The borohydride complex [(Ni2L)-L-II(mu-BH4)](+) (3) where L2-represents a sterically demanding hexaaza-dithiophenolate ligand reacts rapidly with elemental sulfur in acetonitrile at ambient temperature to produce the cationic complexes [(Ni2L)-L-II(mu-SH)(+) (4) and [{(Ni2L)-L-II}(2)(mu-S-6)(2+) (6). Both complexes were isolated as CIO4- or BPh4- salts and characterized by IR and UV/vis spectroscopy and X-ray crystallography. Complex 4 (also accessible from [(Ni2L)-L-II(CIO4)](+) (5) and Na2S center dot 9H(2)O) features an unprecedented N3NiII(mu-SR)(2)(mu-SH)(NiN3)-N-II core structure, the hydrosulfide ligand being deeply buried in the binding-cavity of the bowl-shaped [(Ni2L)-L-II](2+) complex. In 6, a helical S-6(2-) chain, with a structure reminiscent to that of plastic sulfur, is almost completely encapsulated by two ((Ni2L)-L-II](2+) subunits, In contrast to other triply sulfur-bridged N3NiII(SR)(3)(NiN3)-N-II structures whose ground states are typically of S = 0, 4 reveals an S = 2 ground-state which is attained by a ferromagnetic exchange interaction between the two Ni(II) (S = 1) ions P = 18 cm(-1), H = -2JS(1)S(2)). Intradimer ferromagnetic exchange interactions are also present in 6 (J = 23 cm(-1)). A qualitative explanation for this difference is offered.