Ferromagnetic coupling in the malonato-bridged copper(II) chains [Cu(Im)2(mal)]n and [Cu(2-MeIm)2(mal)]n(H2mal=malonic acid, Im=imidazole and 2-MeIm=2-methylimidazole)

Two new malonato-bridged copper(II) complexes of formula [Cu(Im)2(mal)]n (1) and [Cu(2-MeIm)2(mal)]n (2) (Im=imidazole, 2-MeIm=2-methylimidazole and mal=malonate dianion) have been prepared and their structures solved by X-ray diffraction methods. The [Cu(Im)2(mal)] and [Cu(2-MeIm)2(mal)] neutral entities act as monodentate ligands towards the adjacent copper(II) units through one of the two carboxylate groups, the OCO bridge exhibiting an anti-anti conformation. The environment of each copper atom in 1 and 2 is distorted square pyramidal: two carboxylate oxygen atoms from a bidentate malonate and two nitrogen atoms from two imidazole (1) or 2-methylimidazole (2) ligands form the equatorial plane whereas the apical position is occupied by a carboxylate oxygen from the malonate group of the neighbouring complex unit. The intrachain copper-copper separation is 6.036(2) (1) and 6.099(2) A (2). The magnetic properties of 1 and 2 have been investigated in the temperature range 1.9–290 K. Overall, ferromagnetic behaviour is observed in both cases and the intrachain magnetic coupling (J) between the copper(II) ions through the carboxylato group is found to be 1.64 (1) and 0.39 cm−1 (2) (the Hamiltonian being H=−JΣiSi·Si+1).

[1]  N. Masciocchi,et al.  Structure and Magnetism of a Polycrystalline Transition Metal Soap − CoII[OOC(CH2)10COO](H2O)2 , 2001 .

[2]  J. Sanchiz,et al.  Crystal structure and magnetic properties of the flexible self-assembled two-dimensional square network complex [Cu2(mal)2(H2O)2(4,4′-bpy)] (H2mal=malonic acid and 4,4′-bpy=4,4′-bipyridine) , 2001 .

[3]  C. Ruiz-Pérez,et al.  Magnetic coupling through the carbon skeleton of malonate in two polymorphs of ([Cu(bpy)(H2O)][Cu(bpy)(mal)(H2O)])(ClO4)2 (H2mal = malonic acid; bpy = 2,2'-bipyridine). , 2000, Inorganic chemistry.

[4]  Xintao Wu,et al.  Microporous networks co-assembled by both rigid and flexible building blocks , 2000 .

[5]  J. Sanchiz,et al.  Ferromagnetism in malonato-bridged copper(II) complexes. Synthesis, crystal structures, and magnetic properties of [[Cu(H2O)3][Cu(mal)2(H2O)]]n and [[Cu(H2O)4]2[Cu(mal)2(H2O)]][Cu(mal)2(H2O)2][[Cu(H2O)4][Cu(mal)2(H2O)2][(H2mal = malonic acid). , 2000, Inorganic chemistry.

[6]  J. Sanchiz,et al.  Synthesis, crystal structure and magnetic properties of the malonato-bridged bimetallic chain [Mn(II)Cu(II)(mal)2(H2O)4]·2H2O , 2000 .

[7]  E. Colacio,et al.  SINGLY ANTI-ANTI CARBOXYLATE-BRIDGED ZIG-ZAG CHAIN COMPLEXES FROM A CARBOXYLATE-CONTAINING TRIDENTATE SCHIFF BASE LIGAND AND M(HFAC)2 M = MNII, NIII, AND CUII : SYNTHESIS, CRYSTAL STRUCTURE, AND MAGNETIC PROPERTIES , 1999 .

[8]  Maria Cristina Burla,et al.  SIR97: a new tool for crystal structure determination and refinement , 1999 .

[9]  T. Rojo,et al.  Study of the Two-Dimensional [MM‘(C3H2O4)2(H2O)4] (M = Ba, Sr and M‘ = Cu, Mn) Systems: Synthesis, Structure, Magnetic Properties, and Thermal Decomposition , 1998 .

[10]  D. Srinivas,et al.  Copper(II) diethylenetriamine perchlorato complexes bridged through varying length dicarboxylato spacers: synthesis, characterization and EPR studies , 1998 .

[11]  M. Bhadbhade,et al.  Metal–α,ω-Dicarboxylate Complexes. I. Aqua(2,2'-bipyridyl-N,N')(malonato-O,O')copper(II) Monohydrate , 1997 .

