Abstract: | Two new molecular metal chalcogenides, tris(ethylenediamine‐N,N′)manganese(II) tetratelluride, Mn(C2H8N2)3]Te4, (I), and bistris(ethylenediamine‐N,N′)iron(II)] pentaselenodiantimonate(III), Fe(C2H8N2)3]2(Sb2Se5), (II), containing the isolated molecular building blocks Te42? and Sb2Se54?, have been synthesized by solvothermal reactions in an ethylenediamine solution at 433 K. The anion Te42? in (I) is a zigzag oligometric chain with Te—Te bond lengths in the range 2.709–2.751 Å. There is a very short contact 3.329 (1) Å] between a pair of neighboring Te42? anions. In (II), each Sb atom is surrounded by three Se atoms to give a tripodal coordination. One of the three independent Se atoms is a μ2‐bridging ligand between two Sb atoms; the other two are terminal. |