Journal
INORGANICA CHIMICA ACTA
Volume 455, Issue -, Pages 204-212Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2016.10.028
Keywords
Manganese; Complex nuclearity; Crystal engineering; Self-assembly; Solvent effect
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Funding
- University of Maragheh
- MINECO (Spain) [CTQ2014-57393-C2-1-P]
- MINECO (Spain) (CONSOLIDER-Ingenio project) [CSD2010-0065]
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The reaction of Mn(II) chloride with the 2-benzoylpyridyl-(2-picolyl)-hydrazone ligand (HL) and thiocyanate anions in different solvent systems affords mono- [Mn(HL)(2)(SCN)(2)] (1), di- [Mn-2(HL)(2)(SCN)(4)] (2) and a tetra-nuclear complex [Mn-4(L)(4)(SCN)(4)]center dot 2(CH3CN) (3) with concomitant different coordination modes of the ligands. Remarkably, the nuclearity of the complexes only depends on the solvent used, ethanol for 1, n-propanol for 2 and acetonitrile for 3. The complexes have been characterized by elemental analysis, IR spectroscopy technique and the molecular structures determined by single crystal X-ray analysis. In 1 and 2 the ligands are present in its neutral form, while they are deprotonated in 3, but more significantly in all structures a different denticity of ligands was detected: in complex 1 one molecule is tridentate coordinated though the N,N,O donor set, the other bidentate through N,O; in 2 the ligands are N,N,O-tridentate; finally in 3 each ligand, acting as N,N,O,N-tetradentate species, bridges two metals to form a tetranuclear assembly. The crystal structures have been described using the Hirshfeld surface analysis. Finally, we have studied the ability of the thiocyanato ligand to participate in H-bonding and C H/pi interactions by means of DFT calculations (B3LYP/6-31+G**). (C) 2016 Elsevier B.V. All rights reserved.
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