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A POMs-based 3D zeolike ionic crystal 1,{[Co(dpdo)2(CH3CN)(H2O)2]2(SiMo12O40)-(H2O)2}n (dpdo = 4,4'-bipyridine-N,N'-dioxide),was constructed via self-assembly by embedding Keggintype [SiMo12O40]4-polyanions within the intercrystalline voids as pil