SYNTHESIS AND SPECTROSCOPY OF COORDINATION-COMPOUNDS OF A VERSATILE BRIDGING LIGAND - MOLECULAR-STRUCTURES OF THE DINUCLEAR COMPOUNDS [CO-2(BDNOL)(NCS)(3)], [ZN-2(BDNOL)CL(NCS)(2)], AND [CU(BDNOL)(NO3)(3)] AND OF THE POLYMERIC COPPER(I) COMPOUND [CU-2(HBDNOL)(NCS)(2)]

The synthesis and characterization are described of transition metal coordination with the novel pentadentate ligand 1,9-bis(3,5-dimethyl-1-pyrazolyl)-3,7-dithia-5-nonanol (Hbdnol). Most of the compounds are of the general formula [M(2)(bdnol)X(3)]. n(solvent) with M = Co2+, Ni2+, CU2+, Zn2+ and Cd2+ and X(-) = Cl-. Br-, NO3-, and NCS-, Additionally, a polymeric copper(I) compound of the formula [Cu2H(bdnol)(NCS)(2)] and an unusual trinuclear nickel compound of the formula [Ni-3(bdnol)Cl-5(EtOH)]. 3EtOH are described. Hbdnol acts as a pentadentate ligand in all compounds; the alcohol group is generally dehydronated and bridging between the metal ions, except in the case of the Copper(I) compound, where the alcohol group is noncoordinating. Single crystals of [Co-2(bdnol)(NCS)(3)]. MeCN (A), [Zn-2(bdnol)Cl(NCS)(2)]. 1/2MeCN (B), [Cu-2(bdnol)(NO3)(3)] (C), and [Cu-2(Hbdnol)(NCS)(2)] (D) were used for X-ray structure determinations, [Co-2(bdnol)(NCS)(3)]. MeCN orthorhombic, space group Pnma, a = 17.7487(7) Angstrom, b = 20.095(2) Angstrom, c = 8.569(2) Angstrom, Z = 4, and T = 150 K: R(F) = 0.060, wR2 = 0.108 for 3606 reflections, [Zn-2(bdnol)Cl(NCS)(2)]. 1/2MeCN: monoclinic, space group P2(1), a = 8.7369(7) Angstrom, b = 16.416(1) Angstrom, c = 11.222(1) Angstrom, beta = 108.84(1)degrees, Z = 2, and T = 293 K; R(F) = 0.051, R(W) = 0.062 for 2983 reflections. [Cu-2(bdnol)(NO3)(3)]: triclinic, space group P-1. a = 8.012(4) Angstrom, b = 12.430(6), Angstrom, c = 13.702(16) Angstrom, alpha = 95.61(7)degrees, beta = 102.34(5), gamma = 97.46(5)degrees, Z = 2, and T = 293 K: R(F) = 0.042, R(W) = 0.041 for 3805 reflections. [Cu-2(Hbdnol)(NCS)(2)]: triclinic space group P-1 a = 9.241(4) Angstrom, b = 10.32(2) Angstrom, c = 15.27(1) Angstrom, alpha = 103.1(1)degrees, beta = 98.92(8)degrees, gamma = 113.85(5)degrees Z = 2, and T = 293 K; R(F) = 0.050, R(W) = 0.052 for 2999 reflections. The compounds were further characterized by IR, ligand field spectroscopy, EPR, and magnetic susceptibility measurements. The dinuclear compound [Ni-2(bdnol)Cl-3] shows a ferromagnetic intramolecular interaction J and an antiferromagnetic ordering between adjacent diners with interaction j. Using a model taking into account the zero-field splitting effect (D), the experimental data are shown to fit well with the calculated values J = 9.0 K, zj = -1.29 K, D = -0.22 K (1 K = 0.6951 cm(-1)), and g = 2.25. The behavior of the trinuclear [Ni-3(bdnol)Cl-5(EtOH)] hints toward ferromagnetic interactions with a transition to a long-range antiferrornagnetic order below 5.5 K. The properties of the latter suggest the presence of 1d or 2d arrangements of the magnetic moments. The dinuclear copper(II) compounds are strongly antiferromagnetically coupled: they are EPR silent at room temperature.