A series of three new compounds obtained from the reaction of Rh2(OAc)4 and 2, 2′ -dipyridylamine (Hdpa) under various conditions have been characterized. All are diamagnetic and have a Rh–Rh single bond. In Rh2(dpa)4, 1, there are four bridging dpa anions which bind the two Rh atoms through one pyridyl N atom and one amido N atom though two of these ligands interact further with a rhodium atom through the third N atom. In the other two compounds the Hdpa ligand is neutral. Thus Rh2(OAc)4(Hdpa)2, 2, is an adduct of the well known complex dirhodium tetraacetate in which the two Hdpa ligands occupy axial positions. In the third compound, Rh2(Hdpa)2(OAc)2Cl2, 3, only two acetate bridges are present. One Hdpa molecule chelates equatorially each rhodium atom and the chloride ions are axially coordinated. The Rh–Rh distances are 2. 4005(6) and 2. 4042(8) Å for 1 and 2, respectively. For 3, the Rh–Rh distance of 2. 593(1) Å is significantly longer than those in 1 and 2 because of the presence of fewer bridging ligands.