(2) is bonded in a tetrahedral geometry to one O(2), one O(4), one O(6), and one O(8) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Rb(1), one Rb(3), and one V(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(2), two equivalent Rb(3), and one V(2) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to two equivalent Rb(2), one Tb(1), and one V(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Rb(1), one Rb(2), one Li(1), one Tb(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted water-like geometry to two equivalent Rb(2), one Li(1), one Tb(1), and one V(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to two equivalent Rb(1), one Tb(1), and one V(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to two equivalent Rb(2), one Tb(1), and one V(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Rb(1), one Rb(2), one Li(1), one Tb(1), and one V(2) atom.
Rb3LiTbV2O8 crystallizes in the triclinic P1 space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one Li(1), one O(1), one O(2), one O(4), one O(8), and two equivalent O(6) atoms. The Rb(1)-Li(1) bond length is 2.73 Å. The Rb(1)-O(1) bond length is 2.59 Å. The Rb(1)-O(2) bond length is 2.88 Å. The Rb(1)-O(4) bond length is 3.02 Å. The Rb(1)-O(8) bond length is 2.96 Å. There is one shorter (3.12 Å) and one longer (3.18 Å) Rb(1)-O(6) bond length. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to one O(2), one O(4), one O(8), two equivalent O(3), two equivalent O(5), and two equivalent O(7) atoms. The Rb(2)-O(2) bond length is 2.97 Å. The Rb(2)-O(4) bond length is 3.33 Å. The Rb(2)-O(8) bond length is 3.32 Å. There is one shorter (3.15 Å) and one longer (3.25 Å) Rb(2)-O(3) bond length. There is one shorter (3.02 Å) and one longer (3.05 Å) Rb(2)-O(5) bond length. There is one shorter (3.12 Å) and one longer (3.28 Å) Rb(2)-O(7) bond length. In the third Rb site, Rb(3) is bonded in a 3-coordinate geometry to one O(1) and two equivalent O(2) atoms. The Rb(3)-O(1) bond length is 2.93 Å. Both Rb(3)-O(2) bond lengths are 3.12 Å. Li(1) is bonded in a distorted trigonal non-coplanar geometry to one Rb(1), one O(4), one O(5), and one O(8) atom. The Li(1)-O(4) bond length is 1.91 Å. The Li(1)-O(5) bond length is 1.90 Å. The Li(1)-O(8) bond length is 1.90 Å. Tb(1) is bonded in a 6-coordinate geometry to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. The Tb(1)-O(3) bond length is 2.28 Å. The Tb(1)-O(4) bond length is 2.31 Å. The Tb(1)-O(5) bond length is 2.61 Å. The Tb(1)-O(6) bond length is 2.19 Å. The Tb(1)-O(7) bond length is 2.28 Å. The Tb(1)-O(8) bond length is 2.30 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a tetrahedral geometry to one O(1), one O(3), one O(5), and one O(7) atom. The V(1)-O(1) bond length is 1.69 Å. The V(1)-O(3) bond length is 1.76 Å. The V(1)-O(5) bond length is 1.77 Å. The V(1)-O(7) bond length is 1.76 Å. In the second V site, V(2) is bonded in a tetrahedral geometry to one O(2), one O(4), one O(6), and one O(8) atom. The V(2)-O(2) bond length is 1.74 Å. The V(2)-O(4) bond length is 1.89 Å. The V(2)-O(6) bond length is 1.85 Å. The V(2)-O(8) bond length is 1.89 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Rb(1), one Rb(3), and one V(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(2), two equivalent Rb(3), and one V(2) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to two equivalent Rb(2), one Tb(1), and one V(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Rb(1), one Rb(2), one Li(1), one Tb(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted water-like geometry to two equivalent Rb(2), one Li(1), one Tb(1), and one V(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to two equivalent Rb(1), one Tb(1), and one V(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to two equivalent Rb(2), one Tb(1), and one V(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Rb(1), one Rb(2), one Li(1), one Tb(1), and one V(2) atom.