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RhTe2 is pyrite-like structured and crystallizes in the cubic Pa-3 space group. The structure is three-dimensional. Rh4+ is bonded to six equivalent Te2- atoms to form corner-sharing RhTe6 octahedra. The corner-sharing octahedral tilt angles are 62°. All Rh–Te bond lengths are 2.70 Å. Te2- is bonded in a 3-coordinate geometry to three equivalent Rh4+ atoms.
Cr(RhTe2)2 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. Cr2+ is bonded to six Te2- atoms to form CrTe6 octahedra that share corners with twelve equivalent RhTe6 octahedra, edges with two equivalent CrTe6 octahedra, and faces with two equivalent RhTe6 octahedra. The corner-sharing octahedra tilt angles range from 52–53°. There are four shorter (2.78 Å) and two longer (2.80 Å) Cr–Te bond lengths. Rh3+ is bonded to six Te2- atoms to form RhTe6 octahedra that share corners with six equivalent CrTe6 octahedra, edges with six equivalent RhTe6 octahedra, and a faceface with one CrTe6 octahedra. The corner-sharing octahedra tilt angles range from 52–53°. There are a spread of Rh–Te bond distances ranging from 2.67–2.76 Å. There are two inequivalent Te2- sites. In the first Te2- site, Te2- is bonded in a 5-coordinate geometry to two equivalent Cr2+ and three equivalent Rh3+ atoms. In the second Te2- site, Te2- is bonded in a 4-coordinate geometry to one Cr2+ and three equivalent Rh3+ atoms.