title: Spectroscopic and structural characterization of the [Fe(imidazole)(6)](2+) cation.
abstract: Spectroscopic, structural, and magnetic data are presented for Fe(C(3)H(4)N(2))(6)(NO(3))(2), which facilitate a precise definition of the electronic and molecular structure of the [Fe(Im)(6)](2+) cation. The structure was determined at 120(1) K by X-ray diffraction methods. The salt crystallizes in the trigonal space group R3 with unit-cell parameters a = 12.4380(14) A, c = 14.5511(18) A, and Z = 3. All the imidazole ligands are equivalent with an Fe-N bond distance of 2.204(1) A. Variable-temperature inelastic neutron scattering (INS) measurements identify a cold magnetic transition at 19.4(2) cm(-1) and a hot transition at 75.7(6) cm(-1). The data are interpreted using a ligand field Hamiltonian acting in the weak-field (5)D basis, from which the diagonal trigonal field splitting of the (5)T(2g) (O(h)) term is estimated as approximately 485 cm(-1), with the (5)A(g) (S(6)) component lower lying. High-field multifrequency (HFMF) EPR data and measurements of the magnetic susceptibility are also reported and can be satisfactorily modeled using the energies and wave functions derived from analysis of the INS data. The electronic and molecular structures are related through angular overlap model calculations, treating the imidazole ligand as a weak pi-donor.
authors.affiliation: Department of Chemistry, University of Bern, Freiestrasse 3, Bern 9, CH-3000 Switzerland.
authors.forename: Graham
authors.initials: G
authors.lastname: Carver
authors.forename: Philip L W
authors.initials: PL
authors.lastname: Tregenna-Piggott
authors.forename: Anne-Laure
authors.initials: AL
authors.lastname: Barra
authors.forename: Antonia
authors.initials: A
authors.lastname: Neels
authors.forename: John A
authors.initials: JA
authors.lastname: Stride
mesh_terms: D000465:Algorithms; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D005296:Ferrous Compounds / Q000737:chemistry*; D007093:Imidazoles / Q000737:chemistry*; D007202:Indicators and Reagents; D007501:Iron / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009502:Neutrons; D012542:Scattering, Radiation; D014961:X-Ray Diffraction
chemical_list: C482778:(Fe(imidazole)(6))(2+); D005296:Ferrous Compounds; D007093:Imidazoles; D007202:Indicators and Reagents; D007501:Iron