CsV3(TeO6)2 crystallizes in the hexagonal P6_3 space group. Cs(1) is bonded in a 6-coordinate geometry to three equivalent O(2) and three equivalent O(3) atoms. V(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form distorted corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 34-37°. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded in a distorted trigonal non-coplanar geometry to three equivalent O(1) atoms. In the second Te site, Te(2) is bonded in a 3-coordinate geometry to three equivalent O(3) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one V(1) and one Te(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Cs(1) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Cs(1), one V(1), and one Te(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to two equivalent V(1) atoms.
CsV3(TeO6)2 crystallizes in the hexagonal P6_3 space group. Cs(1) is bonded in a 6-coordinate geometry to three equivalent O(2) and three equivalent O(3) atoms. All Cs(1)-O(2) bond lengths are 3.17 Å. All Cs(1)-O(3) bond lengths are 3.22 Å. V(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form distorted corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 34-37°. The V(1)-O(1) bond length is 2.03 Å. The V(1)-O(3) bond length is 1.91 Å. There is one shorter (1.71 Å) and one longer (2.17 Å) V(1)-O(2) bond length. There is one shorter (1.70 Å) and one longer (2.12 Å) V(1)-O(4) bond length. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded in a distorted trigonal non-coplanar geometry to three equivalent O(1) atoms. All Te(1)-O(1) bond lengths are 1.90 Å. In the second Te site, Te(2) is bonded in a 3-coordinate geometry to three equivalent O(3) atoms. All Te(2)-O(3) bond lengths are 1.92 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one V(1) and one Te(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Cs(1) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Cs(1), one V(1), and one Te(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to two equivalent V(1) atoms.