Coordination behavior of 1,4-diallylpiperazinium and 1-allyloxybenzotriazole toward silver(I) in the crystalline π-complexes [Ag2(C4H8N2(C3H5)2(H+)2)(H2O)2(NO3)2](NO3)2 and [Ag(C6H4N3(OC3H5)(NO3))

Abstract

Reactions of a solution of AgNO3 in aqueous methanol with solutions of 1,4-diallylpiperazine (acidified with HNO3 to pH = 4) and 1-allyloxybenzotriazole in ethanol gave the crystalline silver(I) π-complexes [Ag2(C4H8N2(C3H5)2(H+)2)(H2O)2(NO3)2](NO3)2 (I) and [Ag(C6H4N3(OC3H5)(NO3))] (II). Their crystal structures were determined by X-ray diffraction. Crystals of complexes I and II are monoclinic, space group P21/c; for I: a = 7.053(3)A, b = 9.389(3)A, c = 15.488(4)A, β = 91.60°, V = 1025.3(6)A3, Z = 4; for II: a = 10.650(4)A, b = 15.062(5)A, c = 7.412(4)A, β = 104.20(3)°, V = 1152.6(8)A3, Z = 4. In both structures, the organic components act as bidentate ligands forming with AgNO3 34- and 14-membered topological rings, respectively. In complex I, the nearly tetrahedral environment of the Ag(I) atom is made up of the olefinic C=C bond, the O atoms of the nitrate anions, and the water molecule. 1-Allyloxybenzotriazole in structure II causes the deformation of the coordination polyhedron of Ag into a trigonal pyramid via inclusion of the ligand N atom in its coordination sphere. The topological units of the complexes form infinite polymer layers linked by anionic NO 3 − bridges. In structure I, these layers are united through a system of hydrogen bonds into a three-dimensional framework.