Mixed-ligand MnII and CuII complexes with alternating 2,2'-bipyrimidine and terephthalate bridges.

摘要: The novel polymeric complexes catena-poly[[diaquamanganese(II)]-μ-2,2'-bipyrimidine-κ(4)N(1),N(1'):N(3),N(3')-[diaquamanganese(II)]-bis(μ-terephthalato-κ(2)O(1):O(4))], [Mn2(C8H4O4)2(C8H6N4)(H2O)4]n, (I), and catena-poly[[[aquacopper(II)]-μ-aqua-μ-hydroxido-μ-terephthalato-κ(2)O(1):O(1')-copper(II)-μ-aqua-μ-hydroxido-μ-terephthalato-κ(2)O(1):O(1')-[aquacopper(II)]-μ-2,2'-bipyrimidine-κ(4)N(1),N(1'):N(3),N(3')] tetrahydrate], {[Cu3(C8H4O4)2(OH)2(C8H6N4)(H2O)4]·4H2O}n, (II), containing bridging 2,2'-bipyrimidine (bpym) ligands coordinated as bis-chelates, have been prepared via a ligand-exchange reaction. In both cases, quite unusual coordination modes of the terephthalate (tpht(2-)) anions were found. two tpht(2-) acting bis-monodentate bridge Mn(II) centres in parallel fashion. act endo-bridges connect Cu(II) combination with additional aqua hydroxide bridges. this way, binuclear [Mn2(tpht)2(bpym)(H2O)4] entity (I) trinuclear [Cu3(tpht)2(OH)2(bpym)(H2O)4]·4H2O (II) build up one-dimensional chains along b axis. cation lies on twofold axis, whereas four central C atoms bpym ligand are located mirror plane. is also special position (site symmetry -1). crystal structures, packing further strengthened by system hydrogen bonds [in (II)] weak face-to-face π-π interactions (I)], forming three-dimensional metal-organic frameworks. has trigonally deformed octahedral geometry, cations distorted environments. polyhedra inclined relative to each other share common edges.