Di-mu-olato dinuclear copper(II) compounds. The structure of bis-mu-o-[(4,6,6-trimethyl-9-(pyridin-2-yl)-3,7-diazanon-3-en-1-olato)copper(II)] perchlorate

Preparations are reported for blue-green [{Cu(pyen)(eto)}(2)](ClO4)(2) [pye n is 2-(2-aminoethyl)pyridine, eto(-) is deprotonated 2-aminoethanol] and o f green [{Cu(pyaceto)}(2)](ClO4)(2), formed by reaction of this compound wi th acetone [pyaceto(-) is deprotonated 4,6,6-trimethyl-9-(pyridin-2-yl)-3,7 -diazanon-3-en-1-ol]. The structure of [{Cu( pyaceto)}(2)](ClO4)(2) shows a unit cell containing two independent, but closely similar, centrosymmetric al dinuclear diolato-bridged cations. The copper(II) ions are in square pyr amidal coordination, with the two bridging oxygen atoms, and the imine and secondary amine nitrogen atoms in the basal plane, with the pyridine nitrog en atom more weakly coordinated axially. Mean dimensions for the two cation s are Cu-Cu# 2.99, Cu-N-basal 2.01, Cu-O 1.96, Cu-N-axial 2.24 , O-Cu-O# 99 , Cu-O-Cu# 81, C-O- Cu 110, C-O-Cu# 130 degrees [C30H46Cl2Cu2N6O10, monocli nic, space group P2(1)/n, a 13.487(1), b 13.356(1), c 20.921(2) , beta 103. 235(3)degrees, R-1 = 0.0516 for 4694 reflections]. Magnetic susceptibilitie s (100-300 K) show antiferromagnetic spin coupling for [{Cu(pyaceto)}(2)](C lO4)(2) and [{Cu(pyen)(eto)}(2)](ClO4)(2) with singlet-triplet level separa tion J of -110(10) and -65(10) cm(-1), respectively, indicating that [{Cu(p yen)(eto)}(2)](ClO4)(2) also has a dinuclear structure.