COORDINATION-COMPOUNDS WITH THE N2S-DONOR LIGAND 1,5-BIS(3,5-DIMETHYLPYRAZOL-1-YL)-3-THIAPENTANE

With the ligand 1,5-bis(3,5-dimethylpyrazol-1-yl)-3-thiapentane (bdtp) the compounds [M(bdtp)(NCS)2] (M = Co or Zn), [Ni(bdtp)(NCS)2(H2O)], Cu(bdtp)(F)(BF4), M(bdtp)Cl2 (M = Co or Cu), Zn(bdtp) Cl2.0.5EtOH, M(bdtp)(NO3)2 (M = Co or Cu), Cu(bdtp)X (X = Br or Cl), [Cu(bdtp)]BF4.H2O and Ag(bdtp)(NO3) have been isolated. X-Ray single-crystal structures of [Co(bdtp)(NO3)2], Cu(bdtp)Br and Ag(bdtp)(NO3) were determined. The compound [Co(bdtp)(NO3)2] crystallizes in the monoclinic space group P2(1)/n, with a = 8.984(2), b = 15.342(3), c = 14.888(3) angstrom, beta = 107.28(2)-degrees, Z = 4 and R 0.038 for 2727 observed [F > 2-sigma(F)] reflections. The cobalt(II) atom is pseudo-octahedrally co-ordinated by three ligand donors, one mono- and one di-dentate nitrate. The Co-N [2.072(3) and 2.083(3) angstrom] and Co-S bond lengths [2.584(1) angstrom] are normal. The compound Cu(mu(bdtp)Br crystallizes in the monoclinic space group P2(1)/n, with a = 9.017(2), b = 14.09(2), c = 13.660(3) angstrom, beta = 97.80(2)-degrees, Z = 4 and R 0.040 for 1655 observed reflections. The pseudo-tetrahedral co-ordination environment of the copper(I) atom is made up by two pyrazole nitrogens [2.120(5) and 2.014(5) angstrom], one thioether [2.461(2) angstrom] and one bromide [2.432(1) angstrom]. The ligand acts as a link between two successive copper centres, resulting in a polymeric compound structurally isomorphous to Cu(bdtp)CI. The compound Ag(bdtp)(NO3) crystallizes in the monoclinic space group P2(1)/n, with a = 18.710(4), b = 8.828(2), c = 11.162(5) angstrom, beta = 103.13(3)-degrees, Z = 4 and R 0.038 for 2346 observed reflections. The structure, with bridging ligands, is similar to that of Cu(bdtp)Br. The silver(I) atoms are co-ordinated, in a very distorted-tetrahedral fashion, by two nitrogens [2.483(5) and 2.216(4) angstrom], one thioether [2.571(2) angstrom] and a monodentate nitrate anion [2.503(5) angstrom].