Tri‐, Penta‐, and Octaiodide Salts of Transition Metal Polyether Complexes

Salts of transition metal cations complexed by 12‐crown‐4, benzo‐15‐crown‐5 or 18‐crown‐6 with I 3 – , I 5 – and I 8 2– anions, are synthesized and their crystal structures are determined bysingle X‐ray diffraction. The crystal structures of 1 , 2 and 3 are built up by three different cations with the compositions [Fe(H 2 O) 6 (12c4) 6 ] 2+ , [Zn(H 2 O) 2 (b15c5) 3 ] 2+ , [Zn(H 2 O) 5 (18c6) 2 ] 2+ , and isolated triiodide anions I 3 – , respectively. Aside from the cations, the isotypic iron and copper compounds ( 4 , 5 ) contain crystallographically independent V‐shaped pentaiodide anions which are linked to dimers by weak interionic contacts. Furthermore, the structures contain centrosymmetric I 8 2– anions. An investigation of possible secondary contacts reveals that the iodine substructure of 4 and 5 consists of essentially isolated octaiodide units.