Reactions of a Coordination Polymer Based on the Triangular Cluster [Cu_3(μ_3-OH)(μ-pz)_3]~(2+) with Strong Acids. Crystal Structure and Supramolecular Assemblies of New Mono-, Tri-, and Hexanuclear Complexes and Coordination Polymers

摘要

A series of mono-, tri-, hexanuclear compounds, and coordination polymers were obtained from the reaction of [Cu_3(μ_3-OH)(μ-pz)_3(MeCOO)_2(Hpz)], 1, (Hpz = pyrazole) with H_2SO_4, H_3PO_4, HClO_4, HNO_3, CF_3COOH, and CF_3SO_3H. The trinuclear [Cu_3(μ_3-OH)(μ-pz)_3(SO_4)(Hpz)_3] .H_2O, 2t, forms a one-dimensional coordination polymer through bridging SO_4 ~(2-). The mononuclear [Cu(H_2PO_4)_2(Hpz)_4], 3m, is instead the unique (pure) compound isolated in our conditions from the reaction of 1 with H_3PO_4, whereas both [Cu(ClO_4)_2(Hpz)_4], 4m, and [{Cu_3(μ_3-OH)(μ-pz)_3(ClO_4)(Hpz)_3}_2(μ_2-ClO_4)_2], 4h, have been isolated from the reaction with aqueousHClO_4, the latter being a hexanuclear species formed by two trinuclear triangular units connected through two bridging perchlorates. Moreover, the three already reported species [Cu_3(μ_3-OH)(μ-pz)_3(NO_3)(μ_3-NO_3)(Hpz)_2], 5t, [{Cu_3(μ_3-OH)- (μ-pz)_3(NO_3)(Hpz)_3}2(μ_2-NO_3)_2], 5h, and [Cu(NO_3)_2(Hpz)_4], 5m, are formed in the reaction of 1 with HNO_3. Three pure fractions, containing crystals of the trinuclear [Cu_3(μ_3-OH)(μ-pz)_3(CF_3COO)_2(Hpz)_2], 6t, and two mononuclear adducts, [Cu(CF_3COO)~(2-) (HPz_)4], 6m(a), and [Cu(CF3COO)2(Hpz)2], 6m(b), have been isolated when 1 was reacted with aqueousCF3COOH.Analogously, in the reaction of 1 with CF_3SO_3H, three different species were obtained, the mononuclear [Cu(CF_3SO_3H)_2(Hpz)_4], 7m, the trinuclear [Cu_3(μ_3-OH)(μ-pz)_3(CF_3SO_3)2(Hpz)_3] .H_2O, 7t, and the hexanuclear [{Cu_3(μ_3-OH)(μ-pz)_3(Hpz)_3}{Cu_3(μ_3-O)(μ-pz)_3(Hpz)_3}]- (CF_3SO_3)_3, 7h, where the two trinuclear units are strongly bonded through an unequally shared H-bond involving (μ_3-OH) and (μ_3-O) [O...O 2.54(1) A °, O(2)-H(2) .... O(1) 180]. All compounds were fully characterized by single-crystal X-ray diffraction determinations, UV-vis and IR spectra, electrospray ionization mass spectrometry, and magnetic susceptibility measurements.