Synthesis,Crystal Structures,and Properties of Mn(NCS)2 Coordination Compounds with 4-Picoline as Coligand and Crystal Structure of Mn(NCS)2 |
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| Authors: | Tristan Neumann Gianpiero Gallo Robert E. Dinnebier Christian Näther |
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| Affiliation: | 1. Institute of Inorganic Chemistry, Christian-Albrechts-University of Kiel, Max-Eyth-Straße 2, 24118 Kiel, Germany;2. Max-Planck-Institute for Solid State Research, Heisenbergstraße 1, 70569 Stuttgart, Germany Department of Chemistry and Biology “A. Zambelli“, University of Salerno, via Giovanni Paolo II, 132, 84084 Fisciano, SA, Italy;3. Max-Planck-Institute for Solid State Research, Heisenbergstraße 1, 70569 Stuttgart, Germany |
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| Abstract: | Reaction of Mn(NCS)2 with 4-picoline (4-methylpyridine) leads to the formation of [Mn(NCS)2(4-picoline)4] · 0.67 · 4-picoline · 0.33 · H2O ( 1 - Mn ) reported in literature, Mn(NCS)2(4-picoline)2(H2O)2 ( 2-Mn/H2O ), and of [Mn(NCS)2(4-picoline)2]n ( 2-Mn/I ). 1-Mn and 2-Mn/H2O consist of discrete complexes, in which the metal cations are octahedrally coordinated, whereas in 2-Mn/I the metal cations are linked by pairs of μ-1,3-bridging thiocyanate anions into corrugated chains. Measurements using thermogravimetry and differential scanning calorimetry as well as temperature dependent X-ray powder diffraction on 1-Mn and 2-Mn/H2O reveal that upon heating both compounds transform into [Mn(NCS)2(4-picoline)]n ( 3-Mn ) via 2-Mn/I as intermediate. 3-Mn shows a very rare chain topology in which the metal cations are linked by μ-1,3,3 (N,S,S) coordinating anionic ligands which was never observed before with MnII. From these investigations there is no hint that a further modification of 2-Mn can be prepared as recently observed for [M(NCS)2(4-picoline)2]n (M = Fe, Cd) and such a form is also not available if the metastable forms of the FeII or CdII compounds were used as template during thermal decomposition. Magnetic investigations on 2-Mn/H2O show only paramagnetic behavior, whereas for 2-Mn/I antiferromagnetic ordering is observed. Finally, the crystal structure of Mn(NCS)2 was determined from XRPD data, which shows that it is strongly related to that of 3-Mn . |
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| Keywords: | Thiocyanate Coordination polymer Manganese Crystal structure Solid state synthesis |
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