One-pot template synthesis and crystal structure of two new polyaza copper(II) complexes

A new 14-membered hexazamacrocyclic copper(II) complex Cu(H₂L¹)](ClO₄)₄(L¹=1,8-bis(2-aminoethyl)-1,3,6,8,10,13-hexaazacyclotetradecane) has been prepared by the one-pot reaction of ethylenediamine and formaldehyde in the presence of the Cu(II) ion. The crystal structure of Cu(H₂L¹)](ClO₄)₄ was determined by X-ray diffraction. It crystallizes in the triclinic space group P?1 with a=12.118(2) Å, b=12.438(2) Å, c=12.466(2) Å, α=102.26(1)°, β=112.82(1)°, γ=111.51(1)°, and Z=2. The coordination geometry around the copper(II) ions is axially elongated octahedral with four nitrogen atoms of the macrocycle Cu–N 2.012(7) Å for Cu(1) and 2.013(6) Å for Cu(2), average value] and two oxygen atoms of two ClO₄^? anions Cu–O=2.550 Å for Cu(1) and 2.601(6) Å for Cu(2)]. CuL²](ClO₄)₂(L²=3,7-bis(2-aminoethyl)-1,3,5,7-tetraazabicyclo3,3,2]decane) with a novel tetraazabicyclic ligand was obtained from the same reaction system as an additional product. Crystal structure of CuL²](ClO₄)₂: monoclinic space group Cc, a=16.393(3) Å, b=8.8640(18) Å, c= 13.085(3) Å, β=105.01(3)°, and Z=4.