The present study deals with one dimer-of-dinuclear type compound, [{CuIILAgI(NO3)}2] (1), one pentametallic and metal-centered rectangle type compound, [BaII(CuIIL)4](ClO4)2 (2), and one dinuclear based two-dimensional coordination polymer, [CuIILCdII(μ1,5-dicyanamide)2]n (3), where H2L=N,N′-bis(salicylidene)-1,4-butanediamine. The syntheses and crystal structures of 1–3, electrospray ionization mass spectra in positive mode of 1 and 2 and variable-temperature magnetic properties of 2, are described. Two symmetry related diphenoxo-bridged dinuclear CuIIAgI moieties are interlinked in 1 by Ag–π (η2-) bonds to form dimer-of-dinuclear type structure. One diphenoxo-bridged dinuclear CuIICdII moiety is interlinked with four symmetry related dinuclear moieties by four μ1,5-dicyanamide ligands, which link CdII centers, to generate two-dimensional polymeric structure in 3. In the [BaII(CuIIL)4]2+ cation in 2, the BaII ion is coordinated to two μ-phenoxo oxygen atoms of each of the four [CuIIL] fragments; the four copper(II) ions are positioned to form an approximate rectangle, i. e., the pentametallic [BaII(CuIIL)4]2+ cation in 2 is a metal-centered rectangle. ESI-MS positive of 1 and 2 have been recorded and the ions in the spectra have been reasonably assigned. Variable-temperature magnetic studies of 2 reveal very weak antiferromagnetic interaction (J=–0.14 cm–1) between the copper(II) ions. The structure of 2 represents a new type among compounds from related ligands. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim