Four- and five-coordinate metal atoms in a supramolecular polymeric assembly of silver(I) with (4-methyl-2-quinolylthio)acetate

Abstract

The coordination compound [Ag₂L₂(H₂O)₂] · ₂H₂O (I), L = C₁₂H₁₀NO₂S has been synthesized by the reaction of AgNO₃ with 4-methyl-2-quinolylthioacetic acid (HL) preliminarily neutralized with an equimolar amount of NBu₄OH. Its crystal structure has been determined, and luminescence properties have been studied. Crystals of I are monoclinic, space group C2/_c, _a = 31.239(6) Å, _b = 12.056(2) Å, _c = 16.846(3) Å, β = 122.17(3)°, V = 5370.4(2) ų, ρ_calc = 1.861 g/cm³, Z = 16. The structure is formed by two crystallographically nonequivalent silver atoms Ag(1) and Ag(2) and two tridentate bridging ligands L coordinated through the S, N, and O atoms. These atoms, together with water molecules, form the coordination environments of the metal atoms with CN = 5 and 4, respectively. The Ag⁺ ions and the tridentate ligands form infinite [Ag₄L₄]_n bands extended in the [001] direction. The presence of outer-sphere water molecules involved in O–H···O hydrogen bonding is responsible for the formation of a supramolecular framework structure. The photoluminescence spectrum of compound I shows two bands at ~450 and ~485 nm corresponding to the blue spectral range.