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Modulation of coordination in pincer-type isonicotinohydrazone Schiff base ligands by proton transfer
- Source :
- CrystEngComm. 21:108-117
- Publication Year :
- 2019
- Publisher :
- Royal Society of Chemistry (RSC), 2019.
-
Abstract
- We present here two different coordination polyhedra of pincer type N2O hydrazone based ligands supplemented with thiocyanate ions. The compounds namely [Hg(SCN)2(HL1)] (1) and [Hg(SCN)2(HL2)] (2) have a common isonicotinohydrazone fragment and have been prepared by using a coordination driven self-assembly of the Hg(SCN)2 with two different ligands including 2-benzoylpyridine-isonicotinoylhydrazone (HL1), and 2-acetylpyridineisonicotinoylhydrazone (HL2). In compound 1 the ligand coordinated to the mercury center in the keto form (=N–NH=C=O) whereas, in compound 2, the proton at the hydrazine group have been shifted to the uncoordinated pyridine ring and the ligand acted as a zwitterion. The structures provide a complementary system for proton transfer within the ligand molecule involving the keto-enol tautomerization of amide group and 4-pyridyl N protonation. As a result, the relative location of orbitals and ligands in the complexes are different as well as the bonding strength and the coordination polyhedra. We have also studied electrostatically enhanced π···π (either conventional or involving the chelate ring) interactions observed in the solid state of both compounds and analyzed them using DFT calculations, Molecular Electrostatic Potential surface and the Bader’s theory of atoms in molecules.
- Subjects :
- Schiff base
Thiocyanate
Ligand
Atoms in molecules
Protonation
02 engineering and technology
General Chemistry
010402 general chemistry
021001 nanoscience & nanotechnology
Condensed Matter Physics
01 natural sciences
Tautomer
0104 chemical sciences
chemistry.chemical_compound
Crystallography
chemistry
Zwitterion
Pyridine
QD
General Materials Science
0210 nano-technology
Subjects
Details
- ISSN :
- 14668033
- Volume :
- 21
- Database :
- OpenAIRE
- Journal :
- CrystEngComm
- Accession number :
- edsair.doi.dedup.....4c861d3405b3b18468f3ef8df7b1f912