A Polymeric Arched Chain and a Chair‐like M 2 L 2 ‐Metallamacrocycle Crystal Engineered of [ 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)(H 2 O)}(ClO 4 ) 2 ·2CH 3 OH·1.5H 2 O] n ( 1 ) crystallised from a mixture of Cd(ClO 4 ) 2 ·H 2 O, phen and dtdp in methanol. The reaction of [Cu(phen)(H 2 O) 2 ](CF 3 SO 3 ) 2 ( 2 ) with dtdp in an ethanol/water mixture yielded a chair‐like metallamacrocycle, [{Cu(phen)(CF 3 SO 3 ) 2 } 2 (μ‐dtpd) 2 ] ( 3 ). The crystal structure of the precursor complex 2 is also reported.