A Novel Triangular Trinuclear μ3‐CO3 Ferromagnetic CuII Compound Prepared in situ from CO2 Uptake in Air. X‐ray Structure, Spectroscopy and Magnetism

The new trinuclear compound [Cu3(bpy)6(μ3-CO3)](BF4)4(H2O)2(C2H6O) (in which bpy = 2,2′-bipyridine) has been synthesized from Cu(BF4)2 and bpy in aqueous ethanol by rapid uptake of atmospheric CO2. The structure of the compound has been determined by X-ray crystallography; it was found to crystallise in the triclinic space group P1¯ with a = 13.405(7), b = 13.691(7), c = 21.446(8) A, α = 82.87(4), β = 73.57(4), γ = 64.32(4)°, Z = 2. The three copper atoms are connected to each other through the oxygen atoms from the bridging carbonato group, giving a triangular array of copper atoms. Each copper has a distorted square-pyramidal environment with a basal plane formed by three nitrogen atoms of the two chelating bipyridine groups and the oxygen atom of the bridging carbonato group (Cu−N/O distances about 2.0 A). The apical position is formed at each copper by the fourth nitrogen atom of the bipyridines with distances varying from 2.120(5) to 2.188(5) A. A weak ferromagnetic interaction is observed between the copper(II) ions. All data were fitted using the Hamiltonian H = −J12 (S1·S2) −J13 (S1·S3) −J23 (S2·S3). Observed parameters are J = 10.6 cm−1 and a very weak antiferromagnetic intercluster interaction with zj′ = −1.2 cm−1.

[1]  I. Mutikainen,et al.  Synthesis, Structure, Spectroscopy, and Magnetism of Unique Propeller‐Type Linear Trinuclear CuII Complexes with In‐situ Prepared Formamidine Ligands , 1999 .

[2]  P. Cheng,et al.  Trinuclear Cu(II) and Zn(II) complexes bridged by μ3-carbonato anion , 1999 .

[3]  D. H. Gibson.  Carbon dioxide coordination chemistry: metal complexes and surface-bound species. What relationships? , 1999 .

[4]  J. Reedijk,et al.  Alkoxo-bridged dinuclear copper(II) compounds with 2-amino-picolines as ligands: Synthesis, spectroscopy, magnetism and X-ray crystal structures , 1999 .

[5]  A. Spek,et al.  Synthesis, spectroscopic, magnetic properties and X-ray crystal structure of di-μ-hydroxo-bis(μ-perchlorato- O , O ′)-bis-[bis(2-amino-4-methylpyrimidine)copper(II)]: bridging perchlorate results in significant deviation from the predicted magnetic exchange , 1999 .

[6]  Sven Rau,et al.  Carbon dioxide and metal centres: from reactions inspired by nature to reactions in compressed carbon dioxide as solvent , 1999 .

[7]  Shinnichiro Suzuki,et al.  The Formation of a Hydrogencarbonato-bridged Dinuclear Copper(II) Complex by Fixation and Activation of Atmospheric CO2 , 1999 .

[8]  I. Mutikainen,et al.  An Unprecedented, Copper‐Mediated, In‐Situ Multi‐Step Ligand Formation – Synthesis, Structure, and Magnetism of Bis(μ‐methoxo)bis[nitrato(2‐methoxy‐ methylamino‐3‐methylpyridine)copper(II)] , 1998 .

[9]  G. Enright,et al.  The chemistry of dinitrato-2, 2′-bipyridinecopper(II): preparation and characterization of binuclear complexes having a Cu(μ-OH)2Cu and Cu(μ-N3)2Cu core , 1998 .

[10]  J. Reedijk,et al.  A Unique Copper-Controlled Template Synthesis of Tetradentate N4-Donor Ligands and Their Propeller-Type Linear Trinuclear CuII Complexes , 1998 .

[11]  A. Spek,et al.  Synthesis, spectroscopic properties and X-ray crystal structures of two dinuclear alkoxo-bridged copper(II) compounds with the ligand bis(1-methyl-2-benzimidazolyl) propane. A unique alkoxo-bridged Cu(II) dinuclear compound with an additional bidentate bridging triflate anion , 1997 .

[12]  Xiao‐Ming Chen,et al.  The first μ3-carbonato-bridged trinuclear zinc(II) complex containing metal atoms in two different coordination enviroments , 1994 .

[13]  D. Stalke,et al.  Crystal handling at low temperatures , 1993 .

