Mercury(II) thiolate complexes of two flexible benzimidazole‐based ligands

The structure of catena‐poly[[{bis[4‐(trimethylammonio)benzenethiolate‐κS]mercury(II)}‐μ‐1,1′‐(ethane‐1,2‐diyl)bis(1H‐benzimidazole)‐κ²N³:N^3′] bis(hexafluoridophosphate) 0.25‐hydrate], {[Hg(C₁₆H₁₄N₄)(C₉H₁₃NS)₂](PF₆)₂·0.25H₂O}_n, contains a one‐dimensional zigzag chain. The Hg^II cation is coordinated by two S atoms of two 4‐(trimethylammonio)benzenethiolate (Tab) ligands and by two N atoms from two different 1,1′‐(ethane‐1,2‐diyl)bis(1H‐benzimidazole) ligands, forming a distorted seesaw‐shaped coordination geometry. The F atoms of the hexafluoridophosphate anion interact with the H atoms of the Tab ligand, generating a two‐dimensional network. Furthermore, this layer is connected to neighbouring layers via H...π interactions, thereby forming a three‐dimensional hydrogen‐bonded structure. In catena‐poly[[{[4‐(trimethylammonio)benzenethiolate‐κS]mercury(II)}bis[μ‐4‐(trimethylammonio)benzenethiolate‐κ²S:S]{[4‐(trimethylammonio)benzenethiolate‐κS]mercury(II)}‐μ‐1,1′‐(hexane‐1,6‐diyl)bis(1H‐benzimidazole)‐κ²N³:N^3′] tetrakis(hexafluoridophosphate)], {[Hg₂(C₂₀H₂₂N₄)(C₉H₁₃NS)₄](PF₆)₄}_n, each Hg^II cation is coordinated by two S atoms of two Tab ligands and one N atom of the 1,1′‐(hexane‐1,6‐diyl)bis(1H‐benzimidazole) (hbbm) ligand, forming a distorted T‐shaped coordination geometry, while longer secondary Hg...S bonds join two such units across a centre of inversion to give the tetravalent cation. Adjacent {[Hg(Tab)₂]₂(μ‐hbbm)}⁴⁺ cations are linked through the centrosymmetric hbbm ligands to afford a one‐dimensional chain extending along the b axis. Several F atoms interact with the H atoms of the Tab and hbbm ligands, while the S atom interacts with an aromatic H atom of a different Tab ligand, to afford a complex intra‐ and intermolecular hydrogen‐bonding arrangement in a three‐dimensional structure.