Synthesis, geometrical and electronic structure of iron mononitrosyl complexes with bis(S-alkylisothiosemicarbazones) of β-dicarbonyl compounds

N. V. Gerbeleu, V. B. Arion, Yu A. Simonov, V. E. Zavodnik, S. S. Stavrov, K. I. Turta, D. I. Gradinaru, M. S. Birca, A. A. Pasynskii, O. Ellert

Research output: Contribution to journalArticlepeer-review

Abstract

Complex [Fe(HL)NO]NO3 (1), where H3L=2,4-pentanedione bis(S-methylisothiosemicarbazone), has been synthesized by template reaction of S-methylisothiosemicarbazidehydrogen-nitrate, sodium acetylacetonate monohydrate and Fe(NO3)3·9H2O in ethanol, while [Fe(R2Q)NO] (2), where RCH3 (2a), C2H5 (2b), n-C3H7 (2c), n-C4H9 (2d), has been obtained by the interaction of Fe(NO3)3·9H2O with nitromalondialdehyde bis(S-methylisothiosemicarbazone) (R3H3Q) in the presence of nitric oxide in ethanol. The crystal structures of 1 and 2c have been determined by X-ray diffraction methods. Crystal 1 belongs to the monoclinic system, space group P21/n; a=7.660(1), b=21.092(2), c=10.385(2) Å, γ=96.15(2)°, ρ{variant}calc=1.367 g cm-3, Z=4, molecular formula C9H16FeN8O3S2. Crystal 2c is triclinic, space group P1; a=8.108(2), b=9.489(2), c=12.872(3) Å, α=103.51(2), β=106.02(2), γ=75.09(2)°, ρ{variant}calc=1.578 g cm-3, Z=2, molecular formula C11H18FeN8O3S2. The structures 1 (2c) were solved by direct methods. Least-squares refinement using 1829 (1794) unique reflections with I≥3σ(I) has led to the final R of 0.026 (0.034) for 1 (2c). The cation [Fe(HL)NO]+ and complex 2c have a square-pyramidal structure with the corresponding quadridentate ligand (HL2- and C3H7Q3-) around the central ion in the basal plane (deviation from the pyramid base plane 0.477 (1) and 0.473 (2c) Å) and the NO in the apical position. The FeNO group is approximately linear (the FeNO angle is equal to 172.7 (175.5°)). The data of the 1H NMR, IR, Mössbauer and electronic absorption spectra indicate that 2a-2d have a similarly structured coordination polyhedron. On the basis of X-ray analysis, IR, Mössbauer spectra and calculations of the electronic structures, it was concluded that the FeNO group is a highly covalent entity.

Original languageEnglish
Pages (from-to)173-181
Number of pages9
JournalInorganica Chimica Acta
Volume202
Issue number2
DOIs
StatePublished - 15 Dec 1992
Externally publishedYes

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