Synthesis, Crystal Structure and Spectral Properties of Copper(II) 2-Chloronicotinato Complexes with N-Heterocyclic Ligands

Abstract The synthesis and characterization of nine new copper(II) complexes [Cu(2-Clnic)2L2] (where 2-Clnic is 2-chloronicotinate anion, L is imidazole – Im, benzimidazole – Bim, furo[3,2-c]pyridine – FP, 2-methylfuro[3,2-c]pyridine – MFP, or [1]benzofuro[3,2-c]pyridine – BFP), [Cu(2-Clnic)2(INA)] (where INA is isonicotinamide), [Cu(2-Clnic)2(4-py)]·H2O (where 4-py is 4-methylpyridine) and [Cu2(2-Clnic)4(IQ)2] (where IQ is isoquinoline) are reported. The characterizations were based on elemental analysis, infrared, electronic and EPR spectra. The dimeric character of [Cu2(2-Clnic)4(IQ)2] is assumed on the EPR spectrum and the other spectral methods. The crystal structure of the [Cu(2-Clnic)2(Bim)2] and [Cu(2-Clnic)2(FP)2] complexes have been determined by X-ray crystal structure analysis. Both complexes exhibit the hexacoordination coordination polyhedra around copper atom that lies in the crystallographic center of symmetry. The distorted tetragonal-bipyramidal (4+2) arrangement is in good agreement with spectral data that have suggested an asymmetric chelate coordination of the carboxylic group.

[1]  Da-qi Wang,et al.  Syntheses and crystal structures of copper(II), zinc(II) and cadmium(II) complexes containing pyridine, quinoline and 2-methylquinoline , 2015 .

[2]  Richard J. Gildea,et al.  The anatomy of a comprehensive constrained, restrained refinement program for the modern computing environment – Olex2 dissected , 2015, Acta crystallographica. Section A, Foundations and advances.

[3]  G. Sheldrick Crystal structure refinement with SHELXL , 2015, Acta crystallographica. Section C, Structural chemistry.

[4]  G. Sheldrick SHELXT – Integrated space-group and crystal-structure determination , 2015, Acta crystallographica. Section A, Foundations and advances.

[5]  Da-qi Wang,et al.  Syntheses and structural characterization of nine coordination compounds assembled from copper acetate, 3,5-dimethylpyrazole and carboxylates , 2014 .

[6]  Da-qi Wang,et al.  Five new metal(II) complexes with 3-D network structures based on carboxylate and bis(imidazole) ligands: syntheses and structures , 2012 .

[7]  Richard J. Gildea,et al.  OLEX2: a complete structure solution, refinement and analysis program , 2009 .

[8]  J. Moncol’,et al.  Preparation, Structure, Spectral, and Magnetic Properties of Copper(II) Halogenonicotinates: Crystal and Molecular Structure of Tetrakis(μ-2-chloronicotinato-O,O′)-diaquadicopper(II) , 2007 .

[9]  M. Valko,et al.  Structural diversity of coordination polymers with bridging 3-pyridylmethanol ligand: New type of coordination polymer with different stereochemistry of copper(II) atom , 2006 .

[10]  J. Moncol’,et al.  Copper(ii) halogenopropionates: low-temperature crystal and molecular structure of bis(2,2-dichloropropionato)-di(methyl-3-pyridylcarbamate)copper(ii) and bis(2-bromopropionato)-di (2-pyridylmethanol)copper(ii) , 2004 .

[11]  C. Rao,et al.  Metal carboxylates with open architectures. , 2004, Angewandte Chemie.

[12]  M. Valko,et al.  Structure and spectral study of copper(II) pyridinecarboxylates: crystal and molecular structure of trans-diaqua-bis(N,N-diethylnicotinamide-N)bis(2-chloronicotinate-O)copper(II) , 2002 .

[13]  C. Janiak A Critical Account on π—π Stacking in Metal Complexes with Aromatic Nitrogen‐Containing Ligands , 2001 .

[14]  Y. Muto,et al.  Factors affecting the magnetic properties of dimeric copper(II) complexes , 1988 .

[15]  Glen B. Deacon,et al.  Relationships between the carbon-oxygen stretching frequencies of carboxylato complexes and the type of carboxylate coordination , 1980 .

[16]  F. Eloy,et al.  Sur la synthèse des furo[3,2-c] pyridines , 1971 .