SELF-ASSEMBLY OF COPPER(I) AND SILVER(I) BUTTERFLY CLUSTERS WITH 2-MERCAPTOTHIAZOLINE

X-ray data obtained from poor crystals which formed from the reaction of copper(II) acetate with 2-mercaptothiazoline reveal the formation o f a product that is a polymer formed of tetranuclear, butterfly shaped Cu-4(NIT)(4), 1, clusters. Preparation, isolation and structural char acterization of a series of isostructural butterfly complexes was acco mplished by addition of a Lewis base (pyridine, PPh(3), or AsPh(3)) to the precipitate obtained from the reaction of copper(II) and/or silve r(I) acetate with the appropriate stoichiometric amount of 2-mercaptot hiazoline. The general formula of these clusters is L(2)M(4)(MT)(4); 2 , L = PPh(3) and M = Cu; 3, L = AsPh(3) and M = Cu; 6, L = PPh(3) and M = Ag; MT = C3H4NS2-, known as 2-mercaptothiazolinate. The polymer [p yCu(4)(MT)(4)](n), 4, formed by the addition of pyridine to 1, was als o characterized crystallographically. A mixed metal butterfly complex, (PPh(3))(2)Ag2Cu2(MT)(4), 8, is formed by addition of PPh(3) to a sus pension of the precipitate formed upon reaction of the free HMT ligand with a 1:1 mixture of copper(II) and silver(I) acetates in CH2Cl2. FD -MS results of each of the precipitates obtained from the metal acetat es and the free ligand indicate that the monomeric unit, is M(4)(MT)(4 ) H-1-NMR and P-31{H-1}-NMR, both in solution and in the solid state a re presented and interpreted. The solid state structures of these mole cular complexes were determined by single crystal X-ray analysis. Four of them crystallize in the monoclinic space group C2/c (No. 15) with Z = 4, and unit cell dimensions: 2, a = 15.558(6), b = 11.945(5), c = 27.927(9) Angstrom, beta = 94.676(3)degrees 3, a = 15.632(8), b = 11.9 51(6), c = 28.156(16) Angstrom, beta = 94.04(4)degrees; 8, a 14.656(6) , b = 12.231(6), c = 29.613(7) Angstrom, beta = 97.71(3)degrees; 8, a = 15.559(3), b = 11.939(2), c = 28.201(6) Angstrom, beta = 94.71(3)deg rees. Polymer 4 crystallizes in the space group P1 (No. 2) with Z = 2 and unit cell dimensions: a = 8.900(6), b = 12.537(9), c = 12.887(9) A ngstrom, alpha = 72.34(5)degrees, beta = 78.06(5)degrees, gamma = 88.2 3(6)degrees.