Protonated malonate: the influence of the hydrogen bonds on the magnetic behaviour

One hydrogen malonato-bridged complex of formula [Cu(Hmal)2] (1) and two polymorphous malonato-bridged complexes of formula [Cu(H2O)(H2mal)(mal)] (2 and 3), in which the three species of the malonate (H2mal, Hmal−, and mal2−) are present, were synthesised and characterized by X-ray diffraction [H2mal = malonic acid]. Their structures consist of corrugated malonate layers of [Cu(Hmal)2] (1) and [Cu(H2O)(H2mal)(mal)] (2 and 3) units bridged by carboxylate–malonate groups. The layers are linked through hydrogen bonds leading to a three-dimensional network. Variable-temperature (1.9–290 K) magnetic susceptibility measurements indicate the occurrence of weak ferromagnetic interactions between the copper(II) ions through the carboxylate–malonate bridge. The effectiveness of magnetic exchange coupling is related to the degree of protonation of the malonate group.

[1]  J. Pasán,et al.  {[Cu(H2O)3][Cu(phmal)2]}n: a new two-dimensional copper(II) complex with intralayer ferromagnetic interactions (phmal = phenylmalonate dianion) , 2003 .

[2]  J. Sanchiz,et al.  Design of high-dimensional copper(II) malonate complexes with exo-polydentate N-donor ligands. , 2003, Inorganic chemistry.

[3]  J. Pasán,et al.  Malonate-based copper(II) coordination compounds: ferromagnetic coupling controlled by dicarboxylates , 2003 .

[4]  J. Pasán,et al.  Malonic acid: a multi-modal bridging ligand for new architectures and properties on molecule-based magnets , 2003 .

[5]  Song Gao,et al.  Ferromagnetic ordering and metamagnetism in malonate bridged 3D diamond-like and honeycomb-like networks: [Cu(mal)(DMF)]n and [[Cu(mal)(0.5pyz)].H2O]n (mal = Malonate Dianion, DMF = N,N-dimethylformamide, pyz = Pyrazine). , 2003, Inorganic Chemistry.

[6]  M. Drew,et al.  Syntheses of two new 1D and 3D networks of Cu(II) and Co(II) using malonate and urotropine as bridging ligands: crystal structures and magnetic studies. , 2003, Inorganic chemistry.

[7]  Canzhong Lu,et al.  Synthesis, Structure and Characterization of Two New Complexes [Cu2(C3H2O4)2(C4H4N2)]·2H2O and [Zn2(OH2)2(C3H2O4)2(C4H4N2)] , 2003 .

[8]  T. Maji,et al.  A novel layered and pillared topology in a 3D open framework: synthesis, crystal structure and magnetic properties , 2003 .

[9]  S. Alvarez,et al.  Early-late transition metal ferromagnetic coupling mediated by hydrogen bonding. , 2002, Chemical communications.

[10]  J. Sanchiz,et al.  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) , 2002 .

[11]  J. Pasán,et al.  Structural versatility of the malonate ligand as a tool for crystal engineering in the design of molecular magnets , 2002 .

[12]  J. Pasán,et al.  The flexibility of molecular components as a suitable tool in designing extended magnetic systems , 2002 .

[13]  S. Alvarez,et al.  Exchange coupling of transition-metal ions through hydrogen bonding: a theoretical investigation. , 2002, Journal of the American Chemical Society.

[14]  J. Sanchiz,et al.  Synthesis, crystal structure and magnetic properties of [Cu(bpym)(mal)(H2O)]·6H2O and [Cu2(bpym)(mal)2(H2O)2]·4H2O (bpym=2,2′-bipyrimidine, H2mal=malonic acid) , 2001 .

[15]  W. Plass,et al.  Magnetic Interactions as Supramolecular Function: Structure and Magnetic Properties of Hydrogen-Bridged Dinuclear Copper(II) Complexes. , 2001, Angewandte Chemie.

[16]  A. Lenstra,et al.  Structures of copper(II) and manganese(II) di(hydrogen malonate) dihydrate; effects of intensity profile truncation and background modelling on structure models. , 2001, Acta crystallographica. Section B, Structural science.

[17]  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 .

[18]  S. Alvarez,et al.  Exchange coupling in carboxylato-bridged dinuclear copper(II) compounds: a density functional study. , 2001, Chemistry.

[19]  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.

[20]  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.

[21]  J. Sanchiz,et al.  Synthesis, crystal structure and magnetic properties of the three-dimensional compound [Na2Ni(mal)2(H2O)6]n (H2mal=malonic acid) , 2000 .

[22]  Louis J. Farrugia,et al.  WinGX suite for small-molecule single-crystal crystallography , 1999 .

[23]  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 .

[24]  L. Jianmin,et al.  New Maze-Type Network Assembled by Copper(II) and 4,4‘-Diaminodiphenylmethane: {[Cu(C13H14N2)(C3H4O4)Cl]Cl}2 , 1999 .

[25]  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 .

[26]  J. Yakhmi,et al.  Dramatic Modifications of Magnetic Properties through Dehydration−Rehydration Processes of the Molecular Magnetic Sponges CoCu(obbz)(H2O)4·2H2O and CoCu(obze)(H2O)4·2H2O, with obbz = N,N‘-Bis(2-carboxyphenyl)oxamido and obze = N-(2-Carboxyphenyl)-N‘-(carboxymethyl)oxamido , 1997 .

[27]  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 .

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

[29]  R. Navarro,et al.  Application Of High- and Low-Temperature Series Expansions to Two-Dimensional Magnetic Systems , 1990 .

[30]  J. Renard,et al.  Magnetic ordering of manganese(II) copper(II) bimetallic chains; design of a molecular based ferromagnet , 1988 .

[31]  D. Cremer,et al.  General definition of ring puckering coordinates , 1975 .

[32]  E. Stiefel,et al.  Detailed nature of the six-coordinate polyhedra in tris(bidentate ligand) complexes , 1972 .

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

[34]  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 .