[12]  Xintao Wu,et al.  Crystal structure of a flexible self-assembled two-dimensionalsquare network complex[Cu2(C3H2O4)2(H2O)2(4,4′-bpy)]·H2O , 1997 .

[13]  L. Sieroń,et al.  catena-Poly[aqua(benzimidazole-N3)copper(II)-μ-malonato-O,O'':O'] , 1995 .

[14]  M. Nardelli,et al.  PARST95 – an update to PARST: a system of Fortran routines for calculating molecular structure parameters from the results of crystal structure analyses , 1995 .

[15]  J. Ruiz,et al.  Preparation, crystal structures and magnetic properties of a syn-anti carboxylate-bridged dinuclear copper(II) complex and its precursor, a hydrogen-bonded polynuclear copper(II) complex , 1994 .

[16]  J. Ruiz,et al.  Structure and magnetic properties of a syn-anti carboxylate bridged linear trinuclear copper(II) complex with ferromagnetic exchange interaction , 1993 .

[17]  S. Chattopadhyay,et al.  Synthesis and structural studies of tetraaquacopper(II) diaquabis(malonato)cuprate(II) , 1993 .

[18]  J. Ruiz,et al.  Structural and magnetic studies of a syn-anti carboxylate-bridged helix-like chain copper(II) complex , 1992 .

[19]  J. Ruiz,et al.  A quasi-tetrahedral tetracopper cluster with syn-anti bridging carboxylate groups: crystal and molecular structure and magnetic properties , 1990 .

[20]  P. Chaudhuri,et al.  Magnetic and structural properties of acetato(dien)copper(1+) perchlorate: a .mu.-acetato-bridged quasi-one-dimensional complex , 1988 .

[21]  J. Reedijk,et al.  Crystal structures and magnetic behavior of pyridinium bis(oxalato)cuprate(II)-oxalic acid and bis(2-methylimidazole)copper(II) oxalate , 1987 .

[22]  K. Kopinga,et al.  Magnetochemistry of copper(II): exchange interactions in catenated acetatodiamminebromocopper , 1986 .

[23]  K. Ang,et al.  Thermal, spectroscopic, and structural properties of aqua(malonato-O,O′)(1,10-phenanthroline)copper(II) hydrate (1/1.5) , 1986 .

[24]  A. Gleizes,et al.  Design of .mu.-oxalato copper(II) binuclear complexes exhibiting expected magnetic properties , 1984 .

[25]  S. Lippard,et al.  Copper(II) chemistry in hexaaza binucleating macrocycles: hydroxide and acetate derivatives , 1984 .

[26]  A. W. Addison,et al.  Synthesis, structure, and spectroscopic properties of copper(II) compounds containing nitrogen–sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper(II) perchlorate , 1984 .

[27]  A. Leclaire,et al.  Structure du di--actato-bis[actatobis(mthyl-1 imidazole)cuivre(II)] hexahydrat , 1982 .

[28]  W. Hatfield,et al.  Ferromagnetic exchange coupling in sodium biscarbonatocuprate(II) trihydrate , 1982 .

[29]  W. E. Estes,et al.  FERROMAGNETISM IN COPPER(II) OXYDIACETATE HEMIHYDRATE , 1980 .

[30]  A. McPhail,et al.  Crystal and molecular structure, electron spin resonance, and electronic spectrum of tetrakis(imidazole)dinitratocopper(II) , 1976 .

[31]  A. McPhail,et al.  Crystal and molecular structure, electron spin resonance, and electronic spectrum of hexakis(imidazole)copper(II) nitrate , 1975 .

[32]  C. Swahn,et al.  Metal Complexes with Mixed Ligands. 8. The Crystal Structure of Diperchlorato-tetraimidazolocopper(II); Cu(C3H4N2)4(ClO4)2. , 1973 .

[33]  J. Møller,et al.  Metal Complexes with Mixed Ligands. 4. The Crystal Structure of Tetrakisimidazole Cu(II) Sulphate, Cu(C3H4N2)4SO4. , 1972 .

[34]  F. Rossotti,et al.  Structure and stability of carboxylate complexes. Part VI. Crystal and molecular structure of bis(methoxyacetato)tetrakis(imidazole)copper(II) , 1971 .

[35]  A. Earnshaw Introduction to Magnetochemistry , 1968 .

[36]  G. S. Rushbrooke,et al.  High-Temperature Series Expansions for the Spin-½ Heisenberg Model by the Method of Irreducible Representations of the Symmetric Group , 1964 .

[37]  G. D. Rieck,et al.  International tables for X-ray crystallography , 1962 .