Wheel-like MnII6 and NiII6 complexes from the use of 2-pyridinealdoxime and carboxylates

Suyun Zhang, Lina Zhen, Bin Xu, Ross Inglis, Kai Li, Wenqian Chen, Yong Zhang, Konstantis F. Konidaris, Spyros P. Perlepes, Euan K. Brechin, Yahong Li

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Abstract

The employment of 2-pyridinealdoxime, (py)C(H)NOH, in nickel(ii) and manganese(ii) carboxylate chemistry under solvothermal conditions is reported. The syntheses, crystal structures and magnetochemical characterization (for two representative compounds) are described for [Ni6(O 2CMe)6{(py)C(H)NO}6]·H2O (1·H2O), [Ni6(O2CPh)6{(py) C(H)NO}6]·2EtOH (2·2EtOH), [Ni6{(4-Cl)O 2CPh}6{(py)C(H)NO}6]·2EtOH (3·2EtOH) and [Mn6(O2CMe)6{(py)C(H)NO} 6]·H2O (4·H2O), where (4-Cl)PhCO2- is 4-chlorobenzoate. The reactions of M(O2CMe)2·4H2O (M = Ni, Mn) with one equivalent of (py)C(H)NOH in EtOH at 120 °C under autogenous pressure give isostructural 1·H2O and 4·H2O. Complexes 2·2EtOH and 3·2EtOH were obtained from the 1:1:1 Ni(O 2CMe)2·4H2O/{(py)C(H)NOH/(X)PhCO 2H reaction mixtures in EtOH under solvothermal conditions (X = H, 4-Cl). The structurally similar clusters 1-4 have a wheel-like topology with the six metal ions in a chair conformation. Each metal site is bound to four oxygen and two nitrogen atoms; the donor atoms come from two carboxylate oxygens, two oximate oxygens, one pyridyl nitrogen and one oximate nitrogen atom. The carboxylate ligands show the syn, synη11:μ mode, while the (py)C(H)NO- ions behave as η1: η123 ligands. Each metal⋯metal vector is bridged by one carboxylate group, one μ-O derived from a (py)C(H)NO- ligand and by one diatomic oximate-NO- group from an adjacent (py)C(H)NO- group. The IR spectra of the complexes are discussed in terms of the coordination modes of the ligands. Variable-temperature, solid-state dc magnetic susceptibility studies were carried out on polycrystalline samples of 1 and 4. The data in the 2.0-300 K range have been fit to a model with one J value revealing moderate (1) or weak (2) antiferromagnetic MII⋯MII exchange interactions. This work demonstrates the synthetic potential of combining (py)C(H)NOH with carboxylate ligands and the usefulness of solvothermal techniques in 3d-metal cluster chemistry.

Original languageEnglish
Pages (from-to)3563-3571
Number of pages9
JournalDalton Transactions
Volume39
Issue number15
DOIs
Publication statusPublished - 2010 Apr 6

ASJC Scopus subject areas

  • Inorganic Chemistry

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    Zhang, S., Zhen, L., Xu, B., Inglis, R., Li, K., Chen, W., Zhang, Y., Konidaris, K. F., Perlepes, S. P., Brechin, E. K., & Li, Y. (2010). Wheel-like MnII6 and NiII6 complexes from the use of 2-pyridinealdoxime and carboxylates. Dalton Transactions, 39(15), 3563-3571. https://doi.org/10.1039/b922672a