Cs2Te5 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to one Te(2) and eight equivalent Te(1) atoms. In the second Cs site, Cs(2) is bonded in a 9-coordinate geometry to one Te(2) and eight equivalent Te(1) atoms. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded to two equivalent Cs(1), two equivalent Cs(2), one Te(1), and one Te(2) atom to form distorted TeCs4Te2 octahedra that share corners with three equivalent Te(2)Cs2Te4 octahedra, corners with thirteen equivalent Te(1)Cs4Te2 octahedra,  an edgeedge with one Te(2)Cs2Te4 octahedra, edges with six equivalent Te(1)Cs4Te2 octahedra, and faces with two equivalent Te(1)Cs4Te2 octahedra. The corner-sharing octahedral tilt angles range from 2-96°. In the second Te site, Te(2) is bonded to one Cs(1), one Cs(2), and four equivalent Te(1) atoms to form a mixture of edge and corner-sharing TeCs2Te4 octahedra. The corner-sharing octahedral tilt angles range from 56-96°.
Cs2Te5 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to one Te(2) and eight equivalent Te(1) atoms. The Cs(1)-Te(2) bond length is 4.01 Å. There are four shorter (4.05 Å) and four longer (4.07 Å) Cs(1)-Te(1) bond lengths. In the second Cs site, Cs(2) is bonded in a 9-coordinate geometry to one Te(2) and eight equivalent Te(1) atoms. The Cs(2)-Te(2) bond length is 3.97 Å. There are four shorter (3.95 Å) and four longer (4.13 Å) Cs(2)-Te(1) bond lengths. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded to two equivalent Cs(1), two equivalent Cs(2), one Te(1), and one Te(2) atom to form distorted TeCs4Te2 octahedra that share corners with three equivalent Te(2)Cs2Te4 octahedra, corners with thirteen equivalent Te(1)Cs4Te2 octahedra,  an edgeedge with one Te(2)Cs2Te4 octahedra, edges with six equivalent Te(1)Cs4Te2 octahedra, and faces with two equivalent Te(1)Cs4Te2 octahedra. The corner-sharing octahedral tilt angles range from 2-96°. The Te(1)-Te(1) bond length is 2.80 Å. The Te(1)-Te(2) bond length is 3.08 Å. In the second Te site, Te(2) is bonded to one Cs(1), one Cs(2), and four equivalent Te(1) atoms to form a mixture of edge and corner-sharing TeCs2Te4 octahedra. The corner-sharing octahedral tilt angles range from 56-96°.