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Structural characterization of pyridin-2-, -3-, and -4-yl functionalized (iminodimethanediyl)bis(phosphonic) acids : insight into the cobalt(II) and copper(II) complexes of pyridin-2-yl derivative.
Autorzy
Rok wydania
2013
Czasopismo
Numer woluminu
50
Strony
398-409
DOI
10.1016/j.poly.2012.11.023
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
Three representatives of a new family of C-functionalized derivatives of (iminodimethanediyl)bis(phos-phonic) acid, namely pyridin-2-, 3-, and -4-yl derivatives (1–3, respectively) are characterized in solutionby the NMR method and in the solid state by single crystal X-ray diffraction. Detailed crystallographicstructural studies are provided for1and2. For3, the model of molecular structure is proposed. Com-pounds1and2crystallize as zwitterions with one and five water molecules in the asymmetric units,respectively. In1, zwitterions are arranged into two-dimensional hydrogen-bonded layers parallel to(101) plane. In2, one-dimensional chains running alongadirection are observed. Hydrogen bondingmediated by water molecules hold above mentioned motifs into three-dimensional structures.The reaction of1with Co(II) and Cu(II) afforded two isomorphous crystals, namely, Co(LH2)0.7H2O(1-a)and Cu(LH2)0.9H2O(1-b).Both compounds are characterized by means of X-ray crystallography,NIR–Vis–UV spectroscopy, and their magnetic properties are reported.Compounds1-aand1-breveal similar overall structures and packing schemes. Each M(II) ion is five-coordinate, displays distorted trigonal–bipyramidal geometry and is surrounded by three anions of1. Thefive-coordination sphere of M(II) is formed by N2, N1 and O4 atoms of tridentate chelating dianion andO1, O2 oxygen atoms of two remaining dianions. Observed transition energies in the NIR–Vis–UV spectraand their assignments are consistent with distorted trigonal-bypyramid geometry found for [MN2O3]chromophore around M(II) center. The crystals of1-aand1-bcomprise 1D coordination ribbon-like poly-mers running alongaaxis.The ribbons are assembled into layers parallel to (001) plane throughOHO and NHO hydrogen bonds, and joined into 3D structures by means of weak CHO inter-actions and hydrophobic effects.Analysis of magnetic properties of1-aprovided evidence for the occurrence of weak antiferromagneticinteractions (J=1.5 cm1) between neighboring Co centers linked through O–P–O bridges.
Słowa kluczowe
C-substituted derivatives of(iminodimethanediyl)bis(phosphonic) acid NMR, X-ray structures, Co(II) and Cu(II) complexes, NIR–Vis–UV spectroscopy, Magnetic properties
Adres publiczny
http://dx.doi.org/10.1016/j.poly.2012.11.023
Strona internetowa wydawcy
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