Binuclear copper(II) complexes with N3S-coordinate tripodal ligand and mixed azide-carboxylate bridges: Synthesis, crystal structures and magnetic properties

One new N3S-coordinate tetradentate ligand N,N-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-2-(phenylthio)ethan-1-amine (bdmpe), two double end-on azide bridged copper(II) complexes [Cu(bdmpe)(μ1,1-N3)]2(X)2 [X=ClO4−, PF6−] and two triple bridged copper(II) complexes [Cu2(dmpe)2(μ1,1-N3)2(Y)]PF6 [where, dmpe=N-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-2-(phenylthio)ethan-1-amine, Y=CH3COO− or HCOO−] have been synthesized and characterized. Crystal structure of the three complexes [Cu(bdmpe)(μ1,1-N3)]2(ClO4)2(1), [Cu2(dmpe)2(μ1,1-N3)2(CH3COO)]PF6(3) and [Cu2(dmpe)2(μ1,1-N3)2(HCOO)]PF6(4) have been solved by single crystal X-ray diffraction studies. Variable temperature (4–273K) magnetic measurement have been discussed in detail. [Display omitted] One new N3S-coordinate tetradentate ligand N,N-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-2-(phenylthio)ethan-1-amine (bdmpe) has been synthesized and characterized. Two double end-on azide bridged copper(II) complexes [Cu(bdmpe)(μ1,1-N3)]2(X)2 [X=ClO4−, PF6−] and two triple bridged copper(II) complexes [Cu2(dmpe)2(μ1,1-N3)2(Y)]PF6 [where dmpe=N-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-2-(phenylthio)ethan-1-amine, Y=CH3COO− or HCOO−] have been synthesized and characterized. Ligand (dmpe) has been formed from ligand bdmpe during in situ complexation reaction. Crystal structures of the three complexes [Cu(bdmpe)(N3)]2(ClO4)2 (1), [Cu2(dmpe)2(μ1,1-N3)2(CH3COO)]PF6 (3) and [Cu2(dmpe)2(μ1,1-N3)2(HCOO)]PF6 (4) have been solved by single crystal X-ray diffraction studies and the structural data revealed that the complex [Cu2(bdmpe)2(N3)2](ClO4)2 is binuclear and two copper(II) centers are bridged by a pair of (μ1,1) N3− ion whereas the structures of complexes 3 and 4 are binuclear with triple bridged and two adjacent copper(II) centers are bridged by pair of N3− ions with end-on (μ1,1) coordination mode and one acetate/formate group with syn–syn coordination mode, respectively. Variable temperature (4–273K) magnetic measurement shows that complex 1has no magnetic interaction whereas complexes 3 and 4 have weak antiferromagnetic interactions with J values −15.3(1)cm−1 for complex 3 and −17.8(1)cm−1 for complex 4.