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

Jack M. Harrowfield, Yang Kim, Brian W. Skelton, Alexandre N. Sobolev, Allan H. White

Research output: Contribution to journalArticle

1 Citation (Scopus)

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. Delta,Lambda-[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. Delta-[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, Delta-[Co((NO2)(2)sar)](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.

Original languageEnglish
Pages (from-to)2372-2379
Number of pages8
JournalCrystEngComm
Volume19
Issue number17
DOIs
Publication statusPublished - 7 May 2017

Cite this

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title = "Chiral discrimination in solid-state interactions of cobalt(III)-polyamine complex cations with tris-(dipicolinato)lanthanate(III) anions",
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. Delta,Lambda-[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. Delta-[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, Delta-[Co((NO2)(2)sar)](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.",
keywords = "RARE-EARTH CARBOXYLATES, LANTHANIDE COMPLEXES, CRYSTAL-STRUCTURE, MOLECULAR-STRUCTURE, DIPICOLINATE, RESOLUTION, ION, SPECTROSCOPY, TRANSITION, SYMMETRY",
author = "Harrowfield, {Jack M.} and Yang Kim and Skelton, {Brian W.} and Sobolev, {Alexandre N.} and White, {Allan H.}",
year = "2017",
month = "5",
day = "7",
doi = "10.1039/c6ce02573k",
language = "English",
volume = "19",
pages = "2372--2379",
journal = "CrystEngComm.",
issn = "1466-8033",
publisher = "ROYAL SOC CHEMISTRY",
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Chiral discrimination in solid-state interactions of cobalt(III)-polyamine complex cations with tris-(dipicolinato)lanthanate(III) anions. / Harrowfield, Jack M.; Kim, Yang; Skelton, Brian W.; Sobolev, Alexandre N.; White, Allan H.

In: CrystEngComm, Vol. 19, No. 17, 07.05.2017, p. 2372-2379.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Chiral discrimination in solid-state interactions of cobalt(III)-polyamine complex cations with tris-(dipicolinato)lanthanate(III) anions

AU - Harrowfield, Jack M.

AU - Kim, Yang

AU - Skelton, Brian W.

AU - Sobolev, Alexandre N.

AU - White, Allan H.

PY - 2017/5/7

Y1 - 2017/5/7

N2 - 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. Delta,Lambda-[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. Delta-[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, Delta-[Co((NO2)(2)sar)](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.

AB - 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. Delta,Lambda-[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. Delta-[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, Delta-[Co((NO2)(2)sar)](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.

KW - RARE-EARTH CARBOXYLATES

KW - LANTHANIDE COMPLEXES

KW - CRYSTAL-STRUCTURE

KW - MOLECULAR-STRUCTURE

KW - DIPICOLINATE

KW - RESOLUTION

KW - ION

KW - SPECTROSCOPY

KW - TRANSITION

KW - SYMMETRY

U2 - 10.1039/c6ce02573k

DO - 10.1039/c6ce02573k

M3 - Article

VL - 19

SP - 2372

EP - 2379

JO - CrystEngComm.

JF - CrystEngComm.

SN - 1466-8033

IS - 17

ER -