A One-Dimensional Polymeric Form of the Polycation Te 8 2+ in the Structure of Te 8 [Bi 4 Cl 14 ]

The reaction of Te, TeCl 4 and BiCl 3 in a sealed evacuated glass ampoule in a temperature gradient 160 to 90 °C yields Te 8 [Bi 4 Cl 14 ] as black platelike crystals with a golden lustre which are deposited in the temperature zone 150 to 130 °C. The best yield is obtained with a Te/TeCl 4 /BiCl 3 molar ratio of 15/3/4. The crystal structure determination (orthorhombic, P2 1 2 1 2 1 , a = 879.9(3), b = 1642.3(4), c = 2267.3(8) pm, Z = 4) shows that Te 8 [Bi 4 Cl 14 ] consists of a novel one-dimensional (Te 8 2+ )„ polycation and a two-dimensional chlorobismutate anion Bi4Cl 14 2- . The structure of the cation consists of boat shaped Te 6 rings which are connected in the 1,4-positions by Te 2 groups to a one-dimensional polymeric strand. The structure is substantially different from the previously reported Te 8 2+ polycations in Te8[WCl 6 ] 2 and Te 8 [MCl 6 ] (M = Zr, Hf, Re) where discrete bicyclic clusters with only weak interionic interactions are present. The Bi 4 Cl 14 2- ion can be described as built up of BiCl 3 molecules which are connected by Cl - ions to a two-dimensional network [(BiCl 3 ) 4 (Cl - ) 2 ] n .