Abstract

Four new Zn(II)-azido polymeric complexes with open-chain diazine Schiff-bases as auxiliary bridging ligands have been synthesized and crystallographically characterized. The differences in the constituents of the auxiliary ligands lead to three different types of polymeric structures. Complex 1, [Zn2(L1–H)(N3)3]n (L1 = 1,4-bis(2-pyridyl)-1-amino-4-methyl-2,3-diaza-1,3-butadiene), and complex 2, [Zn2(L2–H)(N3)3·H2O]n (L2 = 1,4-bis(2- pyridyl)-1,4-diamino-2,3-diaza-1,3-butadiene), show a similar one-dimensional (1D) coordination polymeric structure in which the building blocks of tetranuclear rings are interlinked by double end-on (EO) azido bridges, resulting in a “chain of rings” topology. Complex 3, {[Zn17(N3)24(L3–H)2(L3–2H)4(CH3OH)2]·(CH3OH)6·(H2O)3}n (L3 = butanedione monoxime picolinamide hydrazone) has a two-dimensional (2D) structure in which the Zn13 clusters are interlinked by Zn2 binuclear linkers to result in a (4,4) topology. The remaining complex 4, [Zn2(L4–H)(N3)3]n (L4 = 1-(2-pyridyl)-1-amino-4-methyl-4-thiazolyl-2,3-diaza-1,3-butadiene), has a three-dimensional (3D) network with a counterfeit CdSO4 topology, in which the 1D chains similar to those in complexes 1 and 2 are further interlinked by double EO azido bridges.

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