Two polytellurides of double and triple charged organic cations have been synthesized and their crystal structures have been determined.

K₂Te₃ and the iodides of 2,2,5,5-tetramethyl-2,5-diazoniahexane, [TMDH]I₂, and 2,2,5,5,8,8-hexamethyl-2,5,8-triazonianonane, [HMTN]I₃, respectively, are mixed together in aqueous solution in appropriate ratios. After a few hours black crystals of the polytellurides precipitate. The reaction of the double charged cation, TMDH²⁺, results in the tetratelluride, [TMDH]Te₄, whereas that of the triple charged cation, HMTN³⁺, gives the tridecatelluride, [HMTN]₂Te₁₃.

[TMDH]Te₄ crystallizes in the space group P2₁/n (a = 13.321(5) A, b = 15.940(7) A, c = 7.969(3) Å, β = 94.12(3)°). Interconnected Te₄^2--polyanions are found in the structure. [HMTN]₂Te₁₃ crystallizes in the space group PĪ (a = 8.772(2) Å, b = 17.529(4) Å, c = 18.036(4) Å, a = 68.11(3)°, β = 76.73(3)°, γ = 77.08(3)°). No distinct tridecatelluride polyanions occur in the structure, but rather two crystallographically independent Te₄^2--anions and one Te₅^2--anion. As in [TMDH]Te₄, all of the anions are interconnected.