Structure of FeI2·[16]aneS4: Square-Planar or Octahedral Iron Coordination?

H. Paulsen, M. Kröckel, M. Grodzicki, E. Bill, A. X. Trautwein*, G. J. Leigh, J. Silver

*Corresponding author for this work
11 Citations (Scopus)


The adducts FeI2·[16]aneS4 (1) and FeBr2·[16]aneS4 (2) are high-spin iron(II) compounds that may be described as either octahedral or square-planar coordinated complexes. Mössbauer measurements on 1 at various temperatures and applied fields analyzed with the spin-Hamiltonian formalism together with spin-polarized molecular orbital calculations in local density approximation clearly favor the octahedral description. Calculations with different iron-iodine bond lengths elucidate the structural dependence of Mössbauer parameters and orbital energies during the gradual transition from octahedral to square-planar like coordination. A suggestion for the geometry of 2 (dFe,Br = 2.47 Å) is obtained by minimizing the total binding energy. MO calculations provide evidence that unusually large iron-sulfur bond distances in 1 and 2 are forced by the size of the macrocycle [16]aneS4 and are connected with unusually large axial bond distances.

Original languageEnglish
JournalInorganic Chemistry
Issue number25
Pages (from-to)6244-6249
Number of pages6
Publication statusPublished - 01.10.1995


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