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Three kinds of copper(II) complexes with 1,4,7-tris(2-aminoethyl)-1,4,7-triazacyclononane (taetacn), [Cu(taetacn)](ClO4)2 (1), [Cu(Htaetacn)](ClO4)3 (2), and [Cu(Htaetacn)](BF4)3 (3) were synthesized and characterized by elemental analyses, IR and UV-Vis spectroscopies. The spectral features are in harmony with an octahedral geometry for 1 and a square-pyramidal coordination for 2 and 3. The crystal structure of 2 was determined by the single-crystal X-ray diffraction method at 293 K. It crystallizes in the orthorhombic space group Pnma with a = 20.605(3) A, b = 12.7944(18) A, c = 9.8972(14) A, V = 2609.2(6) A3, Dx = 1.582 g/cm 3, and Z = 4. The R1 [I > 2σ(I)] and wR2 (all data) values are 0.0723 and 0.2389, respectively, for all 3253 independent refl ections. The compound consists of squarepyramidal copper(II) cation with protonated Htaetacn and tetrahedral ClO4 – anions. The temperature dependence of magnetic susceptibilities obeyed the Curie-Weiss law with Ɵ = –2.4, –5.2 and –7.2 K for 1, 2, and 3, respectively. Cyclic voltammetry of 2 in DMF showed two quasi-reversible reduction waves (Epc = –0.98, Epc = –0.92; Epc = –1.30, Epc = –1.22 V versus Fc/Fc +).

Synthesis, Crystal Structure, and Properties of Copper(II) Complexes with 1,4,7-Tris(2-Aminoethyl)-1,4,7-Triazacyclononane