Inorganic Chemistry, Vol.48, No.12, 5412-5417, 2009
Hydrothermal Syntheses and Characterizations of Thioarsenates [Fe(phen)(3)] [As3S6]center dot dien center dot 7H(2)O and [Mn-2(phen)(4)(As2S5)]center dot phen center dot 2H(2)O: A New Coordination Mode of the As2S54- Anion
Novel hydrogen-bonded supramolecular thioarsenates [Fe(phen)(3)][As3S6]center dot dien center dot 7H(2)O (1) and [Mn-2(phen)(4)(As2S5)]center dot phen center dot 2H(2)O (2) (dien = diethylenetriamine, phen = 1,10-phenanthroline) were hydrothermally synthesized and characterized. The structure of 1 consists of [As3S6](3-)-H2O anionic layers and [Fe(phen)(3)](3+)-dien cationic layers assembled via O-H center dot center dot center dot S and O-H center dot center dot center dot 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 [As2S5](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)(As2S5)]. This is a new coordination mode for the [As2S5](4-) ion. [Mn-2(phen)(4)(As2S5)], phen, and H2O form a 3D network structure via O-H center dot center dot center dot S, O-H center dot center dot center dot O, and pi-pi stacking interactions.