Approaches to the assembly of (eta(5)-C5Me5)WS3Cu3-based supramolecular compounds from two preformed incomplete cubane-like clusters [PPh4][(eta(5)-C5Me5)WS3(CuX)(3)] (X = CN, 1a; X = Br, 1b) have been investigated. Treatment of 1a with LiBr/1,4-pyrazine (1,4-pyz), pyridine (py), LiCl/py, or 4,4'-bipyridine (4,4'-bipy) and treatment of 1b with 4,4'-bipy gave rise to a new set of W/Cu/S cluster-based compounds, [Li{((eta(5)-C5Me5)WS3Cu3(mu(3)-Br))(2)(mu-CN)(3)}center dot C6H6] (2), [(A(5)-C5Me5)WS3Cu3(A-CN)(2)(py)] (3), {[PPh4][(eta(5)-C5Me)WS3Cu(mu(3)-Cl)(mu-CN)(CN)]center dot py}infinity ( 4), [PPh4](2)-[( eta(5)-C5Me5)WS3Cu3(CN)(2)](2)(mu-CN)(2),(4,4'-bipy) (5), and {[(eta(5)-C5Me5)WS3Cu3Br(mu-Br)(4,4'-bipy)]center dot Et2O}infinity (6). The structures of 2-6 have been characterized by elemental analysis, IR spectra, and single-crystal X-ray crystallography. Compound 2 displays a 1D ladder-shaped chain structure built of squarelike {[(eta(5)-C5Me5)WS3Cu3(mu(3)-Br)(mu-CN)](4)}-( mu-CN)(2)(2-) anions via two pairs of Cu-mu-CN-Cu bridges. Compound 3 consists of a single 3D diamondlike network in which each (eta(5)-C5Me5)WS3Cu3 unit, serving as a tetrahedral node, interconnects with four other nearby units through Cu-mu-CN-Cu bridges. Compound 4 contains a 1D zigzag chain array made of cubane-like [(eta(5)-C5Me5)WS3Cu3( mu(3)-Cl)(mu-CN)(CN)](-) anions linked by a couple of Cu-A-CN-Cu bridges. Compound 5 contains a dimeric structure in which the two incomplete cubane-like [( eta(5)-C5Me5)WS3(CuCN)(2)(mu-CN)](-) anions are strongly held together via a pair of Cu-mu-CN-Cu bridges. Compound 6 contains a 2D brick-wall layer structure in which dimers of [( eta(5)-C5Me5)WS3Cu3Br(4,4'-bipy)](2) are interconnected via four Cu-mu-Br-Cu bridges. The successful construction of (eta(C5Me5)-C-5)WS3Cu3-based supramolecular compounds 2 - 6 from the geometry- fixed clusters 1a and 1b may expand the scope of the rational design and construction of cluster- based supramolecular assemblies.