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Structural Diversity of Nickel and Manganese Chloride Complexes with Pyridin-2-One.

ABSTRACT: Reactions of NiCl2·6H2O and pyridin-2-one (C5H5NO = Hhp) afforded novel molecular complexes, i.e., mononuclear [NiCl2(Hhp)4] (1), dinuclear [NiCl2(Hhp)(H2O)2]2.2Hhp (3) and [Ni2Cl4(Hhp)5]·2MeCN (4), and an ionic complex [Ni(Hhp)6]Cl2 (2). Single-crystal X-ray analyses revealed two modes of Hhp ligation in these complexes: a monodentate coordination of carbonyl oxygen in all of them and an additional µ2-oxygen bridging coordination in the dinuclear complex 4. Three bridging molecules of Hhp span two nickel(II) ions in 4 with a 2.9802 (5) Å separation of the metal ions. Complex 3 is a chlorido-bridged nickel dimer with a planar Ni2(µ-Cl)2 framework. Hydrogen bonds and parallel stacking arrangements of the Hhp molecules govern the connectivity patterns in the crystals, resulting in 1D structures in 1 and 5 or 2D in 3. A single manganese compound [MnCl2(Hhp)4] (5), isostructural to 1, was isolated under the similar conditions. This is in contrast to four nickel(II) chloride complexes with Hhp. Thermal analyses proved the stability of complexes 1 and 3 in argon up to 145 °C and 100 °C, respectively. The decomposition of 1 and 3 yielded nickel in argon and nickel(II) oxide in air at 800 °C.

SUBMITTER: Petricek S

PROVIDER: S-EPMC7070377 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature

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Structural Diversity of Nickel and Manganese Chloride Complexes with Pyridin-2-One.

Petriček Saša S

Molecules (Basel, Switzerland) 20200214 4

Reactions of NiCl2·6H2O and pyridin-2-one (C5H5NO = Hhp) afforded novel molecular complexes, i.e., mononuclear [NiCl2(Hhp)4] (1), dinuclear [NiCl2(Hhp)(H2O)2]2.2Hhp (3) and [Ni2Cl4(Hhp)5]·2MeCN (4), and an ionic complex [Ni(Hhp)6]Cl2 (2). Single-crystal X-ray analyses revealed two modes of Hhp l ...[more]

PMID: 32075095

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Project description:The new heterometallic compounds, [{Cu(pn)2}2Ni(NCS)6]n·2nH2O (1), [{CuII(trien)}2Ni(NCS)6CuI(NCS)]n (2) and [Cu(tren)(NCS)]4[Ni(NCS)6] (3) (pn = 1,2-diaminopropane, trien = triethylenetetramine and tren = tris(2-aminoethylo)amine), were obtained and characterized by X-ray analysis, IR spectra, XAS and magnetic measurements. Compounds 1, 2 and 3 show the structural diversity of 2D, 1D and 0D compounds, respectively. Depending on the polyamine used, different coordination polyhedron for Cu(II) was found, i.e., distorted octahedral (1), square pyramidal (2) and trigonal bipyramidal (3), whereas coordination polyhedron for nickel(II) was always octahedral. It provides an approach for tailoring magnetic properties by proper selection of auxiliary ligands determining the topology. In 1, thiocyanate ligands form bridges between the copper and nickel ions, creating 2D layers of sql topology with weak ferromagnetic interactions. Compound 2 is a mixed-valence copper coordination polymer and shows the rare ladder topology of 1D chains decorated with [CuII(tren)]2+ antennas as the side chains attached to nickel(II). The ladder rails are formed by alternately arranged Ni(II) and Cu(I) ions connected by N2 thiocyanate anions and rungs made by N3 thiocyanate. For the Cu(I) ions, the tetrahedral thiocyanate environment mixed N/S donor atoms was found, confirming significant coordination spheres rearrangement occurring at the copper precursor together with the reduction in some Cu(II) to Cu(I). Such topology enables significant simplification of the magnetic properties modeling by assuming magnetic coupling inside {NiIICuII2} trinuclear units separated by diamagnetic [Cu(NCS)(SCN)3]3- linkers. Compound 3 shows three discrete mononuclear units connected by N-H…N and N-H…S hydrogen bonds. Analysis of XAS proves that the average ligand character and the covalency of the unoccupied metal d-based orbitals for copper(II) and nickel(II) increase in the following order: 1 → 2 → 3. In 1 and 2, a weak ferromagnetic coupling between copper(II) and nickel(II) was found, but in 2, additional and stronger antiferromagnetic interaction between copper(II) ions prevailed. Compound 3, as an ionic pair, shows, as expected, a spin-only magnetic moment.

Dataset Information

Structural Diversity of Nickel and Manganese Chloride Complexes with Pyridin-2-One.

Publications

Structural Diversity of Nickel and Manganese Chloride Complexes with Pyridin-2-One.

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