The reaction of [RhCl 2 (HPhL)(PhL)] with M II (ClO 4 ) 2 ⋅6H 2 O in presence of alkali has furnished trinuclear [RhCl 2 (PhL) 2 ] 2 M(H 2 O) 2 ⋅H 2 O (HPhL is phenylazobenzaldoxime; M = Mn, Co, Ni). A similar reaction with M I (PPh 3 ) 2 NO 3 yielded binuclear [RhCl 2 (PhL) 2 ]M(PPh 3 ) 2 (M = Cu, Ag). In these molecules the oximato group acts as a bridge between Rh III (bonded at N) and M II or M I (bonded at O). In structurally characterizedMnO 6 coordination sphere is spanned by four oximato oxygen atoms and two water molecules lying in trans position. In the lattice the neighbouring molecules are held together by H 2 O⋅⋅⋅H 2 O⋅⋅⋅H 2 O hydrogen bonds generating infinite zigzag chains. The manganese atoms lie parallel to the C-axis, the shortest Mn…Mn distance being 7⋅992 Å. Magnetic exchange interactions if any are small as seen in room temperature magnetic moments. The manganese system displays a strong EPR signal near g = 2⋅00. In the complex [RhCl 2 (PhL) 2 ]Cu(PPh 3 ) 2 the copper atom is coordinated to two oximato oxygen atoms and the two phosphorus atoms in a distorted tetrahedral geometry. The softness of the phosphine ligand is believed to sustain the stable coordination of hard oximato oxygen to soft Cu I . The coordination sphere of the Rh III atom in both the complexes is uniformly trans-RhN 4 Cl 2 .