Crystal structure and magnetism of 4,4'-bipyridylium di-μ-bromotetrabromodicuprate(II)

Abstract A new bromocuprate complex of formula C10HI0N2Cu2Br6 has been synthesized and its crystal structure investigated by single-crystal X-ray methods. Stable, black, needle-like crystals are isostructural with the analogous chloride compound.1 The crystals are triclinic, a = 4.1018(5), b = 10.2755(10), c = 11.0355(9) A, a = 113.894(7), β = 94.975(8), γ = 95.935(9)°. The structure was refined by least-squares methods to R = 0.031 and R w = 0.038 for 1930 reflections. It consists of cationic columns formed by stacking of planar (4,4′-bipy H2)2+ cations and anionic columns formed by stacking of nearly planar Cu2Br6 2- anions. Cationic and anionic columns are parallel to the needle axis. The geometry and interionic interactions for the chloride and bromide crystals were compared. The EPR spectrum of a polycrystalline sample of the complex displayed only one broad line centred at 2.08 (T = 293 K). Variable temperature (ca 4.2–290 K.) magnetic susceptibility data indicated an antiferromagnetic superexchange...

[1]  R. Willett Structural correlations in pseudo-planar bibridged CunCl2nL2 oligomers , 1988 .

[2]  B. Scott,et al.  Alternating exchange in homonuclear ferrimagnetic linear chains. Tetrakis(tetramethylene sulfoxide)copper(II) hexahalodicuprate(II) (halo = chloro, bromo): crystal structures and magnetic susceptibilities , 1988 .

[3]  C. Landee,et al.  Strong antiferromagnetic exchange in a bromide-bridged copper dimer, bis(.mu.-bromo)bis[bromobis(tetramethylene sulfoxide)copper(II)]. Structure, susceptibility, and magnetostructural correlations , 1986 .

[4]  M. J. Lindbeck,et al.  Crystal structure of bis(trimethylammonium) decabromotetracuprate(II): a review of stacking patterns in pseudoplanar CunX2n+22− and CunX2nL2 oligomers , 1986 .

[5]  R. Willett Magneto-Structural Correlations in Copper(II) Compounds , 1985 .

[6]  D. Gatteschi,et al.  Magneto-structural correlations in exchange coupled systems , 1984 .

[7]  B. Hathaway A new look at the stereochemistry and electronic properties of complexes of the copper(II) ion , 1984 .

[8]  J. Mroziňski,et al.  The structure and magnetism of the (4,4'-bipy h2)cu2cl6 complex with infinite linear chains of dimeric units , 1980 .

[9]  Jack L. Smith,et al.  THALLIUM DERIVATIVES OF CLOSO-CARBORANES. 1. PYROLYSIS OF TL2R1R2C2B9H9 SPECIES , 1977 .

[10]  B. C. Gerstein,et al.  Magnetic susceptibility of one-dimensional linear chains of ferromagnetically coupled hexahalodicuprate(2-) dimers , 1975 .

[11]  M. Inoue,et al.  Magnetic interaction between binuclear clusters in potassium trihalocuprates(II) and dimethylammonium trihalocuprates(II) , 1971 .

[12]  R. Willett,et al.  Electronic absorption spectrum and bonding in the Cu2Cl62-dimer , 1967 .

[13]  K. Hellwege,et al.  Magnetic Properties of Coordination and Organometallic Transition Metal Compounds , 1966 .

[14]  R. E. Rundle,et al.  Crystal Structures of KCuCl3 and NH4CuCl3 , 1963 .

[15]  J. W. Stout,et al.  Heat Capacity and Entropy of CuCl2 and CrCl2 from 11° to 300°K. Magnetic Ordering in Linear Chain Crystals , 1962 .

[16]  K. Bowers,et al.  Anomalous paramagnetism of copper acetate , 1952, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.