The structure of the 11-coordinate barium complex of the pendant-donor macrocycle 1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane: an analysis of the coordination numbers of barium(II) in its complexes

The crystal structure of [Ba(DOTAM)Cl]2(ClO4)2 · 2.7H2O, is reported, where DOTAM is 1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane [triclinic, space group, , a=937.6(2), b=1050.4(2), c=1476.6(3) pm, α=110.41(2), β=97.48(2), γ=97.75(2)°, Z=2, R=0.0423]. The structure consists of a dimer held together by four oxygen atoms bridging between the two Ba atoms. Each Ba is 11-coordinate, coordinated to four nitrogens from the macrocyclic ring, and four oxygens from the four pendant amide groups of DOTAM. In addition, each Ba has a coordinated chloride ion, as well as two bridging amide oxygens from the other member of the dimer. An analysis of the coordination numbers (CN) of Ba(II) complexes is presented. It is found that the CN of Ba(II) complexes ranges from 3 to 12, and is most commonly 9 with unidentate ligands. Higher coordination numbers of 10 and above are promoted by either polydentate ligands of denticity greater than six, or the presence of several ligands such as nitrate or acetate that form four-membered chelate rings. Lower coordination numbers of seven and below are promoted by increasingly large substitutents attached directly to the donor atoms of the ligand.