Reversible and non-reversible inclusion compounds of the nickel xanthate adducts with 4,4′-bipyridyl and with 2,2′-dipyridylamine

Abstract

The crystal structures of the benzene inclusion compound of the 2,2′dipyridylamine nickel ethylxanthate adduct, [Ni(S 2COEt) 2(2,2′-dpa)·C 6H 6], and the carbon tetrachloride inclusion compound of the 4,4′-bipyridyl nickel butylxanthate adduct, [Ni(S 2COBu) 2(4,4′-bipy)·2CCl 4] n, have been determined by single crystal X-ray diffraction methods. Crystals of [Ni(S 2COEt) 2(2,2′-dpa)·C 6H 6] are triclinic, space group P 1 , a = 8.755(2), b = 12.680(3), c = 13.012(3) Å, and α = 110.12(2), β = 106.09(2), γ = 92.56(2)° with Z = 2; R and Rw were 0.060 and 0.064 respectively for 3073 unique observed reflections. The nickel atom is in an octahedral environment, surrounded by two chelating xanthate ligands and one chelating 2,2′-dpa molecule. The benzene molecules sit in cavities formed by the packing of the [Ni(S 2-COEt) 2(2,2′-dpa)] molecules, there being two benzene molecules in each cavity. Crystals of [Ni(S 2COBu) 2(4,4′-bipy)·2CCl 4] n are triclinic, space group P 1 , a = 6.6349(8), b = 11.3135(9), c = 13.1101(9) Å, α 64.454(7), β = 79.551(8), γ = 84.984(8)°, Z = 2; R and Rw were 0.040 and 0.044 respectively for 3018 unique reflections. The nickel atom is in an octahedral environment which results from two chelating xanthate ligands and two nitrogen atoms, one from each of two, 4,4′-bipyridyl ligands. The nitrogen atoms are in a trans configuration which gives rise to a linear polymer of composition [Ni(S 2COBu) 2(4,4-bipy)] n. The CCl 4 molecules sit in open channels, parallel to the a-axis, which are formed by the packing of the linear polymeric chains of the complex.