Cr2CoTe4 crystallizes in the monoclinic C2/m space group. Cr(1) is bonded to one Co(1), three equivalent Te(1), and three equivalent Te(2) atoms to form distorted CrCoTe6 octahedra that share  a cornercorner with one Cr(1)CoTe6 octahedra, corners with four equivalent Te(2)Cr3Co2 square pyramids, and edges with six equivalent Cr(1)CoTe6 octahedra. The corner-sharing octahedra are not tilted. Co(1) is bonded in a 8-coordinate geometry to two equivalent Cr(1), two equivalent Te(1), and four equivalent Te(2) atoms. There are two inequivalent Te sites. In the first Te site, Te(2) is bonded to three equivalent Cr(1) and two equivalent Co(1) atoms to form distorted TeCr3Co2 square pyramids that share corners with four equivalent Cr(1)CoTe6 octahedra, corners with two equivalent Te(2)Cr3Co2 square pyramids, and edges with five equivalent Te(2)Cr3Co2 square pyramids. The corner-sharing octahedral tilt angles range from 59-121°. In the second Te site, Te(1) is bonded in a rectangular see-saw-like geometry to three equivalent Cr(1) and one Co(1) atom.
Cr2CoTe4 crystallizes in the monoclinic C2/m space group. Cr(1) is bonded to one Co(1), three equivalent Te(1), and three equivalent Te(2) atoms to form distorted CrCoTe6 octahedra that share  a cornercorner with one Cr(1)CoTe6 octahedra, corners with four equivalent Te(2)Cr3Co2 square pyramids, and edges with six equivalent Cr(1)CoTe6 octahedra. The corner-sharing octahedra are not tilted. The Cr(1)-Co(1) bond length is 2.97 Å. There is one shorter (2.69 Å) and two longer (2.70 Å) Cr(1)-Te(1) bond lengths. There are two shorter (2.79 Å) and one longer (2.80 Å) Cr(1)-Te(2) bond length. Co(1) is bonded in a 8-coordinate geometry to two equivalent Cr(1), two equivalent Te(1), and four equivalent Te(2) atoms. Both Co(1)-Te(1) bond lengths are 2.65 Å. All Co(1)-Te(2) bond lengths are 2.70 Å. There are two inequivalent Te sites. In the first Te site, Te(2) is bonded to three equivalent Cr(1) and two equivalent Co(1) atoms to form distorted TeCr3Co2 square pyramids that share corners with four equivalent Cr(1)CoTe6 octahedra, corners with two equivalent Te(2)Cr3Co2 square pyramids, and edges with five equivalent Te(2)Cr3Co2 square pyramids. The corner-sharing octahedral tilt angles range from 59-121°. In the second Te site, Te(1) is bonded in a rectangular see-saw-like geometry to three equivalent Cr(1) and one Co(1) atom.