X-ray crystallographic study of Ni(II) bis(morpholine-N-carbodithioate) and epr studies of Cu(II) bis(morpholine-N-carbodithioate) and Cu(II) bis(pyrrolidine-N-carbodithioate)

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Abstract
Crystals of Ni(II) bis(morpholine-N-carbodithioate) are monoclinic, a = 4.291(1), b = 20.584(2), c = 8.365(1) Å, β = 97.39(2)°, Z = 2, space group P21/n. The structure was solved by Patterson and Fourier syntheses and was refined by full-matrix least-squares procedures to R = 0.036 and Rw = 0.044 for 1800 reflections with I ≥ 3σ(I). The crystal structure consists of discrete molecules having approximate C2h and exact (crystallographic) Ci symmetry. The nickel atom is coordinated to four sulphur atoms in a planar arrangement with Ni—S = 2.2122(7) and 2.2134(6) Å and S—Ni—S = 79.16(2) and 100.84(2)°.The electron paramagnetic resonance spectra of 63Cu(II) bis(morpholine-N-carbodithioate) and 63Cu(II) bis(pyrrolidine-N-carbodithioate) doped in the respective Ni(II) analogues have been recorded at room temperature. The spin Hamiltonian parameters obtained from an analysis of the spectra of the polycrystalline samples have been used to investigate the bonding in these complexes. The results are compared to previous studies in carbodithioates.

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