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Crystal structures of a series of bis-(acetyl-aceto-nato)oxovanadium(IV) complexes containing N-donor pyridyl ligands.

ABSTRACT: Crystal structures for a series of bis-(acetyl-acetonato)oxovanadium(IV) complexes containing N-donor pyridyl ligands are reported, namely, bis-(acetyl-acetonato-κ² O,O')oxido(pyridine-κN)vanadium(IV), [V(C₅H₇O₂)₂O(C₅H₅N)], 1, bis-(acetyl-acetonato-κ² O,O')oxido(pyridine-4-carbo-nitrile-κN)vanadium(IV), [V(C₅H₇O₂)₂O(C₆H₄N₂)], 2, and bis-(acetyl-acetonato-κ² O,O')(4-meth-oxy-pyridine-κN)oxidovanadium(IV), [V(C₅H₇O₂)₂O(C₆H₇NO)], 3, Compounds 1-3 have the formulae VO(C₅H₇O₂)₂ L, where L = pyridine (1), 4-cyano-pyridine (2), and 4-meth-oxy-pyridine (3). Compound 1 was previously reported [Meicheng et al. (1984 ▸). Kexue Tongbao, 29, 759-764 and DaSilva, Spiazzi, Bortolotto & Burrow (2007). Acta Crystallogr., E63, m2422] and redetermined here at cryogenic temperatures. Compounds 1 and 2 as pyridine and 4-cyano-pyridine adducts, respectively, crystallize as distorted octa-hedral structures with the oxo and pyridyl ligands trans to one another. A crystallographic twofold axis runs through the O-V-N bonds. Compound 3 containing a 4-meth-oxy-pyridine ligand crystallizes as a distorted octa-hedral structure with the oxo and pyridyl ligands cis to one other, removing the twofold symmetry seen in the other complexes.

SUBMITTER: Rood JA

PROVIDER: S-EPMC7273989 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

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Crystal structures of a series of bis-(acetyl-aceto-nato)oxovanadium(IV) complexes containing N-donor pyridyl ligands.

Rood Jeffrey A JA Reehl Steven R SR Jacoby Kaitlyn A KA Oliver Allen A

Acta crystallographica. Section E, Crystallographic communications 20200515 Pt 6

Crystal structures for a series of bis-(acetyl-acetonato)oxovanadium(IV) complexes containing N-donor pyridyl ligands are reported, namely, bis-(acetyl-acetonato-κ2 O,O')oxido(pyridine-κN)vanadium(IV), [V(C5H7O2)2O(C5H5N)], 1, bis-(acetyl-acetonato-κ2 O,O')oxido(pyridine-4-carbo-nitrile-κN)vanadium(IV), [V(C5H7O2)2</ ...[more]

PMID: 32523748

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Project description:Five new polyoxometalate (POM)-based metal-organic complexes (MOCs) with different rigid pyridyl-bis(triazole) ligands, namely, H{Co2(Hpyttz-I)2(H2O)6[CrMo6(OH)6O18]}·8H2O (1), {Co2(H2pyttz-I)2(H2O)4[TeMo6O24]}[Co(H2O)6]·3H2O (2), {Co3(Hpyttz-II)2(H2O)6[γ-Mo8O26]}·10H2O (3), {Ni3(Hpyttz-II)2(H2O)6[γ-Mo8O26]}·10H2O (4), {Ni3(Hpyttz-III)2(H2O)8[γ-Mo8O26]}·10H2O (5) (H2pyttz-I = 3-(pyrid-2-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl, H2pyttz-II = 3-(pyrid-3-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl, H2pyttz -III = 3-(pyrid-4-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl), were successfully synthesized and structurally characterized by single-crystal X-ray diffraction, IR spectra, powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Complex 1 is a two-dimensional (2D) supramolecular network based on the binuclear complex unit: [Co2(Hpyttz-I)2(H2O)6 [CrMo6(OH)6O18]]. Complex 2 is a 1D supramolecular chain derived from the binuclear cobalt complex: {Co2(H2pyttz-I)2(H2O)4[TeMo6O24]}2-, the discrete [Co(H2O)6]2+ units act as counter cations. Complexes 3 and 4 are isostructural with different center metals (M = Co or Ni), the adjacent γ-Mo8O26 4- anions are linked by the MII ions to form a 1D M-γ-Mo8O26 inorganic chain. Then 1D M-γ-Mo8O26 inorganic chains are linked together by the 1D metal-organic M-(Hpyttz-II) chains to form a 3D framework. In complex 5, γ-Mo8O26 4- anions are bridged by the NiII ions to give a 1D Ni-γ-Mo8O26 inorganic chain, the adjacent 1D Ni-γ-Mo8O26 chains are connected through [Ni(Hpyttz-III)2] units to form a 2D layer. The effect of POM type and coordination site of the ligands on the structures of the title complexes were discussed. The title complexes 1, 2 and 5 exhibit excellent bifunctional electrocatalytic activities toward the reduction of bromate/hydrogen peroxide and the oxidation of ascorbic acid. In addition, the redox potentials of complexes 1, 2 and 5 are highly sensitive to pH and may be used as a kind of potential pH sensor.

Dataset Information

Crystal structures of a series of bis-(acetyl-aceto-nato)oxovanadium(IV) complexes containing N-donor pyridyl ligands.

Publications

Crystal structures of a series of bis-(acetyl-aceto-nato)oxovanadium(IV) complexes containing N-donor pyridyl ligands.

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