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Synthesis and spectroscopic characterisation of copper(II) complexes with 5-methyl-1-(2′-pyridyl) pyrazole-3-carboxamide (MPyPzCA): X-ray crystal structure of [Cu(MPyPzCA)2(H2O)](ClO 4)2
N ADHIKARI, S CHAUDHURI, R J BUTCHER, N SAHA
Published in Elsevier Ltd
1999
Volume: 18
   
Issue: 43686
Pages: 1323 - 1328
Abstract
The coordination mode of the title ligand, MPyPzCA (synthesised for the first time and characterised by elemental analyses, mass, IR and PMR spectral parameters), is reported by solid state isolation and physicochemical identification of copper(II) complexes, Cu(MPyPzCA)2X2.H2O (X=Cl/Br/NO3/ClO4). Magnetic and electronic spectral features classify the reported complexes as six coordinate distorted octahedral ones. IR spectra (4000-200 cm-1) of MPyPzCA and its complexes indicate different denticity of the two ligand moities namely neutral bidentate function through pyrazolyl 2N and pyridyl 1′N of one ligand (A) and the neutral tridentate behaviour through pyrazolyl 2N, pyridyl 1′N and the amidic oxygen of the second ligand system (B). The sixth apical coordination site is occupied by a water molecule in the perchlorate complex (as evident by X-ray data) or by the counter ion, X (X=Cl/Br/NO3). The electrochemical studies demonstrate easy oxidative nature of Cu(II) in the reported species. X-ray crystallographic studies of the perchlorate complex, [Cu(MPyPzCA)2(H2O)](ClO 4)2, (Pna21, orthorhombic), has substantiated the conjecture that the geometry is distorted octahedral. The Cu-N (pyrazolyl) and Cu-N (pyridyl) bond lengths are 2.001(3) and 1.969(3) Å and 2.020(4) and 2.206(4) Å in the ligand systems, A and B. respectively; Cu-O (amidic oxygen) for ligand system B and Cu-O (water) bond lengths are 2.783(3) and 2.010(3) Å, respectively. The crystal structure is highly stabilised through extensive hydrogen bonding.
About the journal
JournalData powered by TypesetPolyhedron
PublisherData powered by TypesetElsevier Ltd
ISSN0277-5387