Morphological variation in self-assembled copper(I) paddle-wheel complexes

The preparation of the two 4-alkyl-2(1H) pyridinethione ligands mpySH and epySH is described. The coordination behaviour of these ligands with copper(I) is reported. In general the patterns of reactivity resemble those of 2(1H)pyridinethione itself. A variety of dinuclear complexes is described together with the structural characterisation of the paddle-wheel complexes [Cu-6(mpyS)(6)] (space group P (1) over bar, a=9.392(2), b=9.642(2), c=11.527(2) Angstrom, alpha=80.79(2), beta=87.66(2), gamma=86.31(2)degrees) and [Cu-6(epyS)(6)]. 2H(2)O (space group P (1) over bar, a=11.131(4), b=11.929(4), c=11.992(4) Angstrom, alpha=109.94(1), beta=106.61(1), gamma=109.33(1)degrees). Although the gross paddle-wheel structure is similar in each case, the variation of the substituent results in significant variation in the geometry of the hexanuclear cluster.