A new tetranuclear complex, [Cu4L4](ClO4)(4)center dot 2H(2)O (1), has been synthesized from the self-assembly of copper(II) perchlorate and the tridentate Schiff base ligand (2E,3E)-3-(2-aminopropylimino) butan-2-one oxime (HL). Single-crystal X-ray diffraction studies reveal that complex 1 consists of a Cu-4(NO)(4) core where the four copper(II) centers having square pyramidal environment are arranged in a distorted tetrahedral geometry. They are linked together by a rare bridging mode (mu(3)-eta(1),eta(2),eta(1)) of oximato ligands. Analysis of magnetic susceptibility data indicates moderate antiferromagnetic (J(1) = -48 cm(-1), J(2) = -40 cm(-1) and J(3) = -52 cm(-1)) exchange interaction through r-superexchange pathways (in-plane bridging) of the oxime group. Theoretical calculations based on DFT technique have been used to obtain the energy states of different spin configurations and estimate the coupling constants and to understand the exact magnetic exchange pathways. (C) 2011 Elsevier B. V. All rights reserved.