Tuning the Framework Formation of Silver(I) Complexes with Flexible Bis(benzothiazol-2-ylsulfanyl)alkanes by Varying the Ligand Spacers and Counteranions

In our efforts to systematically investigate the influences of terminal groups, ligand spacers, and
counteranions on the framework formations of the AgI complexes with thioether ligands, four structurally related
flexible N-containing heterocyclic thioethers, bis(benzothiazol-2-ylsulfanyl)methane (L), 1,3-bis(benzothiazol-2-ylsulfanyl)propane (L), 1,4-bis(benzothiazol-2-ylsulfanyl)butane (L) and 1,5-bis(benzothiazol-2-ylsulfanyl)pentane
(L), and seven new AgI complexes of these ligands, [AgL1(NO3)]∞ 1, {[AgL1](ClO4)(H2O)}2 2, {[AgL2(NO3)](CHCl3)}2
3, {[AgL3](ClO4)}∞ 4, {[AgL3](BF4)}∞ 5, {[AgL4(NO3)]CHCl3}2 6, and {[AgL4(ClO4)]2}∞ 7, have been synthesized and
characterized. The crystal structures of these complexes show that all the other complexes except 4 and 5 form
ligand-supported dinuclear clusters, and in 1 and 7 the dinuclear cluster units are further linked by anions to form
1D chains, and complexes 4 and 5 exhibit 1D zigzag chain structures. Furthermore, these ligands coordinate to AgI
ions in N,N-bidentate rather than N,N,S-tridentate or N,N,S,S-tetradentate modes, and the AgI centers adopt 2- to
5-coordination geometries with different coordination environments. In 1, 2, 3, 6, and 7, the coordination modes of
the ligands are not sensitive to the changes of the spacers, and the terminal groups seem to be the determining
factor in controlling the coordination modes of the ligands. However, the differences of the -(CH2)n- ligand spacers
also contribute to the geometrical differences of the dinuclear units. The structural differences between 1 and 2, 6,
and 7 show the influences of the counteranions on the coordination geometries of AgI ions and the structures of the
complexes.