Conformation Restriction of Nonplanar Di-2-pyrimidyl Sulfide with Intramolecular N···C Interaction and Its Supramolecular Silver(I) Complexes

A series of silver­(I) complexes with semirigid di-2-pyrimidyl sulfide (DprS), namely, {[Ag<sub>2</sub>(DprS)<sub>2</sub>(CF<sub>3</sub>CO<sub>2</sub>)]­(CF<sub>3</sub>CO<sub>2</sub>)·2H<sub>2</sub>O}<sub>∞</sub> (<b>1</b>), {[Ag<sub>6</sub>(DprS)<sub>6</sub>(CF<sub>3</sub>SO<sub>3</sub>)<sub>5</sub>]­(CF<sub>3</sub>SO<sub>3</sub>)·3.5H<sub>2</sub>O}<sub>∞</sub> (<b>2</b>), {[Ag<sub>2</sub>(DprS)­(C<sub>2</sub>F<sub>5</sub>CO<sub>2</sub>)<sub>2</sub>]}<sub>∞</sub> (<b>3</b>), [Ag­(DprS)­(NO<sub>3</sub>)<sub>∞</sub> (<b>4</b>), and {[Ag<sub>3</sub>(DprS)<sub>3</sub>]­(ClO<sub>4</sub>)<sub>3</sub>}<sub>∞</sub> (<b>5</b>), have been synthesized and characterized by single-crystal X-ray analysis. The silver­(I) complexes <b>1</b>–<b>2</b> and <b>4</b>–<b>5</b> exhibit one-dimensional tape-like coordination polymers with different topological structures, while complex <b>3</b> has a two-dimensional coordination network. In these complexes, the two pyrimidyl rings of each DprS are almost in an orthogonal orientation, a rigid nonplanar conformation, and the multidentate ligand adopts an unvaried <i>N</i>,<i>N′</i>,<i>N″</i>-μ<sub>3</sub> ligation mode despite the different anions (CH<sub>3</sub>COO<sup>–</sup> in <b>1</b>, CF<sub>3</sub>SO<sub>3</sub><sup>–</sup> in <b>2</b>, C<sub>2</sub>F<sub>5</sub>COO<sup>–</sup> in <b>3</b>, NO<sub>3</sub><sup>–</sup> in <b>4</b>, and ClO<sub>4</sub><sup>–</sup> in <b>5</b>). Attractive intramolecular N<sub>pyrimidyl</sub>···C<sub>pyrimidyl</sub> interaction between a 1-positional N atom of one pyrimidyl ring and an electrophilic 2-positional C atom of the other ring of DprS is a common dominant interaction, which drives and stabilizes the nonplanar ligand conformation in these crystalline structures. Calculation through the self-consistent field crystal orbital method based on density functional theory indicates the presence of the N···C contact, a nucleophile–electrophile affinity. Unconventional anion−π<sub>pyrimidyl</sub> interactions engaged in the construction of the supramolecular architectures of <b>1</b>–<b>5</b> also are presented and discussed.