Syntheses And Structures Of Mo(W)/Cu/S Cluster Compounds Containing Nitrogen Donor Ligands

Reactions of [Et4N]2[WOS3] with CuI and bis(3,5-dimethylpyrazolyl)methane (dmpzm) in MeCN afforded one tetranuclear cluster [WOS3Cu3I(dmpzm)2]·2(MeCN)0.5 (1·2(MeCN)0.5) while those of [PPh4]2[WS4] with CuI and dmpzm in DMF/MeCN gave rise to a pentanuclear cluster [WS4Cu4I2(dmpzm)2]·DMF (2·DMF). Both compounds were characterized by elemental analysis, IR, and single-crystal X-ray diffraction analysis. 1·2(MeCN)0.5 crystallizes in triclinic system with space group Pīand a = 11.4552(5), b = 11.6735(3), c = 16.2278(9) ?,α= 99.537(9),β= 101.986(2) ,γ= 118.464(13)o, V = 1775.5(3) ?3, Z = 2,μ= 6.080 mm-1, Dc = 1.983 Mg/m3, T = 193(2) K, C24H35Cu3IN9OS3W, Mr = 1063.22, F(000) = 1018, S = 1.060, R = 0.0376 and wR = 0.0870. 2·DMF crystallizes in the orthorhombic system with space group Pmn21 and a = 22.145(4), b = 11.464(2), c = 7.7370(15) ?, V = 1964.2(6) ?3, Z = 2,μ= 6.865 mm-1, Dc = 2.189 Mg/m3, T = 193(2) K, C25H39Cu4I2N9OS4W, Mr = 1301.72, F(000) = 1226, R = 0.0632, wR = 0.1706 and S = 1.130. 1·2(MeCN)0.5 consists of one CuI and two [Cu(dmpzm)]+ fragments that are linked by the [WOS3]2- species via six Cu-S bonds, forming a nido-like [WS3Cu3] core. 2·DMF contains a saddle-shaped [WS4Cu4] core with two iodides being coordinated at two Cu centers in a cis position and two dmpzm ligands being chelated at another two Cu centers in a cis position.Reactions of a preformed cluster [PPh4][(η5-C5Me5)MoS3(CuNCS)3] (3) with three 4-pyridyl-based bridging ligands with different spacer lengths, 4,4'-bipyridine (4,4'-bipy), 1,2-bis(4-pyridyl)ethylene (bpe) and 1,2-bis(4-pyridyl)ethane (bpa), afforded three new cluster-based supramolecular compounds {[(η5-C5Me5)MoS3Cu3(4,4'-bipy)1.5(μ-NCS)(NCS)]·DMF·MeCN}n (4), {[(η5-C5Me5)MoS3Cu3(bpe)1.5(μ-NCS)(NCS)]·0.5(bpe)·2(DMF)}n (5) and {[(η5-C5Me5)MoS3Cu3(bpa)1.5(μ-NCS)(NCS)]·0.5(bpa)·0.25(DMF)}n (6). Compounds 4-6 were characterized by elemental analysis, IR, UV-Vis, 1H NMR and single-crystal X-ray crystallography. Compound 4 has a 2D waterfall-like (4,4) network while 5 or 6 has a 2D brick-wall (6,3) network.