Tuning of the charge in octahedral ferric complexes based on pyridoxal-N substituted thiosemicarbazone ligands

Eddy W. Yemeli Tido, Christophe Faulmann, Robby Roswanda, Auke Meetsma, Petra J. van Koningsbruggen

Research output: Contribution to journalArticle

Abstract

Four novel mononuclear coordination compounds namely: [Fe(Hthpy)2](SO4)1/2·3.5H2O 1, [Fe(Hthpy)2]NO3·3H2O 2, [Fe(H2mthpy)2](CH3C6H4SO3)3·CH3CH2OH 3 and [Fe(Hethpy)(ethpy)]·8H2O 4, (H2thpy = pyridoxalthiosemicarbazone, H2mthpy = pyridoxal-4-methylthiosemicarbazone, H2ethpy = pyridoxal-4-ethylthiosemicarbazone), were synthesized in the absence or presence of organic base, Et3N and NH3. Compounds 1 and 2 are monocationic, and were prepared using the singly deprotonated form of pyridoxalthiosemicarbazone. Both compounds crystallise in the monoclinic system, C2/c and P21/c space group for 1 and 2, respectively. Complex 3 is tricationic, it is formed with neutral bis(ligand) complex and possesses an interesting 3D channel architecture, the unit cell is triclinic, P1 space group. For complex 4, the pH value plays an important role during its synthesis; 4 is neutral and crystallises with two inequivalent forms of the ligand: the singly and the doubly deprotonated chelate of H2ethpy, the unit cell is monoclinic, C2/c space group. Notably, in 1 and 4, there is an attractive infinite three dimensional hydrogen bonding network in the crystal lattice. Magnetic measurements of 1 and 4 revealed that a rather steep spin transition from the low spin to high spin Fe(III) states occurs above 300 K in the first heating step. This transition is accompanied by the elimination of solvate molecules and thus, stabilizes the high spin form due to the breaking of hydrogen bonding networks; compared to 2 and 3, which keep their low spin state up to 400 K.
Original languageEnglish
Pages (from-to)1643-1651
Number of pages9
JournalDalton Transactions
Volume39
Issue number6
DOIs
Publication statusPublished - 2010

Keywords

  • Four novel mononuclear coordination compounds namely
  • [Fe(Hthpy)2](SO4)1/2·3.5H2O 1
  • [Fe(Hthpy)2]NO3·3H2O 2
  • [Fe(H2mthpy)2](CH3C6H4SO3)3·CH3CH2OH 3 and [Fe(Hethpy)(ethpy)]·8H2O 4
  • (H2thpy = pyridoxalthiosemicarbazone
  • H2mthpy = pyridoxal-4-methylthiosemicarbazone
  • H2ethpy = pyridoxal-4-ethylthiosemicarbazone)
  • Et3N and NH3. Compounds 1 and 2 are monocationic
  • singly deprotonated form of pyridoxalthiosemicarbazone
  • crystallise in the monoclinic system
  • C2/c and P21/c space group for 1 and 2
  • respectively
  • complex 3 is tricationic
  • the singly and the doubly deprotonated chelate of H2ethpy
  • solvate molecules

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