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Metal ion influences distortion of the ligand in the structure of $[M\{2-MeO(O)CC_6H_4NHC(S)NP(S)(OiPr)_2\}_2] (M = Zn^{II}, Cd^{II})$ complexes : a driving force for intermolecular aggregation

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Metal ion influences distortion of the ligand in the structure of $[M\{2-MeO(O)CC_6H_4NHC(S)NP(S)(OiPr)_2\}_2] (M = Zn^{II}, Cd^{II})$ complexes : a driving force for intermolecular aggregation

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dc.contributor.author Safin, Damir A. pl
dc.contributor.author Babashkina, Maria G. pl
dc.contributor.author Bolte, Michael pl
dc.contributor.author Mitoraj, Mariusz [SAP11019444] pl
dc.contributor.author Klein, Axel pl
dc.date.accessioned 2015-12-15T10:48:59Z
dc.date.available 2015-12-15T10:48:59Z
dc.date.issued 2015 pl
dc.identifier.issn 1477-9226 pl
dc.identifier.uri http://ruj.uj.edu.pl/xmlui/handle/item/18274
dc.language eng pl
dc.rights Udzielam licencji. Uznanie autorstwa 3.0 *
dc.rights.uri http://creativecommons.org/licenses/by/3.0/legalcode *
dc.title Metal ion influences distortion of the ligand in the structure of $[M\{2-MeO(O)CC_6H_4NHC(S)NP(S)(OiPr)_2\}_2] (M = Zn^{II}, Cd^{II})$ complexes : a driving force for intermolecular aggregation pl
dc.type JournalArticle pl
dc.description.physical 14101-14109 pl
dc.identifier.weblink http://pubs.rsc.org/en/content/articlelanding/2015/dt/c5dt02189h#!divAbstract pl
dc.identifier.weblink http://www.researchgate.net/publication/279969348 pl
dc.abstract.en Reaction of the in situ deprotonated N-thiophosphorylated thiourea $2-MeO(O)CC_6H_4NHC(S)NHP(S)(OiPr)_2 (HL)$ with $MCl_2 (M = Zn^{II}, Cd^{II})$ in aqueous ethanol leads to complexes of the formula $[ML_2]$. Both compounds crystallise in the triclinic space group P[1 with combining macron] with Z = 2 and the metal cations are found in a tetrahedral S_2S′_2 coordination environment formed by the C–S and P–S sulfur atoms. The crystal structures reveal intramolecular N–H⋯O[double bond, length as m-dash]C hydrogen bonds formed within the $2-MeO(O)CC_6H_4NH$ fragments. Both structures are further stabilised by intermolecular π⋯π stacking interactions, which are more efficient in $[CdL_2]$. Here, a pronounced dimeric intermolecular aggregate is observed which goes along with a pronounced distortion of the chelate [(S)CNP(S)]− backbone of the ligand upon coordination to $Cd^{II}$ as well as a significantly distorted coordination tetrahedron $CdS_2S′_2$. The aggregation is also reflected in the positive electrospray ionisation (ESI) mass spectrum of the CdII complex, which exhibits peaks for the dimeric cations $[Cd_2L_3]+$, $[Cd_2L_4 + H]+$ and $[Cd_2L_4 + Na]+$, while for the ZnII analogue only monomeric species were observed. Quantum chemical ETS-NOCV (ADF) calculations confirm the higher stability of dimers in $[CdL_2]$ compared with $[ZnL_2]$. The π⋯π stacking interactions are prodominantly due to dispersion contributions, though the electrostatic and orbital interaction components are also important. QTAIM (ADF) type calculations additionally quantify the covalent and non-covalent interactions in the momomers. pl
dc.description.volume 44 pl
dc.description.number 31 pl
dc.identifier.doi 10.1039/C5DT02189H pl
dc.identifier.eissn 1477-9234 pl
dc.title.journal Dalton Transactions pl
dc.language.container eng pl
dc.date.accession 2015-11-27 pl
dc.affiliation Wydział Chemii : Zakład Metod Obliczeniowych Chemii pl
dc.subtype Article pl
dc.rights.original CC-BY; inne; ostateczna wersja wydawcy; w momencie opublikowania; 0; pl
dc.identifier.project ROD UJ / P pl
.pointsMNiSW [2015 A]: 40


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Udzielam licencji. Uznanie autorstwa 3.0 Except where otherwise noted, this item's license is described as Udzielam licencji. Uznanie autorstwa 3.0