Protonated Organic Diamines as Templates for Layered and Microporous Structures: Synthesis, Crystal Chemistry, and Structural Trends among the Compounds Formed in Aqueous Systems Transition Metal Halide or Nitrate-Diamine-Selenious Acid

Systematic studies of crystalline compounds formed in aqueous systems containing aliphatic diamines, divalent transition metal halides, and selenious acid resulted in the discovery of a large family of new complex species corresponding to several new structure types. With ethylenediamine (en), layered (enH(2))[M(HSeO3)(2)X-2] compounds are the most commonly formed species which constitute a significant contribution to the family of layered hydrogen selenites containing neutral [M(HSeO3)(2)] (M = Mg, Mn, Co, Ni, Cu, Zn, Cd) 2D building blocks. In contrast to some previous suggestions, piperazine (pip), as well as its homologue N-methylpiperazine, mostly give rise to quite different, sometimes more complex, structures of varied dimensionality while the (pipH(2))[M(HSeO3)(2)X-2] compounds are formed only with M = Cu and Cd. In addition, metal-, halide-, or selenium-free by-product species are observed. The Se-IV can be present in a multitude of forms, including H2SeO3, HSeO3-, SeO32-, and Se2O52-, reflecting amazing adaptability to the shape of the templating cations.