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Issue 17, 2017
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Chiral discrimination in solid-state interactions of cobalt(III)–polyamine complex cations with tris-(dipicolinato)lanthanate(III) anions

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Abstract

Structural characterisation of a further series of crystalline solids in which [Ln(dipic)3]3− anions (dipic = pyridine-2,6-dicarboxylate; Ln = La, Gd) are accompanied by chiral Co(III)-containing cations provides new examples of layered lattices where sheets of anions and (cations + water) alternate. Δ,Λ-[Co(en)3]3+ (en = ethane-1,2-diamine) forms crystals where, depending on the degree of hydration, the cation sheets are either homo- or heterochiral but the anion sheets are always heterochiral. Δ-[Co(en)3]3+ provides lattices where the anion sheets remain heterochiral, resulting in unusual solids containing a single enantiomer of the cation along with both enantiomers of the chiral anion, rather than two diastereomeric crystals containing the separate anions. Classical resolution of the anions only appears to occur in the presence of a functionalised cage amine complex cation, Δ-[Co((NO2)2sar)]3+ (sar = sarcophagine = 3,6,10,13,16,19-hexa-azabicyclo[6.6.6]icosane) which gives crystals in which direct H-bonding interactions between the cations and anions are surprisingly limited and the success of the resolution requires consideration of a variety of other factors.

Graphical abstract: Chiral discrimination in solid-state interactions of cobalt(iii)–polyamine complex cations with tris-(dipicolinato)lanthanate(iii) anions

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Publication details

The article was received on 15 Dec 2016, accepted on 29 Mar 2017 and first published on 04 Apr 2017


Article type: Paper
DOI: 10.1039/C6CE02573K
Citation: CrystEngComm, 2017,19, 2372-2379
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    Chiral discrimination in solid-state interactions of cobalt(III)–polyamine complex cations with tris-(dipicolinato)lanthanate(III) anions

    J. M. Harrowfield, Y. Kim, B. W. Skelton, A. N. Sobolev and A. H. White, CrystEngComm, 2017, 19, 2372
    DOI: 10.1039/C6CE02573K

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