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

• Published in: Journal of solid state chemistry 2005-11, Vol.178 (11), p.3529-3540
• Main Authors: Goforth, Andrea M., Peterson, LeRoy, Smith, Mark D., zur Loye, Hans-Conrad
• Format: Article
• Language: English
• Subjects: AMMONIUM COMPOUNDS; BISMUTH COMPOUNDS; Bismuth iodide; Cross-disciplinary physics: materials science; rheology; CRYSTAL STRUCTURE; Exact sciences and technology; Halobismuthate; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; IODINE COMPOUNDS; Iodobismuthate; Materials science; MONOCRYSTALS; Physics; SYNTHESIS
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/j.jssc.2005.09.010

The inorganic–organic salts (H 2TMDP) 3(Bi 2I 9) 2 ( 1), (H 2TMDP) 2(Bi 4I 16)·2EtOH ( 2), (H 2TMDP) 2(Bi 6I 22)·2EtOH ( 3), and (H 2TMDP) 2(Bi 6I 22) ( 4) were synthesized and structurally characterized from the solvothermal reaction of 1,3-bis-(4-piperidyl)propane (TMDP) and BiI 3 by adjusting the relative ratio of the reactants. The anions of the compounds consist of 2 ( 1), 4 ( 2), or 6 ( 3 and 4) BiI 6 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 BiI 3 to TMDP is increased. A related compound (H 2TMDP)(Bi 3I 11)·(H 2O) ( 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. The syntheses and single-crystal X-ray structures of five new inorganic–organic compounds containing the alkylammonium cation 1,3-bis-(4-piperidinium)propane in addition to a complex iodobismuthate anion are presented and discussed. In general, structures having larger anions are produced from greater relative ratios of the inorganic starting material to the organic starting material.