Reaction of Na4TCM (1) (H4TCM = tetra[4-(carboxyphenyl)oxamethyl]methane) with [Cu(CHA)](ClO4)2 (2)(CHA = 1,3,6,8,11,14-hexaaz atricyclo[126.96.36.199.8,11] octadecane) in a DMF-water mixture yields [Cu(CHA)]2[TCM] (3). Structural analysis of [Cu(CHA)]2[TCM]·11H2O (3·11H2O) by single crystal X-ray diffraction reveals strong copper-oxygen bonds between two complex cations and the tetraanion leading to a 3D coordination network (zwitterionic structure), consolidated through additional NH...O=C hydrogen bonding within the cation/anion association. The resulting coordination geometry around a copper atom is a distorted square pyramidal with an oxygen atom of the anionic ligand in the apical position. A 3D supramolecular network is developed in the crystal based only on NH...OC hydrogen bonds between the macrocyclic metallic tecton and the carboxylate groups of neighboring 3D coordinated (zwitterionic) moieties. The pseudotetrahedral TCM4− tetraanionic ligand induces a diamondoid architecture formed of large distorted adamantanoid cages. <alternatives> [...] </alternatives>
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