SYNTHESIS AND STRUCTURES OF POLAR COORDINATION POLYMERS - [(SALEN)MNO2CCH2D-B]N (D = NH, S - B = 4-PYRIDYL, 4-CYANOPHENYL)

Reaction between [NN'-ethylenebis(salicylaldiminato)]manganese(III) bromide (Mn(SALEN)Br) and N-4-pyridylglycine gives Mn(SALEN)(N-4-pyridylglycinate) (1), which crystallizes as an infinite-chain coordination polymer. The polymer chains consist of metal centers bridged by 4-pyridylglycinate ligands. The Mn atoms are octahedrally coordinated with the SALEN ligand filling four equatorial sites, a carboxylate oxygen occupying one axial site, and a pyridyl nitrogen of an adjacent molecule occupying a trans axial site. This bonding pattern is repeated to give a polymer with head-to-tail alignment along the backbone. The reaction between Mn(SALEN)Br and (4-pyridylthio)acetic acid gives the compound Mn(SALEN)((4-pyridylthio)acetate) (2), with a polymeric structure in the solid state very similar to that of 1. 1, C24H27MnN406, crystallizes in the monoclinic space group P2(1)/c with a = 10.782(2) angstrom, b = 18.100(6) angstrom, c = 12.886(4) angstrom, beta = 105.22(2)-degrees, and Z = 4. 2, C23H22MnN3O5S, crystallizes in the monoclinic space group P2(1)/c with a = 10.670(1) angstrom, b = 17.754(3) angstrom, c = 12.714(2) angstrom, beta = 108.78(l)-degrees, and Z = 4. In contrast, there action of Mn(SALEN) Br with N-(4-cyanophenyl)glycine gives 3, whose crystal structure consists of a mixture of the monomeric (H2O)Mn(SALEN)(N-(4-cyanophenyl)glycinate) and a Mn(SALEN)(N-(4-cyanophenyl)glycinate) polymer. This polymer consists of adjacent Mn(SALEN) moieties bridged by a single carboxylate unit in a syn-anti conformation; thus no head-to-tail alignment is observed along the backbone. 3, C25H2lMnN4O4.C25H23MnN4O5, Crystallizes in the monoclinic space group P2(1)/n, with a 14.295(4) angstrom, b = 11.614(4) angstrom, c = 27.220(7) angstrom, beta = 90.20(2)-degrees, and Z = 4.