Self-assembly of a CuTIM(S2O7) polymer: synthesis and crystallographic studies

A novel self-assembled polymer of Cu(TIM)(+2) (where TIM = Me-4[14]1,3,8,10 -tetraeneN(4), a macrocyclic ligand) with disulfate bridges has been synthe sized and investigated by X-ray crystallography, IR, electronic and ESR spe ctroscopy. The compound crystallizes in the monoclinic space group C2/c wit h cell parameters a = 16.745(4), b = 7.4288(13), c = 16.657(4) Angstrom, be ta = 115.789(19)degrees. The coordination geometry around the Cu(II) center is axially elongated distorted octahedral. The basal plane around the Cu c enter is planar with zero deviation from the weighted least square plane co mprising four nitrogen atoms (N1, N2, N1' and N2') of the macrocyclic ligan d. Two axial positions are occupied by the O atoms of the S2O72 molecules. The Cu . . . Cu distance is quite long (8.328 Angstrom) along the chain. Th e X-band ESR spectra of a powdered solid sample of [CuTIM(S2O7)](n) polymer , recorded at room temperature gives a isotropic spectrum with a g value of 2.22. (C) 2001 Elsevier Science B.V. All rights reserved.