Synthesis, structures, and magnetic properties of two pyrazolato-bridged trinuciear copper(II) complexes

摘要

One nonlinear and one linear trinuciear copper(II) complex [Cu_3(dien)_2(pdc)_2CH_3OH]_2?6CH_3OH (1) and [Cu_3(pdc)_2(CH_3OH)_6(H_2O)_4] (2) were prepared and characterized structurally, where dien is diethylenetriamine and pdc~(3-) the trianion of 3,5-pyrazoledicarboxylic acid. Both complexes consist of 3,5-pyrazoledicarboxylato-bridged trinuciear copper(II) centers. In 1, copper(II) ions are five-coordinate in distorted square pyramids with bond angles 164.78° for Cu(1)-Cu(2)-Cu(3) and 164.51° for Cu(4)-Cu(5)-Cu(6). In 2, the three copper(II) ions are six-coordinate with elongated octahedral geometry. The trinuciear units of 1 and 2 interact through hydrogen bonds to form 3-D and 2-D supramolecular networks, respectively. Variable temperature magnetic susceptibility measurements show that 1 and 2 are antiferfomagnetically coupled with J values of -11.2 and -13.3 cm~(-1).