Beatrix Seidlhofer

Review. Synthesis of Inorganic-Organic Hybrid Thiometallate Materials with a Special Focus on Thioantimonates and Thiostannates and in situ X-Ray Scattering Studies of their Formation

A rich variety of inorganic-organic hybrid thioantimonates and thiostannates were prepared during the last few years under solvothermal conditions applying organic amine molecules or transition metal complexes as structure directors. In this review synthetic approaches to and structural features of these thiometallates are discussed. For thioantimonates(III) the structures range from well isolated thioanions to three-dimensional networks, whereas the structural chemistry of thiostannates(IV) is strongly dominated by the [Sn2S6]4− anion, and no three-dimensional thiostannate has been reported so far. In the structures of thioantimonates(III) several primary building units like the [SbS3] trigonal pyramid, the [SbS4] unit or even the [SbS5] moiety are joined by vertex- and/or edge-linkages to form building blocks of higher structural hierarchy like [Sb3S4] semi-cubes or SbxSx heterocycles. A pronounced difference between thioantimonate and thiostannate chemistry is the tendency of Sb(III) to enhance the coordination geometry via so-called secondary bonds. In most cases the environment of Sb(III) is better described as a 3+n polyhedron with n = 1 - 3. The thioantimonate(V) structural chemistry is less rich than that of thioantimonates(III), and the [SbS4]3− anion shows no tendency for further condensation. By applying suitable multidentate amine molecules, transition metal cations which normally prefer bonding to the N atoms of the amines can be incorporated into the thiometallate frameworks Graphical Abstract Review. Synthesis of Inorganic-Organic Hybrid Thiometallate Materials with a Special Focus on Thioantimonates and Thiostannates and in situ X-Ray Scattering Studies of their Formation

Controlling Nucleation and Crystal Growth of a Distinct Polyoxovanadate Cluster: An In Situ Energy Dispersive X‐ray Diffraction Study under Solvothermal Conditions

The formation of the antimonato polyoxovanadates [V(14)Sb(8)(C(6)H(15)N(3))(4)O(42)(H(2)O)]·4H(2)O (1), (C(6)H(17)N(3))(2)[V(15)Sb(6)(C(6)H(15)N(3))(2)O(42)(H(2)O)]·2.5H(2)O (2), {C(6)H(15)N(3)}(4)[V(16)Sb(4)O(42)]2H(2)O (3) (C(6)H(15)N(3)=1-(2-aminoethyl)piperazine, AEP) has been studied under solvothermal conditions by using in situ energy dispersive X-ray diffraction (EDRXD). The syntheses were performed with an identical ratio for Sb(2)O(3) and NH(4)VO(3). If the reactions slurries are not stirred during the solvothermal reaction and by applying 70-75% amine concentration, the products contain all three compounds, whereas 3 is observed at 80%. Under stirring conditions, variation of the concentration of AEP led to crystallization of the three different compounds at distinct concentrations, that is, 1 is formed at 75%, 1 and 2 between 75 and 80% and 3 at 80%. At an amine concentration of 77.5%, first reflections of 2 occurred and at later stages, compound 1 started to crystallize. The sample with the lowest number of V(IV) species was formed at the lowest amine concentration, whereas crystallization of 3 required the highest concentration. The formation of the compounds occurred without crystalline intermediates and/or precursors. With increasing reaction temperature, the incubation time was significantly reduced.

Using a Ni2+ complex as a structure-directing molecule: solvothermal synthesis and properties of [Ni(en)(tren)]4Sb14S25 featuring an unprecedented three-dimensional network architecture

The new thioantimonate [Ni(en)(tren)]4Sb14S25 (1) (tren = tris(2-aminoethyl)amine, en = ethylendiamine) was synthesized under solvothermal conditions using the complex [Ni(en)3]Cl2 as a structure-directing molecule in a slurry of Sb, S and tren as solvent. Under these reaction conditions two of the three en ligands in the [Ni(en)3]Cl2 complex are exchanged by one tren molecule. Compound 1 crystallises in the monoclinic space group P21/c with 4 formula units in the unit cell. Four unique Ni2+ complexes are chelated by one tetradentate tren and one bidentate en molecule. The three-dimensional 3∞[Sb14S25]8− anion is constructed by interconnection of [SbS3] and [SbS4] units forming [Sb2S2], [Sb3S3], [Sb14S14] and [Sb20S20] heterorings as the next hierarchical building groups. The two largest rings are condensed to form the three-dimensional thioantimonate(III) anions. Three different types of channels are identified with diameters of about 7 × 9, 9 × 17, and 8 × 9 A. The Ni2+ complexes occupy the channels and are located above and below the [Sb14S14] and [Sb20S20] heterorings.

[N,N-Bis(2-amino-eth-yl)ethane-1,2-diamine](ethane-1,2-diamine)-nickel(II) thio-sulfate trihydrate.

The title compound, [Ni(C2H8N2)(C6H18N4)]S2O3·3H2O, was accidentally synthesized under solvothermal conditions applying [Ni(en)3]Cl2 (en is ethane-1,2-diamine) as the Ni source. The asymmetric unit consists of one discrete [Ni(tren)(en)]2+ complex [tren is N,N-bis(2-aminoethyl)ethane-1,2-diamine] in which the Ni2+ cation is sixfold coordinated within a slightly distorted octahedron, one thiosulfate anion and three water molecules. In the crystal, the complex cations, anions and water molecules are linked by an intricate hydrogen-bonding network. One C atom of the tren ligand, as well as one O atom of a water molecule, are disordered over two sites and were refined using a split model (occupancy ratios = 0.85:15 and 0.60:0.40, respectively).