Cs2LiVO4 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent V(1)O4 tetrahedra and  an edgeedge with one V(1)O4 tetrahedra. V(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra and  an edgeedge with one Li(1)O4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Cs(1), one Cs(2), one Li(1), and one V(1) atom. In the second O site, O(2) is bonded in a distorted L-shaped geometry to two equivalent Cs(1), two equivalent Cs(2), one Li(1), and one V(1) atom. In the third O site, O(3) is bonded in a distorted L-shaped geometry to two equivalent Cs(1), two equivalent Cs(2), one Li(1), and one V(1) atom.
Cs2LiVO4 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Cs(1)-O(1) bond lengths are 3.20 Å. There is one shorter (3.14 Å) and one longer (3.26 Å) Cs(1)-O(2) bond length. Both Cs(1)-O(3) bond lengths are 3.15 Å. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Cs(2)-O(1) bond lengths are 3.19 Å. Both Cs(2)-O(2) bond lengths are 3.18 Å. There is one shorter (3.14 Å) and one longer (3.20 Å) Cs(2)-O(3) bond length. Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent V(1)O4 tetrahedra and  an edgeedge with one V(1)O4 tetrahedra. The Li(1)-O(2) bond length is 2.10 Å. The Li(1)-O(3) bond length is 2.04 Å. Both Li(1)-O(1) bond lengths are 1.94 Å. V(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra and  an edgeedge with one Li(1)O4 tetrahedra. The V(1)-O(2) bond length is 1.75 Å. The V(1)-O(3) bond length is 1.75 Å. Both V(1)-O(1) bond lengths are 1.75 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Cs(1), one Cs(2), one Li(1), and one V(1) atom. In the second O site, O(2) is bonded in a distorted L-shaped geometry to two equivalent Cs(1), two equivalent Cs(2), one Li(1), and one V(1) atom. In the third O site, O(3) is bonded in a distorted L-shaped geometry to two equivalent Cs(1), two equivalent Cs(2), one Li(1), and one V(1) atom.