Cationic Silver Coordination Compounds of Polydentate Ligands: Supramolecular Structures of [Ag(Pz bp2 Py) 2 (OSO 2 CF 3 )] and [Ag 2 (Pz bp2 Py) 2 (OSO 2 CF 3 ) 2 ] {Pz bp2 Py = 2‐[3,5‐Bis(4‐butoxyphenyl)pyrazol‐1‐yl]pyridine}

The new silver complexes [Ag(Pz bp2 Py) 2 (OSO 2 CF 3 )], [Ag 2 (Pz bp2 Py) 2 (OSO 2 CF 3 ) 2 ], [Ag(Pz bp Py) 2 (OSO 2 CF 3 )], [Ag 3 (TPz bp2 Tz)(OSO 2 CF 3 ) 3 ] and [Ag 3 (TPz bp Tz)(OSO 2 CF 3 ) 3 ] ( 5 – 9 ) have been obtained by reaction of Ag(OSO 2 CF 3 ) with the corresponding polydentate ligand 2‐[3,5‐bis(4‐butoxyphenyl)pyrazol‐1‐yl]pyridine (Pz bp2 Py, 1 ), 2‐[3‐(4‐butoxyphenyl)pyrazol‐1‐yl]pyridine (Pz bp Py, 2 ), 2,4,6‐tris[3,5‐bis(4‐butoxyphenyl)pyrazol‐1‐yl]‐1,3,5‐triazine (TPz bp2 Tz, 3 ) and 2,4,6‐tris[3‐(4‐butoxyphenyl)pyrazol‐1‐yl]‐1,3,5‐triazine (TPz bp Tz, 4 ), respectively. The coordination effects induced on the 1 H, 13 C and 15 N NMR chemical shifts of the complexes in solution and in the solid state have been quantified, with the 15 N NMR spectra being used as a tool to establish the coordination site. All complexes are consistent with an N , N′ ‐chelating coordination at each silver centre involving nitrogen atoms from pyrazole and pyridine groups for 5 and 7 or from pyrazole and triazine groups for 8 and 9 . An additional Ag ··· OSO 2 CF 3 interaction completes the environment around the silver atom, giving rise to a five‐coordination or a three‐coordination for complexes 5 and 7 and 8 and 9 , respectively. The X‐ray structures of 5 and 6 confirm the presence of the N , N′ ‐chelating coordination of the Pz bp2 Py ligands and the coordinative participation of the CF 3 SO 3 counterion in the metal environment. The Ag ··· η 2 ‐arene bonds between neighbouring units in 6 are responsible for the dimers containing four‐coordinate silver atoms. At a supramolecular level, Ag ··· O, C–H ··· O or C–H ··· F interactions generate a 2D network in both compounds. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)