Macrobicyclic D-Metal Tris-dioximates Obtained by Cross-linking with P-Block Elements. Part VI. Preparation, Molecular Structure and Mössbauer (₅₇Fe, ₁₁₉Sn) Parameters of an Iron (II) Complex with a Macrobiocyclic Tin-containing Tris-nioximate Ligand

Authors

Sergey V. Lindeman, Marquette UniversityFollow
Yu T. Struchkov, Russian Academy of SciencesFollow
Yan Z. Voloshin, Karpov Institute of Physical ChemistryFollow

Document Type

Article

Language

eng

Publication Date

1993

Publisher

Taylor & Francis

Source Publication

Journal of Coordination Chemistry

Source ISSN

0095-8972

Abstract

The tin-containing clathrochelate complex of Fe(II) with cyclohexanedione-1,2-dioxime (nioxime, H₂Nx), [FeNx₃(SnCl₃)₂]^2- · (Et₂NH⁺ ₂)₂ · Et₂NH₂ ⁺ · Cl⁻ · 2Prⁱ OH was prepared by slowly adding diethylamine to a solution containing the macrobicyclic [FeNx₃(SnCl₃)₂]^2- anion. The structure of the complex has been determined by X-ray methods. Crystal data: monoclinic, space group P2₁/c, a = 10.565(2), b = 25.413(5), c = 20.198(4)Å, β=95.40(3)°, Z = 4. The iron atoms is encapsulated by the clathrochelate ligand and surrounded by a distorted trigonal antiprismatic coordination sphere comprising by six nitrogen atoms of three dioxime residues. The experimental value of the distortion angle (ca 37.5°) is close to that predicted by the Mössbauer (⁵⁷Fe) parameters (ca 40°). The average Fe-N bond length of 1.923Å is somewhat greater than that in boron-containing analogues. The Sn atoms have a slightly distorted octahedral coordination, which also correspond to Mössbauer (¹¹⁹Sn) spectroscopic data. The six-membered carbocycles in the dioxime fragments have a half-chair conformation with both β-carbons displaced to the opposite sides of the mid-plane of the remaining atoms. All the active hydrogen atoms of the structure are involved in a hydrogen bond system.

The possibilities of use of Mössbauer parameters and their temperature dependences to determine the geometry of iron(II) tris-dioximates and the sign of Δ in Mössbauer (⁵⁷Fe) spectra are discussed.

Comments

Journal of Coordination Chemistry, Vol. 28, No. 3-4 (1993): 319-328. DOI.

Sergey V. Lindeman was affiliated with the Russian Academy of Sciences at the time of publication.

Recommended Citation

Lindeman, Sergey V.; Struchkov, Yu T.; and Voloshin, Yan Z., "Macrobicyclic D-Metal Tris-dioximates Obtained by Cross-linking with P-Block Elements. Part VI. Preparation, Molecular Structure and Mössbauer (₅₇Fe, ₁₁₉Sn) Parameters of an Iron (II) Complex with a Macrobiocyclic Tin-containing Tris-nioximate Ligand" (1993). Chemistry Faculty Research and Publications. 808.
https://epublications.marquette.edu/chem_fac/808