[14]  F. Lloret,et al.  Synthesis, crystal structure and magnetic properties of di-µ-hydroxo-bis[(2,2′-bipyridine)(trifluoromethanesulfonato-O)-copper(II)] , 1992 .

[15]  E. Gutiérrez‐Puebla,et al.  Synthesis and magnetic properties of bis(μ-hydroxo)bis[(2,2 ′-bipyridyl)copper(II)] squarate. Crystal structure of bis(μ-hydroxo)bis[(2,2′-bipyridyl)copper(II)] squarate tetrahydrate , 1990 .

[16]  Colin Eaborn,et al.  Comprehensive Coordination Chemistry , 1988 .

[17]  A. Clearfield,et al.  The First Determination of the Energy Difference Between Solid-State Conformers by X-Ray Diffraction: 1. The Crystal Structure of the Pseudo-Jahn-Teller Complex (Nitrito)bis(2,2′-bipyridyl)copper(II) Nitrate at 20, 100, 165, and 296 K , 1987 .

[18]  A. Dei,et al.  EPR spectra of and exchange interactions in trinuclear complexes. 3. Synthesis, crystal structure and magnetic properties of the oxovanadium(IV) adduct of a tetradentate Schiff base copper(II) complex , 1985 .

[19]  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 .

[20]  A. Clearfield,et al.  Fluxional behavior of a pseudo-Jahn-Teller complex: x-ray crystal structure of [Cu(bppy)2(ONO)][NO3] at 165 and 296 K , 1983 .

[21]  D. A. Palmer,et al.  THE CHEMISTRY OF METAL CARBONATO AND CARBON DIOXIDE COMPLEXES , 1983 .

[22]  Geoffrey A. Williams,et al.  Spin density and structure of aquabis(2,2′-bipyridine)di-µ-hydroxosulphatodicopper(II) tetrahydrate at 4.2 K , 1983 .

[23]  S. Tyagi,et al.  The crystal structure and electronic properties of catena-bis(2,2′-bipyridyl)-µ-tetrafluoroborato-copper(II) tetrafluoroborate and catena-bis(2,2′-bipyridyl)-µ-perchlorato-copper(II) perchlorate , 1983 .

[24]  A. Clearfield,et al.  The X-ray crystal structure and electronic properties of [Cu(bipy)2(ONO)][NO3](bipy = 2,2′-bipyridyl) at 298 and 165 K, a fluxional cis-distorted octahedral CuN4O2 chromophore , 1983 .

[25]  A. Willis,et al.  Crystal and molecular structure of .mu.-carbonato-di-.mu.-chloro-tetrakis(bis(3-aminopropyl)amine)tetracopper(II) chloride hydrate , 1981 .

[26]  S. Tyagi,et al.  Crystal structure and electronic properties of bis(2,2′-bipyridyl)-nitratocopper(II) nitrate monohydrate , 1981 .

[27]  S. Ooi,et al.  The crystal structure of nitratotriaquo(2,2'-bipyridine)copper(II) nitrate [Cu(NO3)(H2O)3(bipy)]NO3. , 1977 .

[28]  Mahmood Toofan,et al.  Crystal and molecular structure of di-µ-hydroxo-bis[bipyridylcopper(II)] diperchlorate , 1976 .

[29]  B. F. Hoskins,et al.  Crystal and molecular structure of aquabis(2,2′-bipyridine)di-µ-hydroxo-sulphatodicopper(II) tetrahydrate , 1975 .

[30]  O. P. Anderson.  Crystal and molecular structure of tris-(2,2′-bipyridyl)copper(II) perchlorate , 1972 .

[31]  H. Nakai.  The Crystal Structure of Perchlorato-bis(2,2′-bipyridine)copper(II) Perchlorate, [Cu(ClO4)(bipy)2]ClO4 , 1971 .

[32]  E. Meyers,et al.  Crystal and molecular structure of bisbipyridyl-.mu.-dihydroxo-dicopper(II) nitrate , 1970 .

[33]  S. Ooi,et al.  The Crystal Structure of Nitrato-bis(2,2′-bipyridine)copper(II) Nitrate Monohydrate [Cu(NO3)(bipy)2]NO3·H2O , 1970 .

[34]  B. F. Hoskins,et al.  The novel magnetism and crystal structure of the complex di-µ-hydroxybis(bipyridyl)dicopper(II) sulphate pentahydrate , 1970 .

[35]  R. Hay,et al.  Some complexes of dipropylenetriamine with nickel(II), copper(II), zinc(II), and cobalt(III) , 1968 .