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Structural Diversity in Thallium Chemistry. Part VI. Analysis of Structure Correlation in Organoammonium Bromothallates(III)


Linden, A; Petridis, A; James, B D (2009). Structural Diversity in Thallium Chemistry. Part VI. Analysis of Structure Correlation in Organoammonium Bromothallates(III). Helvetica Chimica Acta, 92(1):29-71.

Abstract

New bromothallate(III) complexes have been synthesized using eleven organoammonium cations related to others employed previously. The crystal structure determinations of eight of these have been performed. The diethylenetriammonium cation yields the first compound containing [TlBr6]3 as the only anionic species, while the N,N,N’,N’’,N’’-pentamethyldiethylenetriammonium cation gave a mixed salt containing discrete [TlBr4] and Br ions, in which the [TlBr4] unit does not participate in hydrogen bonding. In the pyrazolinium mixed salt, both the [TlBr4] and Br ions are hydrogen-bonded to cations and disposed in an arrangement similar to a [Tl2Br9]3 unit. The triethylenediammonium dication gives a compound in which a highly distorted trigonal bipyramidal [TlBr5]2 system is present, while the 1-benzylpiperazinium compound also shows a very weak [TlBr4] and Br interaction. Six other monovalent cations provided [TlBr4] derivatives that were characterized either crystallographically or via their Raman spectra. In a comprehensive structural summary, the various interactions between cations and bromothallate(III) anionic groupings, giving rise to the structural diversity described in this and previous reports, are discussed in terms of the cation charge, quaternization and steric influence, N H··· Br hydrogen bonding, and secondary bonds present in the compounds.

Abstract

New bromothallate(III) complexes have been synthesized using eleven organoammonium cations related to others employed previously. The crystal structure determinations of eight of these have been performed. The diethylenetriammonium cation yields the first compound containing [TlBr6]3 as the only anionic species, while the N,N,N’,N’’,N’’-pentamethyldiethylenetriammonium cation gave a mixed salt containing discrete [TlBr4] and Br ions, in which the [TlBr4] unit does not participate in hydrogen bonding. In the pyrazolinium mixed salt, both the [TlBr4] and Br ions are hydrogen-bonded to cations and disposed in an arrangement similar to a [Tl2Br9]3 unit. The triethylenediammonium dication gives a compound in which a highly distorted trigonal bipyramidal [TlBr5]2 system is present, while the 1-benzylpiperazinium compound also shows a very weak [TlBr4] and Br interaction. Six other monovalent cations provided [TlBr4] derivatives that were characterized either crystallographically or via their Raman spectra. In a comprehensive structural summary, the various interactions between cations and bromothallate(III) anionic groupings, giving rise to the structural diversity described in this and previous reports, are discussed in terms of the cation charge, quaternization and steric influence, N H··· Br hydrogen bonding, and secondary bonds present in the compounds.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:January 2009
Deposited On:15 Mar 2009 11:33
Last Modified:05 Apr 2016 12:55
Publisher:Verlag Helvetica Chimica Acta
ISSN:0018-019X
Funders:Faculty of Science, Technology and Engineering, La Trobe University, Australia
Publisher DOI:https://doi.org/10.1002/hlca.200800316

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