Interaction of 4,4-bi(1,2,4-triazole) (btr) with copper(II) chloride (bromide) in aqueous or aqueous alcohol media led to a series of coordination polymers featuring the formation of mu 3-hydroxotricopper(II) clusters and their integration into 3D frameworks. These unprecedented structures originate in the propagation of trigonal hydroxotricopper(II) clusters bridged by tri- or tetradentate organic ligands. Complex [{Cu3(mu3-OH)}{Cu3(mu3-O)}(mu4-btr)3(H2O)4(OH)2Cl6]Cl.0.5H2O adopts a structure of SrSi2 topology, with eight-fold interpenetration of the coordination frameworks. The structure of [{Cu3(mu3-OH)}2(mu3-btr)6(mu4-btr)(mu-X)X4]X5.nH2O (X = Br, n = 6; X = Cl, n = 8) involves 2D coordination layers [{Cu3(mu3-OH)}(mu3-btr)3]n with an exceptional (3,6)-net topology, which are cross-linked by tetradentate btr ligands and bridging chloride (bromide) ions.

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Nine Cu II coordination compounds based on 4,4'-bi-1,2,4triazole (btr), [Cu 2 (N-btr) 2 nol solution and their structures were established with single X-ray diffraction. The coordination behavior of btr, which changes from simple monodentate, to N1,N1'-bi-, tri-and tetradentate binding modes, and the influence of the counteranions lead to a structural variety of the coordination compounds, ranging from molecular "Chinese lanterns" of type 1, through 2D square grids (2-4, 6, 8) and 3D octahedral networks (7), to 3D eight-connected frameworks (5, 9) that based on the dinuclear [Cu 2 (trz) 2 ] 4+ and linear trinuclear [Cu 3 (μ 2 -OH) 2 (H 2 O) 2 ] 4+ units as nodes. Analytical DataElemental analyses (C, H and N) were performed with a Perkin-Elmer 2400 analyzer.

Chloride-centered hexanuclear hydroxopyrazolate reveals potential as a receptor of halomethane and halometallate species and as a molecular building block for coordination polymers.