A family of trinuclear oximato complexes [((ML)-L-II)(3)(mu(3)-O)]ClO4 (M = Ni, 1-3; Pd, 4 and 5) (HL = 2-alkylamino-3-oximobutane) involving a discrete [M-3(mu(3)-O)](4+) core have been synthesized in moderate to high yields by a simple one-pot reaction. The products were characterized by ESI-mass and H-1 NMR spectroscopy as well as by single-crystal X-ray diffraction analysis of representative compounds viz., 1, 2, and 4. The oximato oxygen atoms from the ligands and the central mu(3)-O atom connect the metal centers, forming an inverse metallacrown topology in these complexes. In the isostructural nickel compounds (1, 2), the metal centers are situated at the vertices of an equilateral triangle with its centroid position being occupied by the mu(3)-O atom; the Ni-O-Ni angles vary in the range 119.0(2)-120.2(2)degrees. In the palladium complex 4, the geometry of the Pd3O core is better described as a regular trigonal pyramid with the metal centers and the mu(3)-O atom occupying the apexes; the Pd-O-Pd angles are close to 109 degrees. The coordination square planes around the individual palladium centers bend appreciably from each other (dihedral angles vary in the range 28.62-34.53 degrees), providing more of a bowl shape compared to the overall metallacrown topology that remains virtually planar in the nickel complexes. The mu(3)-oxygen atom in 4 is displaced by 0.687 angstrom from the center of the triangular plane with corners occupied by the Pd(II) ions. The protons of the metallacrown peripheral rings in 4 and 5 are more deshielded compared to their nickel(II) counterparts, as revealed from their H-1 NMR spectra in dichloromethane-d(2) solution.