NEW 12-MEMBERED AND 24-MEMBERED MACROCYCLES WITH PENDENT ACETATO GROUPS AND X-RAY CRYSTAL-STRUCTURES OF THE COPPER(II) AND MANGANESE(II) COMPLEXES

A condensation reaction between ethylenediaminetetraacetic dianhydride and ethylenediamine provided two new macrocyclic ligands: one is a 12-membered macrocycle with two pendent acetato groups, C8H14N4O2(CH2CO2H)2 [represented as L(12)H-2], and the other is a 24-membered macrocycle with four pendent acetato groups, C16H28N8O4(CH2CO2H)4 [represented as L(24)H-4], in which two ethylenediaminetetraacetato groups and two ethylenediamine groups are linked by amide bonds. The formation of the macrocycles was confirmed by X-ray crystal analyses of their metal complexes, CuL(12).4H2O and Mn2L(24).8H2O. The copper(II) complex crystallized in the orthorhombic space group P2(1)2(1)2(1) with a = 10.070 (1) angstrom, b = 18.832 (2) angstrom, c = 9.425 (1) angstrom, and Z = 4. Each copper atom has a distorted octahedral coordination geometry with two amine nitrogen atoms (Cu-N = 2.088 and 2.485 angstrom), an amide oxygen atom (Cu-O = 1.988 angstrom), two carboxylato oxygen atoms (Cu-O = 1.996 and 2.334 angstrom), and another carboxylato oxygen atom from a neighboring metal chelate (Cu-O = 1.936 angstrom); one of the amide groups is not coordinated to copper. One of the carboxylato groups is coordinated to two copper atoms, forming a one-dimensional -Cu-O-C-O-Cu chain. The manganese complex crystallized in the hexagonal space group P6(2) (or P6(4)) with a = 18.072 (3) angstrom, c = 10.195 (2) angstrom, and Z = 3. Each ligand coordinates two manganese ions, which are located outside the cavity of the macrocycle and are crystallographically equivalent to each other. Each manganese atom has a distorted seven-coordination geometry with two amine nitrogen atoms (Mn-N = 2.358 and 2.445 angstrom), two carboxylato oxygen atoms (Mn-O = 2.111 and 2.212 angstrom), a water molecule (Mn-O = 2.137 angstrom), and two amide oxygen atoms (Mn-O = 2.184 and 2.686 angstrom).