Synthesis and Characterization of the Rubidium Thiophosphate Rb6(PS5)(P2S10) and the Rubidium Silver Thiophosphates Rb2AgPS4, RbAg5(PS4)2 and Rb3Ag9(PS4)4

The metal thiophosphates Rb₂AgPS₄ ( 2 ), RbAg₅(PS₄)₂ ( 3 ), and Rb₃Ag₉(PS₄)₄ ( 4 ) were synthesized by stoichiometric reactions, whereas Rb₆(PS₅)(P₂S₁₀) ( 1 ) was prepared with excess amount of sulfur. The compounds crystallize as follows: 1 monoclinic, P2₁/c (no. 14), a = 17.0123(7) Å, b = 6.9102(2) Å, c = 23.179(1) Å, β = 94.399(4)°; 2 triclinic, P$\bar{1}$ (no. 2), a = 6.600(1) Å, b = 6.856(1) Å, c = 10.943(3) Å, α = 95.150(2)°, β = 107.338(2)°, γ = 111.383(2)°; 3 orthorhombic, Pbca (no. 61), a = 12.607(1) Å, b = 12.612(1) Å, c = 17.759(2) Å; 4 orthorhombic, Pbcm (no. 57), a = 6.3481(2) Å, b = 12.5782(4) Å, c = 35.975(1) Å. The crystal structures contain discrete units, chains, and 3D polyanionic frameworks composed of PS₄ tetrahedral units arranged and connected in different manner. Compounds 1 – 3 melt congruently, whereas incongruent melting behavior was observed for compound 4 . 1 – 4 are semiconductors with bandgaps between 2.3 and 2.6 eV and thermally stable up to 450 °C in an inert atmosphere.     

Reinvestigation and superstructure of La3.67[Fe(C2)3]

The lanthanum iron carbide La_3.67[Fe(C₂)₃] was prepared from the elements by argon arc-melting followed by annealing. The crystal structure of the ternary phase was reported previously (space group P6₃/m with a=878.7(2) pm, and c=535.1(1) pm) [A.M. Witte, W. Jeitschko, Z. Naturforsch. 51b (1996) 249-255]. In the present work the compound was reinvestigated by X-ray powder and single crystal diffraction, and was further characterized by metallographic methods and chemical analyses. Our diffraction data clearly reveal a superstructure with weak superstructure reflections in the space group P6₃/m with a=879.26(8) pm and c=1604.59(15) pm, thus tripling the previously reported subcell. The crystal structure (refinement to R1=0.044 and wR2=0.075 for 1387 unique reflections and 60 variables) contains Fe(C₂)₃ trigonal planar groups with the C₂ ligands bonded end-on to the Fe atoms. The C-C distance is typical for a double bond. La atoms as the least electronegative component surround the complex anions and form a framework of face-sharing tricapped trigonal prisms. The resulting hexagonal channels at 0, 0, z of the partial structure with chemical composition La₃FeC₆ are occupied by four additional La atoms per unit cell. These La atoms are fully ordered within a linear chain and display a Peierls-like distortion pattern. However, no long-range order in the a−b plane has been observed due to the random orientation of the chains. Because of the two different orientations which are possible for each chain the situation is similar to an Ising model on a triangular lattice.     

Synthesis and Characterization of the Ternary Thiobismuthates A9Bi13S24 (A = K,Rb)

Ternary alkali metal thiobismuthates A₉Bi₁₃S₂₄ (A = K, Rb) were synthesized by direct combination reactions at 650 °C. The compounds crystallize in the monoclinic space group C2/m (no. 12) with cell parameters a = 30.919(1) Å, b = 4.1008(2) Å, c = 20.9072(9) Å, β = 105.826(3)° for K₉Bi₁₃S₂₄ ( 1 ) and a = 31.823(6) Å, b = 4.1177(8) Å, c = 21.086(4) Å, β = 105.62(3)° for Rb₉Bi₁₃S₂₄ ( 2 ). The crystal structure of 1 contains a 3D [K₂Bi₁₃S₂₄]^7– polyanionic framework, whereas 2 consists of 2D [RbBi₁₃S₂₄]^8– polyanionic slabs stacked along [201]. Both 1 and 2 are semiconductors with a band gap of 1.4 and 1.3 eV, respectively, which is supported by an electronic structure calculation. 1 melts congruently at 580 °C, while 2 melts incongruently at 575 °C. 1 and 2 are airstable and insoluble in water and organic solvents.     

Synthesis and Characterization of the Quaternary Thio­aluminogermanates A(AlS2)(GeS2) (A = Na,K)

The quaternary thioaluminogermanates Na(AlS₂)(GeS₂) ( 1 ) and K(AlS₂)(GeS₂) ( 2 ) crystallize in the tetragonal space group I4/mcm (no. 140) with unit cell parameters a = 7.4274(11) Å, c = 5.8560(12) Å for Na(AlS₂)(GeS₂) and a = 7.8826(2) Å, c = 5.8642(4) Å for K(AlS₂)(GeS₂). The crystal structure comprises of one‐dimensional [(AlS₂)(GeS₂)]^– anionic chains with Al and Ge sharing the tetrahedral site. The alkali metal cations fill the square antiprismatic voids between chains. Both 1 and 2 are semiconductors with bandgap of around 3.6 eV and 3.5 eV, respectively.     

Potential Anticancer Activities and Catalytic Oxidation Efficiency of Platinum(IV) Complex

The treatment of an aqueous acetonitrile solution of chloroplatinic acid hydrate H₂PtCl₆.xH₂O and pyridine-2-carbaldehyde-oxime (paOH) in the presence of potassium thiocyanate at room temperature (25°) led to the formation of a new Pt(IV) complex with the formula [Pt(SCN)₂(paO)₂], (1). Complex 1 was fully characterized by FT-IR, UV-vis and NMR spectroscopic techniques as well as elemental analysis. The crystallographic structure of complex 1 was obtained by single-crystal X-ray diffraction. The structure of complex 1 consists of a distorted octahedral geometrical environment around the platinum center in which the coordination sites are occupied by two terminal thiocyanate ligands in trans arrangement and two bidentate paO ligands through four nitrogen atoms. In addition, the in vitro evaluation of the cytotoxicity of platinum complex 1 against four different cancer cell lines was performed. The IC₅₀ values for colon (HCT116), liver (HepG2), breast (MCF-7) and erythroid (JK-1) treated with complex 1 are 19 ± 6, 21 ± 5, 22 ± 6, and 13 ± 3 μM, respectively. In HCT116 cells treated with the IC50 dose of our title compound, apoptosis and necrosis were increased by 34% and 27.8%, respectively. Cells halted in the proliferative phase (S phase) to 21.7 % and 29.8% in HCT116 and HepG2 cells treated with complex 1 have anti-proliferative actions. Furthermore, the catalytic activity of synthesized complex 1 was examined in the oxidation reaction of benzyl alcohols in the presence of an oxidant. Finally, the luminescence behavior of complex 1 was investigated.