Synthesis, crystal structure and properties of [Cu(phen)3][Cu(pheida)2]•10H2O and [(phen)2Cu(μ-BAAP)Cu(μ-BAAP)Cu(phen)2][Cu(BAAP)2]•8.5H2O (H2pheida = N-phenetyl-iminodiacetic acid, H2BAAP = N-benzylaminoacetic-2-propionic acid)

The salts [Cu(phen)(3)][Cu(pheida)(2)=](.)10H(2)O (1) and [(phen)(2)Cu(mu-BAAP)Cu(mu-BAAP)Cu(phen)(2)][Cu(BAAP)(2)](.)8.5H(2)O (2) (H(2)pheida = N-phenetyl-iminodiacetic acid, H,BAAP = N-benzylaminoacetic-2-propionic acid, phen = 1,10-phenanthroline) have been prepared and studied by thermal, spectroscopic and X-ray diffraction methods. 1 has the rather unusual [Cu(phen)]= canon and two non-equivalent [Cu(pheida)(2)](2-) anions with a coordination type 4+2 but quite different tetragonality (T = 0.848 and 0.703 for anions 1 and 2, respectively). The crystal consists of multi-pi,pi-stacked chains (...anion 2 - cation - cation - anion 2...) connected by hydrophobic interactions; these chains build channels which are partially filled by anions 1 and water molecules. In contrast, compound 2 has a mixed-ligund trinuclear canon with a bridging central moiety close similar to the counter anion. The formation of such a trinuclear canon is discussed as a consequence of the most advantageous molecular recognition process between [Cu(phen)(2)(H2O)(1) or (2)](2+) and [Cu(BAAP)(2)](2-) in solution. In the crystal of 2, multi-pi,pi-stacked arrays of C-6-rings from phen and (BAAP)(2-) ligands of trinuclear canons generate channels where counter anions and water molecules are located.