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RbMnTe2 crystallizes in the tetragonal I-4m2 space group. The structure is three-dimensional. Rb1+ is bonded in a body-centered cubic geometry to eight equivalent Te2- atoms. All Rb–Te bond lengths are 3.82 Å. Mn3+ is bonded to four equivalent Te2- atoms to form corner-sharing MnTe4 tetrahedra. All Mn–Te bond lengths are 2.65 Å. Te2- is bonded in a 2-coordinate geometry to four equivalent Rb1+ and two equivalent Mn3+ atoms.
Rb2MnTe2 crystallizes in the orthorhombic Ibam space group. The structure is three-dimensional. Rb1+ is bonded in a 6-coordinate geometry to six equivalent Te2- atoms. There are a spread of Rb–Te bond distances ranging from 3.75–4.01 Å. Mn2+ is bonded to four equivalent Te2- atoms to form edge-sharing MnTe4 tetrahedra. All Mn–Te bond lengths are 2.77 Å. Te2- is bonded in a 8-coordinate geometry to six equivalent Rb1+ and two equivalent Mn2+ atoms.