Syntheses, structural characterization, and thermal behaviour of metal complexes with 3-aminopyridine as co-ligands
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Syntheses, structural characterization, and thermal behaviour of metal complexes with 3‑aminopyridine as co‑ligands Franz A. Mautner1 · Patricia V. Jantscher1 · Roland C. Fischer2 · Ana Torvisco2 · Klaus Reichmann3 · Salah S. Massoud4 Received: 23 September 2020 / Accepted: 31 October 2020 © The Author(s) 2020
Abstract Six mixed metal complexes with 3-aminopyridine (3-ampy) as a co-ligand have been synthesized: catena-{[M(μ2-3-ampy) (H2O)4]SO4·H2O} (M=Ni (1) and Co (2)), [Co(3-ampy)4(NCS)2] (3), [Co(3-ampy)2(NCS)2] (4), [Co(3-ampy)4(N3)2] (5) 3− azide ion), and characterized by physio-chemical and and mer-[Co(3-ampy)3(N3)3] (6), (NCS−=isothiocyanate ion, N spectroscopic methods as well as single crystal X-ray and powder diffraction. In the isostructural complexes 1 and 2 single μ2-3-ampy links the Ni(II) and Co(II) centers into polymeric chains. The mononuclear Co(II) and Co(III) pseudohalide complexes 3–6 reveal only terminal 3-ampy ligands. The 3-ampy ligands form supramolecular hydrogen bonded systems via their NH2-groups and non-covalent π-π ring-ring interactions via their pyridine moieties. Thermoanalytical properties were investigated for 1–3.
Introduction Aminopyridine ligands have been extensively studied in the synthesis of many coordination metal compounds ranging from simple mononuclear to coordination polymeric compounds (CPs) with different dimensionality. The construction of CPs is attributed to the intriguing structural diversity and the dual functionality of these ligands, which may lead to the formation of 1D or 3D structures [1–19], especially in the presence of other potentially bridging ligands such as pseudohalides [1–3, 13]. Another feature incorporated in this class of compounds is their affinity to show different Electronic supplementary material The online version of this article (https://doi.org/10.1007/s11243-020-00436-2) contains supplementary material, which is available to authorized users. * Franz A. Mautner [email protected] 1
Institut für Physikalische und Theoretische Chemie, Technische Universität Graz, 8010 Graz, Austria
2
Institut für Anorganische Chemie, Technische Universität Graz, 8010 Graz, Austria
3
Institut für Chemische Technologie von Materialien, Technische Universität Graz, 8010 Graz, Austria
4
Department of Chemistry, University of Louisiana at Lafayette, Lafayette, LA 4437070504, USA
hydrogen bonds, N–H⋯X between the amino NH and a coordinated pseudohalide (X), which tends to extend the structure from 1D to a 3D network. Extra stability can also be generated through π-π stacking interactions between the aromatic pyridyl ligands, which play an important role in stabilizing the resultant polymeric architectures [1–3, 9, 15, 16]. 3-Aminopyridine (3-ampy) as one of the aminopyridine series is a simple molecule which can act as mondentate ligand by binding the metal ions in the most common binding mode via the most basic N-pyridyl nitrogen (II) [2, 7, 15, 19–35] or the least likely binding site of the amino group (III) [33, 34]. The latter b
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