The Effects of Anion Variation and Ligand Derivatization on Silver Coordination Networks Based upon Weaker Interactions

This article presents a series of silver(I) coordination networks based upon nonchelating bidentate thioether ligands.
Frameworks using AgOTs as the silver(I) starting material form two-dimensional frameworks and are quite stable
as shown by differential scanning calorimetry/thermogravimetric analysis (DSC/TGA) data. The networks are
sufficiently robust as to maintain the same layered motif when the basic skeleton of the ligand is sequentially
derivatized with −OEt, OBu, and OHex groups. Crystal structures of the AgOTs complexes of the underivatized
and bis(hexoxy) derivatives, compounds 5 and 8, respectively, are presented as well as powder X-ray diffraction
(PXRD) data of the other complexes. For 5, C20H20S3O3Ag, crystal data are as follows:  monoclinic, space group
P21/n, a = 11.8117(5) Å, b = 7.8813(5) Å, c = 22.3316(10) Å, β = 102.245(5)°, V = 2031.6(2) Å3, Z = 4. For
8, C30H44S3O6Ag, crystal data are as follows:  triclinic, space group P1̄, a = 8.445(4) Å, b = 10.855(5) Å, c =
19.308(9) Å, α = 84.53(1)°, β = 78.76(1)°, γ = 68.43(1)° V = 1613.9(13) Å3, Z = 2. Changing the silver(I)
starting material to AgPF6 results in a shift to a one-dimensional structure, 9, as shown by X-ray crystallography
and in highly compromised stability. For 9, C14H16S2N2PF6Ag, crystal data are as follows:  monoclinic, space
group P2/n, a = 11.9658(11) Å, b = 3.9056(4) Å, c = 19.6400(18) Å, β = 92.87(1)°, V = 916.70(15) Å3, Z =
4.