A Polymeric Arched Chain and a Chair‐like M2L2‐Metallamacrocycle Crystal Engineeredof [M(phen)]2+(M= Cu, Cd; phen = 1,10‐Phenanthroline) Corner Units and the Bent Ligand 4,4′‐Dithiodipyridine

Self‐assembly of Cd(phen)2+and Cu(phen)2+(phen = 1,10‐phenanthroline) building blocks with the bent ligand 4,4′‐dithiodipyridine (dtdp) has been investigated. Both building blocks serve as corner units with constrained cis‐geometry. The arched chain coordination polymer [{Cd(phen)(μ‐dtdp)(dtdp)(H2O)}(ClO4)2·2CH3OH·1.5H2O]n(1) crystallised from a mixture of Cd(ClO4)2·H2O, phen and dtdp in methanol. The reaction of [Cu(phen)(H2O)2](CF3SO3)2(2) with dtdp in an ethanol/water mixture yielded a chair‐like metallamacrocycle, [{Cu(phen)(CF3SO3)2}2(μ‐dtpd)2] (3). The crystal structure of the precursor complex 2is also reported.