Diverse Ag(i) complexes constructed from methyl-4-(5-halopyrimidin-2-ylcarbamoyl)benzoate ligands: roles of the halogen atom and anion

Abstract

The synthesis and structures of eight new silver(I) complexes [Ag(L1111)(NO3)]∞ (L1111 = methyl-4-(pyrimidin-2-ylcarbamoyl)benzoate), 1, [Ag2(L222)(NO3)2]∞ (L222 = methyl-4-(5-chloropyrimidin-2-ylcarbamoyl)benzoate), 2, [Ag2(L33)(NO3)2]∞ (L33 = methyl-4-(5-bromopyrimidin-2-ylcarbamoyl)benzoate), 3, [Ag(L44)(NO3)]∞ (L44 = methyl-4-(5-iodopyrimidin-2-ylcarbamoyl)benzoate), 4, {[Ag(L33)](BF4)·0.5THF}∞, 5, [Ag2(L44)4](BF4)2·2CH3OH, 6, and [Ag2(L44)4](X)2 (X = PF6−, 7; SbF6−, 8) are reported. In complexes 1–3, the L11–L33 ligands adopt the tridentate mode, featuring chelation and bridge through two pyrimidyl nitrogen atoms and one amidecarbonyl oxygen atom and resulting in a 1D chain for 1 and 2D nets for 2 and 3 with the topology of {4·6·8}{4·62·83}{62·8}, while in 4, the L44 ligand coordinates to the silver(I) metal center through one of the two pyrimidyl nitrogen atoms, the amide oxygen atom and the iodine atom to afford a 1D chain. The L33 ligands in 5 coordinate to the silver(I) metal centers in a tetradentate bonding mode through two nitrogen and two oxygen donor atoms, resulting in a 2D net with the topology of {4·62}2{42·62·82}. In complexes 6–8, the L44 ligands show both bidentate and tridentate fashions, showing dinuclear structures with ten-membered metallocycles. While the halogen atoms of 2 and 3 are involved in the X⋯O (X = Cl for 2 and Br for 3) interactions, short Ag–I bond distances of 2.7700(5) Å in 4 and 2.8925(10), 2.8353(9) and 2.8520(8) Å in 6–8 are found, which appear to be due to the high polarizability of the iodine atom.