One linear homo-metallic trinuclear [{CuL 1 (CH 3 OH)} 2 Cu(ClO 4 ) 2 ] (1); five trinuclear hetero-metallic; bent [(CuL 1 ) 2 Ni(H 2 O) 2 ](ClO 4 ) 2 ·H 2 O (2), linear [(CuL 1 ) 2 Zn(ClO 4 ) 2 ] (3), bent [{CuL 2 (ClO 4 )}{CuL 2 (CH 3 OH)} Ni(CH 3 OH) 2 ](ClO 4 )·(CH 3 OH)·0.25(H 2 O) (4), triangular [(CuL 2 ){CuL 2 (CH 3 CN)}Ni(CH 3 CN) 2 ](ClO 4 ) 2 (5), triangular [(CuL 2 ) 2 Ni(H 2 O) 2 ](ClO 4 ) 2 ·3H 2 O (6) and one rare tetranuclear star-shaped [{CuL 2 (H 2 O)} 2 (CuL 2 )Zn](ClO 4 ) 2 ·H 2 O (7) complexes have been synthesized by reacting the "metalloligand", [CuL 1 ] or [CuL 2 ] with corresponding metal perchlorate where the di-Schiff base ligands H 2 L 1 = N,N′-bis(salicylidene)-1,3- propanediamine and H 2 L 2 = (N,N′-bis(α- methylsalicylidene)-1,3-propanediamine. The structures of all the seven complexes have been determined by X-ray crystallography. Structural analysis shows that complexes 1-6 are discrete trinuclear species where phenoxido groups of two terminal "metalloligands" coordinate to a central Cu(II) in 1 or Ni(II) in 2, 4-6 or Zn(II) in 3. In 1 and 3 two trans axial positions of the central Cu(II) are weakly coordinated by the oxygen atoms of perchlorate anions and the molecules are linear. However, in 2, 4-6 two solvent molecules coordinate to the cis positions of the central Ni(II) to complete its distorted octahedral geometry that makes the molecules bent or triangular. On the other hand, complex 7 is a star-shaped tetranuclear species. In which three metalloligands bind a central Zn(II) ion through double phenoxido bridge. © 2013 Elsevier Ltd. All rights reserved.