Syntheses and crystal structures of several novel alkylammonium iodobismuthate materials containing the 1,3-bis-(4-piperidinium)propane cation

The inorganic-organic salts (H2TMDP)(3)(Bi2I9)(2) (1), (H2TMDP)(2)(Bi4I16)center dot 2EtOH (2), (H2TMDP)(2)(Bi6I22)center dot 2EtOH (3), and (H2TMDP)(2)(Bi6I22) (4) were synthesized and structurally characterized from the solvothermal reaction of 1,3-bis-(4-piperidyl)propane (TMDP) and BiI3 by adjusting the relative ratio of the reactants. The anions of the compounds consist of 2 (1), 4 (2), or 6 (3 and 4) BiI6 polyhedra, which are joined by face-(1) or edge-sharing (2-4) to form discrete anions. The size of the discrete anion, in terms of the number of connected polyhedra, is observed to increase as the ratio of BiI3 to TMDP is increased. A related compound (H2TMDP)(Bi3I11) center dot (H2O) (5) was synthesized and structurally characterized using the same two reactants in the presence of HF. The anion of 5 is polymeric rather than discrete, with a trioctahedral repeat unit. (c) 2005 Elsevier Inc. All rights reserved.