Inorganic Chemistry, Vol.34, No.12, 3294-3300, 1995
Laser-Induced Luminescence Studies and Crystal-Structure of the Europium(III) Complex of 1,4,7,10-Tetrakis(Carbamoylmethyl)-1,4,7,10-Tetraazacyclododecane - The Link Between Phosphate Diester Binding and Catalysis by Lanthanide(III) Macrocyclic Complexes
Solution and solid-state properties of the Eu(III) complex of the tetraamide macrocyclic ligand TCMC (TCMC = 1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane) are investigated as part of an effort to develop lanthanide(III) macrocyclic catalysts. [Eu(TCMC)(H2O)](CF3SO3)(3) . 2CH(3)OH crystallizes in the centrosymmetric monoclinic space group P2(1)/n with a = 12.0571(15) Angstrom, b = 13.2196(20) Angstrom, c = 25.4250(40) Angstrom; beta = 91.673(11)degrees, V = 4050.8 Angstrom(3), and Z = 4. The structure was solved and refined to R = 4.02% and R(w) = 4.33% for 3510 reflections with F > 6 sigma(F). (R = 7.04%, R(w) = 6.48% for all 5322 independent reflections.) Four stereoisomers (two enantiomeric pairs) of the [Eu(TCMC)(H2O)](3+) cation appear in the crystal. The structure is disordered, containing two overlapping diastereomers that are interrelated by different conformations of the 1,4,7,10-tetraazacyclododecane ring defining the asymmetric unit. Two enantiomers are related to these by operations of the second kind (i, n-glide). The nine-coordinate Eu(III) center has a 4:4:1 coordination geometry formed by the octadentate TCMC ligand and a single bound water molecule.
Keywords:DYNAMIC PROPERTIES;METAL-IONS;HYDROLYSIS;DOTA;NMR;LANTHANUM(III);STABILITY;HYDROGEN;CLEAVAGE;SPECTRA