Construction of Metal–Organic Frameworks: Versatile Behaviour of a Ligand Containing Mono‐ and Bidentate Coordination Sites

Five new coordination polymers based on a new 2,2′‐bipyridine derived ligand N , N ′‐bis(pyridin‐4‐yl)‐2,2′‐bipyridine‐5,5′‐dicarboxamide (=L) are reported herein. Isostructural three‐dimensional coordination polymers with a rare (4,6)‐connected network of {4 4 .6 2 } 3 {4 6 .8 9 } 2 topology were synthesised from Cu(NO 3 ) 2 , Zn(NO 3 ) 2 or a mixture of Cu(NO 3 ) 2 /Fe(BF 4 ) 2 with L in complexes {[Cu 5 L 6 ]⋅(NO 3 ) 10 ⋅(H 2 O) 18 } ∞ ( 1 ), {[Zn 5 L 6 ]⋅(NO 3 ) 10 ⋅(H 2 O) 18 } ∞ ( 2 ) and {[Fe x Cu y L 6 ]⋅(NO 3 ) 10 ⋅(H 2 O) 18 } ∞ ( 3 ; where x + y =5). Complexes with two‐dimensional grid structures resulted from treatment with CoCl 2 or Cd(NO 3 ) 2 with L in complexes {[CoLCl 2 ]⋅DMF} ∞ ( 4 ) and {CdL(NO 3 ) 2 } ∞ ( 5 ).