2-D Interwoven and 3-D 5-fold Interpenetrating Silver(I) Complexes of 1-(Isocyanidomethyl)-1H-benzotriazole and 1,3-Bis(dicyanomethylidene)indan

This paper presents novel and distinctive organosilver polymers with intriguing structure motifs, constructed from iodoacetonitrile (L¹), 1-(isocyanidomethyl)-1H-benzotriazole (L²), 1,3-bis(dicyanomethylidene)indan (L³), and silver(I) salts, respectively. Treatment of L¹ with AgClO₄ generated [Ag(L¹)(ClO₄)]_n (1), whose X-ray determination revealed a 2-D wavy sheet structure with square grids. Reaction of L² with AgPF₆ gave rise to a novel 2-D wavy interwoven network, {[Ag(L²)(PO₂F₂)_0.5](PF₆)_0.5}_n (2). The complex [Ag₂(L³)₂]_n (3) obtained by reaction of AgClO₄ with L³ can be regarded as unprecedented 3-D 5-fold interpenetrating nets with columnar aromatic stacks and indicates semiconductive behavior. The IR, ESR spectroscopic results, conductivities, and structural features of the complexes are discussed, respectively. The present findings may provide insight into the coordination versatility of silver(I) and polynitrile ligands and an inspiration for the self-assembly of novel supramolecular networks with multifunctional ligands. Crystal data:  1, C₂H₂AgINClO₄, orthorhombic, Pca2₁ (No. 29), a = 14.503(1) Å, b = 5.104(2) Å, c = 10.2019(9) Å, Z = 4; 2, C₈H₆AgN₄PF₄O, orthorhombic, Pnna (No. 52), a = 12.2705(3) Å, b = 21.150(1) Å, c = 10.040(1) Å, Z = 8; 3, C₃₀H₁₀Ag₂N₈, triclinic, P1̄ (No. 2), a = 14.920(2) Å, b = 11.896(2) Å, c = 7.400(4) Å, α = 86.55(2)°, β = 80.87(2)°, γ = 74.47(1)°, Z = 2.