Herein, we report a comprehensive coordination study of the previously reported ligands cyclam , CB-cyclam TMC , DMC , CB-DMC , and of their C -functional analogues, cyclam-E , CB-cyclam-E , TMC-E , DMC-E and CB-DMC-E . This group of ligands includes cyclam , cross-bridged cyclams , their di- or tetramethylated derivatives and the analogues bearing an additional hydroxyethyl group on one β-N position of the ring. These Cu(II) and Zn(II) complexes of these macrocycles have been highlighted previously for the biological interest, but the details of their structures in the solid state and in solution remained largely unexplored.