Self-assembly of copper(II) complexes with substituted aroylhydrazones and monodentate N-heterocycles: synthesis, structure and properties

Two ternary copper(II) complexes [Cu(L1)(py)] (1) and [Cu(L2)(Himdz] · CH3OH (2) with substituted aroylhydrazones, 5-bromo-salicylaldehyde-3,5-dimethoxy-benzoylhydrazone (H2L1) and 5-bromo-salicylaldehyde-p-methyl-benzoylhydrazone (H2L2), pyridine (py) and imidazole (Himdz), have been synthesized. Their crystal structures and spectroscopic properties have been studied. In each complex, the metal is in a square-planar N2O2 coordination formed by the phenolate-O, the imine-N and the deprotonated amide-O atoms of L2−, and the sp2 N atom of the neutral heterocycle. In the solid state, 1 exists as a centrosymmetric dimer due to very weak apical coordination of the metal bound phenolate-O. Complex 2 has no such apical coordination and exists as a monomer. Self-assembly via C–H ··· O, N–H ··· O and O–H ··· N interaction leads to a one-dimensional chain arrangement; other non-covalent interactions such as C–H ··· π and π ··· π are not involved.

[1]  P. G. Aravindan,et al.  Synthesis of new ‘end-off’ μ-phenoxo and bis-μ-acetato tri-bridged copper(II), nickel(II) and zinc(II) complexes: Spectral, magnetic, electrochemical and catalytic studies , 2006 .

[2]  Hui Wu,et al.  Synthesis, structure, and properties of a tetranuclear copper(II) tridentate Schiff-base complex with a pseudo-double-cubane core , 2005 .

[3]  Haibin Song,et al.  Synthesis, structure and properties of a 4,4′-bipyridine bridged dinuclear Cu(II) complex: {Cu2(4,4′-bipy)[HOCH2CH2N(CH2CH2NH2)2]2}· (ClO4)4·1/2(4,4′-bipy)·4H2O , 2005 .

[4]  W. Haase,et al.  Metal complexes derived from hydrazoneoxime ligands: II. Synthesis, electrospray mass spectra and magnetochemical studies of some copper(II) complexes derived from p-substituted aroylhydrazoneoximes , 2005 .

[5]  S. Pal,et al.  Self-assembly of copper(II) complexes with a dibasic tridentate ligand and monodentate N-heterocycles : structural, magnetic and EPR studies , 2005 .

[6]  S. Pal,et al.  A one-dimensional assembly of a square-planar copper(II) complex with alternating short and long Cu⋯Cu distances. Metal ion spin-exchange viaπ-π interactions , 2003 .

[7]  A. Mukhopadhyay,et al.  Square-planar nickel(II) complexes with a tridentate Schiff base and monodentate heterocycles: self-assembly to dimeric and one-dimensional array via hydrogen bonding , 2003 .

[8]  Wenbin Lin,et al.  Crystal engineering of NLO materials based on metal--organic coordination networks. , 2002, Accounts of chemical research.

[9]  E. Spodine,et al.  Electrochemical studies of copper(II) complexes with Schiff-base ligands , 2002 .

[10]  W. Haase,et al.  Synthesis, magnetochemical studies and X-ray molecular structures of some mononuclear copper(II)–1H-pyrazole adducts and mono(μ-pyrazolate) bridged dicopper(II) complexes derived from N-salicylidenearoylhydrazines , 2001 .

[11]  A. Powell,et al.  A one-dimensional assembly of copper(II) polyhedra via dual use of hydrogen-bonding and π–π interaction , 2000 .

[12]  S. Pal,et al.  Dimeric and polymeric square-pyramidal copper(II) complexes containing equatorial–apical chloride or acetate bridges , 2000 .

[13]  W. Haase,et al.  Synthesis, characterization and magnetochemical studies of some imidazole and imidazolate copper(II) ternary complexes derived from N-salicylidenearoylhydrazines. X-ray crystal and molecular structures of [(N-salicylidene-p-chlorobenzoylhydrazine)ONO(−2)imidazole]copper(II) monohydrate and dimeric [ , 2000 .

[14]  R. Gupta,et al.  SYNTHESIS, STRUCTURE AND PROPERTIES OF A DICOPPER(II) COMPLEX , 1999 .

[15]  S. Pal,et al.  Syntheses and structures of square-pyramidal acetonitrile coordinated copper(II) complexes with N-(aroyl)-N′-(5-nitrosalicylidene)hydrazines , 1999 .

[16]  D. Braga,et al.  Crystal Engineering and Organometallic Architecture. , 1998, Chemical reviews.

[17]  O. Kahn,et al.  Spin-Transition Polymers: From Molecular Materials Toward Memory Devices , 1998 .

[18]  Paul N. W. Baxter,et al.  Multicomponent Self‐Assembly: Preferential Generation of a Rectangular [2 × 3]G Grid by Mixed‐Ligand Recognition , 1997 .

[19]  J. Lehn,et al.  Interaction of Double-Helical Polynuclear Copper(I) complexes with double-stranded DNA , 1995 .

[20]  M. Verdaguer,et al.  High-Tc Molecular-Based Magnets: Ferrimagnetic Mixed-Valence Chromium(III)-Chromium(II) Cyanides with Tc at 240 and 190 Kelvin , 1993, Science.

[21]  T. Marks Interfaces between Molecular and Polymeric “Metals”: Electrically Conductive, Structure‐Enforced Assemblies of Metallomacrocycles , 1990 .

[22]  Christopher A. Hunter,et al.  The nature of .pi.-.pi. interactions , 1990 .

[23]  Christoph Janiak,et al.  A critical account on π–π stacking in metal complexes with aromatic nitrogen-containing ligands , 2000 .

[24]  D. Braga Inorganic crystal engineering: a personal perspective , 2000 .