STRUCTURAL AND SPECTROSCOPIC FEATURES OF THE ADAMANTANE TYPE CU4S6 CORE FOUND IN CU(I) THIOLATES WITH BIDENTATE CHELATE LIGANDS

Six tetranuclear Cu(I) thiolate complexes have been synthesized with the bidentate thiolate ligands dithioethane (DTE) and dithiopropane (DTP). The cell dimensions are a = 10.887(3), b = 12.294(6), c = 22.308(3) angstrom, alpha = 96.94(2), beta = 96.66(l), gamma = 108.57(3)-degrees, space group = P1BAR and V = 2772 angstrom3 for [(C6H5)4P+]2[Cu4(DTP2-)3] (A); a = 11.820(6), b = 13.972(5), c = 21.371(6) angstrom, alpha = 71.83(2), beta = 77.01(3), gamma = 63.61(4)-degrees, space group = P1BAR and V = 2988 angstrom3 for [(C6H5)4P+]2[CU4(DTP2-)3].3MeOH (B); a = 9.779(3), b = 9.779(4), c = 17.694(6) angstrom, alpha = 90.0, beta = 90.0, gamma = 120.0-degrees, space group = P6(3) and V = 1465 angstrom3 for [(CH3)4N+]2[Cu4(DTP2-)3].MeOH (C); a = 15.835(3), b = 20.413(4), c = 9.866(1) angstrom, alpha = 90.0, beta = 91.05(l), gamma = 90.0-degrees, space group = P2(1)/n and V = 3188 angstrom3 for [(C2H5)4N+]2[Cu4(DTE2-)3] (D); a = 9.939(5), b = 9.939(8), c = 34.201(7) angstrom, alpha = 90.0, beta = 90.0, gamma = 90.0-degrees, tetragonal, V = 3378 angstrom3 for [C6H5CH2N+(CH3)3]2[Cu4(DTE2-)3] (E) and a = 10.899(2), b = 10.879(2), c = 18.604(3) angstrom, alpha = 90.0, beta = 90.0, gamma = 120.0-degrees, hexagonal, V = 1913 angstrom3 for [(C2H5)4N+]2[CU4(DTP2-)3].MeOH (F). The structures were refined to R/R(w) values (%) of 6.75/5.63, 4.60/5.70, 6.56/7.42 and 5.59/5.35 for A-D, respectively. All compounds exhibit an anionic 'adamantane' type Cu4S6 cluster unit. Within two of the structures, inserted solvent molecules are linked with the Cu-S core by S ... H-O hydrogen bonds. Crystallization of the anionic [Cu4(RS-)6]2- or [Cu4(-SRS-)3]2-units together with bulky ammonium cations yields white or pale yellow compounds, whereas yellow, orange or deep red crystals are formed using the (C6H5)4P+ cation as the counterion. A review of IR data of different [Cu4(RS-)6]2- or [Cu4(-SRS-)3]2- is given.