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DOI: 10.1039/A701138E (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 2315-2320

Two new tetranuclear µ4-carbonato copper(II) complexes. Syntheses, crystal structure and magnetic behaviour of [(µ4-CO3)(µ-Br)2 {Cu4(bapa)4}]Br4 and [(µ4-CO3)(µ-Cl)2 {Cu4(bapma)4}]Cl4 ·12H2O [bapa = bis(aminopropyl)amine and bapma = bis(aminopropyl)methylamine]

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Albert Escuer, Evaristo Peñalba, Ramon Vicente, Xavier Solans and Mercé Font-Bardía

Abstract

The syntheses, by fixation of atmospheric CO2, and the crystal structures of the new tetranuclear µ4-CO32- compounds [(µ4-CO3)(µ-Br)2{Cu4 (bapa)4}]Br4 1 and [(µ4-CO3)(µ-Cl)2{Cu4 (bapma)4}]Cl4·12H2O 2, [bapa and bapma are bis(3-aminopropyl)amine and bis(3-aminopropyl)methylamine respectively] are reported. Crystallographic data for 1 space group C2/c, a = 14.928(5), b = 19.010(3), c = 17.337(4) Å, β = 92.75(4)°, U = 4914(2) Å3 and Z = 4, for 2 space group P21/n, a = 14.947(6), b = 13.047(4), c = 16.084(5) Å, β = 104.75(5)°, U = 3033(2) Å3 and Z = 2. The analogous compound [(µ-CO3)(µ4-Cl)2{Cu4 (bapa)4}]Cl4 3 has been also prepared for comparative purposes; 1–3 show very strong antiferromagnetic coupling. According to the molecular structures, the experimental data were fitted to the expression derived from the Hamiltonian H = -2J12S 1·S2 - 2 J13 (S1·S3 + S2S4) - 2 J14 (S1·S4 + S2·S3) - 2J34 S3·S4, which corresponds to a rectangular array of spins. The best fit parameters were for 1–3 respectively: 2J12 = -275(14), -390(12), -212(8); 2J34 = -31(4), -26(7), -26(3); 2J14 = -57(10), -10(12), -72(9); 2J13 = -8(8), 22(10), -20(7) cm-1; g = 2.03(1), 2.09(1) and 2.12(1).

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