Conformation Restriction of Nonplanar Di-2-pyrimidyl Sulfide with Intramolecular N···C Interaction and Its Supramolecular Silver(I) Complexes
dataset
posted on 2012-01-04, 00:00 authored by Chong-Qing Wan, Zi-Jia Wang, Guo Wang, Hao Liu, Yu-Heng Deng, Qiong-Hua JinA 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.
