Unsupported intermolecular argentophilic interaction in the dimer of trinuclear silver(I) 3,5-diphenylpyrazolates

The reaction of a solution of sodium 3,5-diphenylpyrazolate, Na[Ph(2)pz], with Ag(tht)NO3 in dichloromethane affords thin needles of unsolvated and light-stable dimer of trimers [Ag-3(mu-3,5-Ph(2)pz)(3)](2). The complex is characterized by X-ray crystallography and elemental analysis. The two trimers are rotated anti to each other. Three silver atoms bridged through exobidentate pyrazolate groups form a slightly puckered nine-membered ring with the shortest Ag (...) Ag intramolecular interaction in the metallocycle of 3.3571(8) angstrom. The other two silver centers are weakly interacting, Ag(3) (...) Ag(l) = 3.49 angstrom and Ag(3)... Ag(2) = 3.52 k. The intermolecular interaction between the two trimers is Ag (...) Ag = 2.9712(14) angstrom. Packing diagram shows the dimer of trimer units are independent. Density Functional Theory calculations show that the M (...) M interaction is due to dispersion forces. [Ag-3(mu-3,5-Ph(2)pz)(3)](2) crystallizes in the monoclinic space group C2/c with a = 22.169(4), b = 15.269(3), c = 22.482(5) angstrom, ss = 103.69(3)degrees and V = 7394(3) angstrom(3). (c) 2004 Elsevier B.V. All rights reserved.