TCB bridged binuclear and polynuclear copper(II) complexes:: a novel three dimension-network structure complex [(Cudien)2(Cudien•H2O)TCB(ClO4)2•H2O]n (TCB = tetracarboxylatobenzene, dien = 3-azapentane-1,5-diamine)

The binuclear copper(II) complexes [(Cudipn . H2O)(2) TCB]. 8H(2)O and the three-dimensional network complex [(Cudien)(2)(Cudien . H2O)TCB (ClO4)(2) . H2O](n), where TCB stands for tetracarboxylatobenzene, dipn is N-(3-aminopropyl)-1,3-propanediamine, dien is 3-azapentane-1,5-diamine, were synthesized and characterized by IR, ESR and magnetic susceptibility. The compound [(Cudipn . H2O)(2)TCB]. 8H(2)O is a TCB bridging binuclear Cu(II) complex. The complex [(Cudien)(2) (Cudien . H2O)TCB (ClO4)(2) . H2O](n) crystallizes in the monoclinic system, space group C2/c, with a = 26.257(9), b = 8.087(2), c = 19.301(7) Angstrom, beta = 116.41(3)degrees and Z = 4. The copper atoms have two kinds of coordination environment. Cu(2) atom is coordinated in an elongated octahedral arrangement by three nitrogen atoms from dien, two oxygen atoms from two carboxyl groups of two adjacent TCB molecules and one oxygen atom from the water-molecule. The other kind of copper atoms Cu(1) and Cu(1c) are coordinated in a square pyramidal environment by three nitrogen atoms from dien and two oxygen atoms from two adjacent TCB molecules, one of which lays above or below the 2-D network plane. These form a three-dimensional network structure. Moreover four carboxyl groups of TCB4- are divided to two types by their different coordination mode: (1) two para-carboxyl groups C(14)O(1)O(2) bridge the copper atom Cu(2) with one oxygen atom O(1) in monodentate fashion, (2) other two-carboxyl groups C(15)O(3)O(4) coordinate to Cu(1) and Cu(1d) in a bridging bidentate fashion. The magnetic susceptibility shows the weak antiferromagnetic interaction in two compounds because of the longer distances between two paramagnetic centers. (C) 1998 Elsevier Science Ltd. All rights reserved.