Copper(II) complexes of pentadentate 17-membered macrocyclic diamidodiamines with N, O or S as additional donors

The crystal structures of (2,6-dioxo-1,4,7,11,14-pentaazacyclo-heptadecanato)copper(II) tetrahydrate, [Cu(C 12 H 23 N 5 O 2 )].4H 2 O, (I), (3,16-dioxo-1-oxa-4,8,11,15-tetraazacycloheptadecanato)copper(II) pentahydrate, [Cu(C 12 H 22 N 4 O 3 )].5H 2 O, (II), and (3,16-dioxo-1-thia-4,8,11,15-tetraazacycloheptadecanato)copper(II) trihydrate, [Cu(C 12 H 22 N 4 O 2 S)].3H 2 O, (III), are reported. The coordination geometry in each case is approximately square pyramidal with two amine groups and two deprotonated amide groups in the basal plane. The apical position is occupied by an amine group, an ether O atom or a thio S atom. Trigonal distortion increases in the sequence S < O < N as apical donor. The relation between the distortion in the basal plane of the complexes and the maxima in their electronic spectra is discussed.