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

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journal contribution
posted on 04.01.2012, 00:00 authored by Chong-Qing Wan, Zi-Jia Wang, Guo Wang, Hao Liu, Yu-Heng Deng, Qiong-Hua Jin
A series of silver­(I) complexes with semirigid di-2-pyrimidyl sulfide (DprS), namely, {[Ag2(DprS)2(CF3CO2)]­(CF3CO2)·2H2O} (1), {[Ag6(DprS)6(CF3SO3)5]­(CF3SO3)·3.5H2O} (2), {[Ag2(DprS)­(C2F5CO2)2]} (3), [Ag­(DprS)­(NO3) (4), and {[Ag3(DprS)3]­(ClO4)3} (5), have been synthesized and characterized by single-crystal X-ray analysis. The silver­(I) complexes 12 and 45 exhibit one-dimensional tape-like coordination polymers with different topological structures, while complex 3 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 N,N′,N″3 ligation mode despite the different anions (CH3COO in 1, CF3SO3 in 2, C2F5COO in 3, NO3 in 4, and ClO4 in 5). Attractive intramolecular Npyrimidyl···Cpyrimidyl 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−πpyrimidyl interactions engaged in the construction of the supramolecular architectures of 15 also are presented and discussed.