Influence of the Crystallization Solvent on Molecular and Supramolecular Structures of Silver(I) Tris(3‐Phenylpyrazolyl)methane Complexes

The compound [{HC(3‐Phpz) 3 }Ag](BF 4 ) (pz = pyrazolyl ring) has been prepared and shown to crystallize in four different forms depending on the solvent. Vapor‐phase diffusion of diethyl ether into nitromethane solutions of the complex produces two polymorphs, an orthorhombic form ( 1 ) and triclinic form ( 2 ). Both polymorphs are coordination polymers constructed by a κ 2 −κ 1 coordination of the tris(3‐Phpz)methane units and have similar, but different, supramolecular structures. In 1 there are two independent chains linked by C−H ··· π interactions. In 2 only one type of chain is present, with a different internal structure than in 1 . Non‐covalent forces, mainly C−H ··· π interactions, organize the chains into sheets and the sheets into a final 3‐D supramolecular structure in the case of 1 , while in the case of 2 only a 2‐D supramolecular structure forms. In contrast, vapor‐phase diffusion of diethyl ether into acetonitrile or acetone solutions produces [{HC(3‐Ph‐pz) 3 }Ag{(CH 3 ) 2 CO}](BF 4 ) ( 3 ) and [{HC(3‐Phpz) 3 }Ag{CH 3 CN}](BF 4 ) ( 4 ). In these compounds, the ligand shows tripodal coordination to a single silver center and coordination of one solvent molecule to the metallic center. Both compounds form 3‐D supramolecular structures organized by both C−H ··· π interactions and weak C−H ··· F hydrogen bonds and in the case of 4 π−π stacking. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)