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.

The solvothermal synthetic system Ln/Sb/Se (Ln = La, Eu) was investigated in different ethylene polyamines, and a series of lanthanum and europium selenidoantimonates [La(en)(2)(dien)(eta(2)-SbSe(4))] (Ia), [La(dien)(2)(mu-eta(1),eta(2)-SbSe(4))] (Ib), [La(trien)(2)(H(2)O)]SbSe(4) (Ic), [La(en)(trien)(mu-eta(1),eta(2)-SbSe(4))] (Id), [Eu(en)(2)(dien)(SbSe(4))] (IIa), [Eu(en)(trien)(eta(2)-SbSe(4))] (IIb), and [Eu(dien)(2)(eta(2)-SbSe(4))] (IIc) (en = ethylenediamine, dien = diethylenetriamine, trien = triethylenetetramine) were prepared. A systematic investigation of the crystal structures showed that the soft Lewis basic ligand [SbSe(4)](3-) can be tuned to coordinate to the hard Lewis acidic lanthanide ions as a monodentate ligand, mono-SbSe(4); a bidentate chelating ligand, eta(2)-SbSe(4); or a tridentate bridging ligand, mu-eta(1),eta(2)-SbSe(4), by the ethylene polyamines or mixed ethylene polyamines used in the syntheses. The [SbSe(4)](3-) anion exhibited different coordination modes for La(3+) and Eu(3+) ions in the presence of the same ethylene polyamine because of the different coordination numbers of La(3+) and Eu(3+) ions.

No abstract

New transition metal chalcogenidogermanates [{Co(tepa)} 2 -(μ-Ge 2 S 6 )] (1) and [{M(tepa)} 2 (μ-Ge 2 Se 6 )] (M = Mn (2), Fe (3); tepa = tetraethylenepentamine) were synthesized with GeO 2 , S(Se) and transition metal chloride as starting materials in tepa under solvothermal conditions. Complexes 1-3 crystallize in isostructural tetragonal space group I4 1 /a. In 1-3, the hexachalcogenidodigermanate anions are composed of two GeS 4 or GeSe 4 tetrahedra sharing a common edge, and act as bridging ligands by the trans terminal chalcogen atoms to link

No abstract