The reactions of newly prepared fac(S)-[Cr(aet)(3)] (1) with Zn2+ and Ni2+ gave the polynuclear complexes [{Cr(aet)(3)}(4)Zn4O](6+) (2) and [Ni{Cr(aet)(3)}(2)](2+) (3), respectively, where aet denotes 2-aminoethanethiolate (NH2CH2CH2S-). The structures of complex cations 2 and 3 are determined by the X-ray diffractions. 2Br(6).6H(2)O is spontaneously resolved as single crystals and crystallizes in the cubic space group P2(1)3, a=19.024(1) Angstrom, Z=4, and R=0.044. 3(NO3)(2).2H(2)O crystallizes in the triclinic space group P (1) over bar with a=10.228(2), b=12.265(3), c=13.362(3) Angstrom, alpha=101.08(1), beta=108.02(1), gamma=102.35(1)degrees, Z=2, and R=0.031. 2 consists of four fac(S)-[Cr(aet)(3)] units, four Zn atoms, and one central mu(4)-oxygen atom, forming the T-cage-type octanuclear structure. 3 consists of two fac(S)-[Cr(aet)(3)] units and one Ni atom, forming linear-type trinuclear structure. The electronic absorption and CD spectral behavior of the isolated complexes are discussed in comparison with those of the corresponding polynuclear complexes. The effective magnetic moments are 3.99 mu(B) for 1 at 296 K, and 7.58 mu(B) for 2, and 5.19 mu(B) for 3 at 300 K. 3 indicates the presence of intramolecular antifenomagnetic exchange interactions, but 2 does not show the intramolecular magnetic exchange interactions.