Hydrothermal syntheses and characterizations of thioarsenates [Fe(phen)3][As3S6] x dien x 7 H2O and [Mn2(phen)4(As2S5)] x phen x 2 H2O: a new coordination mode of the As2S5(4-) anion.

Novel hydrogen-bonded supramolecular thioarsenates [Fe(phen)(3)][As(3)S(6)] x dien x 7 H(2)O (1) and [Mn(2)(phen)(4)(As(2)S(5))] x phen x 2 H(2)O (2) (dien = diethylenetriamine, phen = 1,10-phenanthroline) were hydrothermally synthesized and characterized. The structure of 1 consists of [As(3)S(6)](3-)-H(2)O anionic layers and [Fe(phen)(3)](3+)-dien cationic layers assembled via O-H...S and O-H...N hydrogen-bonding interactions. The layers stack alternately and are parallel to each other to give a 3D network structure with channels accommodating unique branched water chains, which are anchored on the anionic and cationic layers via hydrogen bonds. In 2, the [As(2)S(5)](4-) anion acts as a tetradentate brigding ligand via four terminal S atoms to link two [Mn(phen)(2)](2+) cations, forming the neutral complex [Mn(2)(phen)(4)(As(2)S(5))]. This is a new coordination mode for the [As(2)S(5)](4-) ion. [Mn(2)(phen)(4)(As(2)S(5))], phen, and H(2)O form a 3D network structure via O-H...S, O-H...O, and pi-pi stacking interactions.