X-Ray Crystal Structure, Acid - Base Properties and Complexation Characteristics of a Methylenephosphonate Derivative of 1,4,7,10-Tetraazacyclododecane

The X-ray crystal structures of 1,4,7-tris(methylenephosphonate)-1,4,7,10-tetraazacyclododecane (DO3P·3.5H2O) and 1,7-bis(methylenephosphonate)-1,4,7,10-tetraazacyclododecane dihydrochloride trihydrate (DO2P·2HCl·3H2O) reveal that two nitrogen atoms in the trans-annular positions are protonated. The macrocyclic ring adopts a (3,3,3,3)-B conformation stabilized by intramolecular hydrogen bonding involving oxygen atoms from the phosphonate groups and the protonated amines. The acid–base dissociation constants of DO3P and metal complex formation constants (for Ca2+, Mg2+, Zn2+, Fe3+) were determined using potentiometric measurements. The first two protonations of DO3P occur at quite high pH and, consequently, were determined by NMR measurements. The stability constants indicate that DO3P forms more stable complexes with the transition metal ions Zn2+ and Fe3+ (log K [ML] = 21.23(4) and 22.74(5) respectively) than with the alkaline earth metal ions Ca2+ and Mg2+ (log K [ML] = 10.96(6) and 8.72(6) respectively). For Fe3+, Ca2+ and Mg2+, the data support the formation of dinuclear species, presumably through the coordination of an additional metal ion to the phosphonate groups.