3D Coordination Polymer Incorporating Discrete Molecular Octahedra

Abstract

Abstract Copper(II) oxalate coordination polymer [{Cu 4 (C 2 O 4 ) 4 (L) 4 } 3 · {Cu 3 (C 2 O 4 ) 3 (L) 6 } 2 · 3L · 25H 2 O] n (L = 3,3′,5,5′‐tetramethyl‐4,4′‐bipyrazole) reveals a structure that is related to the Pt 3 O 4 net topology. The 3D linkage is sustained with copper‐oxalate squares and copper‐bipyrazole triangles sharing vertices. The framework supports giant icosahedral cages and entraps discrete molecular octahedra formed by two molecular complexes Cu 3 (C 2 O 4 ) 3 (L) 6 associated by means of NH‐‐‐N hydrogen bonding. The coexistence of the discrete and 3D portions formed by the same components suggests self‐templation as a key feature of the system. Simpler copper oxalate compounds [Cu(C 2 O 4 )(L) 2 (H 2 O)] · CH 3 OH · 3.75H 2 O and [Cu 2 (C 2 O 4 ) 2 (L) 5 ] · L · 11H 2 O are concomitant products of the reaction mixture and they exist in the form of molecular mono‐ and binuclear complexes.