HOMONUCLEAR AND HETERONUCLEAR METAL-COMPLEXES WITH A CYCLIC CU(II)4 UNIT - SYNTHESES, CRYSTAL-STRUCTURES, AND MAGNETIC-PROPERTIES OF [CU(II)4(DMAP)3(OH)(O2CCH3)2(HO2CCH3)(H2O)][PF6]2, [CU(II)4(DMAP)2(O2CCH3)4][PF6]2, [CU(II)4(DMAP)2(O2CCH3)2(OH)2][HG(II)(O2CCH3)CL2]2[HG(II)CL2], AND [CU(II)4(DMAP)2(O2CCH3)3(OH)2(H2O)][PF6] (DMAP = 1,3-BIS(DIMETHYLAMINO)-2-PROPANOLATO)

A new class of tetranuclear copper complexes with planar cyclic structures has been synthesized by using 1,3-bis(dimethylamino)-2-propanolato and acetate ligands. Four members of this class of molecules have been characterized structurally. Compound 1 with the formula [Cu(II)4(dmap)3(OH)(O2CCH3)2(HO2CCH3)(H2O)][PF6]2 and compound 2 with the formula [Cu(II)4(dmap)2(O2CCH3)4][PF6]2 are discrete molecular complexes in the solid. Compound 3 with the formula [Cu4II(dmap)2-(O2CCH3)2(OH)2][Hg(II)(O2CCH3)Cl2]2[Hg(II)Cl2] and compound 4 with the formula of [Cu4II(dmap)2(O2CCH3)3(OH)2-(H2O)][PF6] have one-dimensional structures in the solid state. The Cu4 units in 3 are linked through Hg(II)3 chains, while the Cu4 units in 4 are linked through intermolecular hydrogen bonds. 1 crystallizes in the triclinic crystal system, space group P1BAR, a = 13.289 (6) angstrom, b = 15.737 (6) angstrom, c = 13.214 (5) angstrom, alpha = 97.29 (4)-degrees, beta = 96.24 (4)-degrees, gamma = 103.77 (3)-degrees, Z = 2. 2 crystallizes in the monoclinic crystal system, space group P2(1)/n, a = 10.154 (5) angstrom, b = 12.712 (4) angstrom, c = 15.405 (9) angstrom, beta = 99.05 (6)-degrees, Z = 2.3 crystallizes in the monoclinic crystal system, space group P2(1)/n, a = 12.524 (8) angstrom, b = 12.358 (7) angstrom, c = 14.563 (8) angstrom, beta = 94.24 (5)-degrees, Z = 2. 4 crystallizes in the triclinic crystal system, space group P1BAR, a = 13.34 (1) angstrom, b = 13.992 (8) angstrom, c = 11.726 (8) angstrom, alpha = 113.59 (4)-degrees, beta = 95.71 (8)-degrees, gamma = 74.54 (7)-degrees, Z = 2. The magnetic susceptibility of 3 has been measured in the temperature range 5-350 K. Results from the best fitting of the experimental data at 0.5 kG indicate that antiferromagnetic exchange dominates in this compound, j12 = j34 = -186.5 cm-1, j23 = j14 = 39.7 cm-1, j24 = j13 = -4.4 cm-1.