ChemInform Abstract: Growth and Characterization of Acentric BaHf(BO3)2 and BaZr(BO3)2.

Single crystals of BaHf(BO₃)₂ are grown on a Pt wire from BaHfO₃ (3.5 mol%) solved in a BaB₄O₇ melt (1050 °C soaking temperature, 1000-940 °C crystallization temperature gradient).     

ChemInform Abstract: V2O2F4 (H2O)2·H2O: A New V4+ Layer Structure Related to VOF3.

Single crystals of the title compound are prepared by hydrothermal reaction of VF₃ and H₂SeO₃ in ethylene glycol/HF (40%) in the presence of Et₂NH (autoclave, 393 K, 4 d).     

ChemInform Abstract: The Crystal Structures of Ni3+xSn4Zn and Ni6+xSn8Zn and Their Structural Relations to Ni3+xSn4, NiSn and Ni5‐δZnSn4.

Two new compounds, Ni_3+xSn₄Zn (x≈1.35, monoclinic, space group I2/m, Z = 2, single crystal XRD) and Ni_6+xSn₈Zn (x≈1.35, monoclinic, space group C2/m, Z = 2) are prepared by solid state reaction of the elements (Al₂O₃ crucible in evacuated quartz tubes, 1453 K).     

Incorporation of Sulfate or Selenate Groups into Oxotellurates(IV): I. Calcium,Cadmium, and Strontium Compounds

Seven new mixed oxochalcogenate compounds in the systems M^II/X^VI/Te^IV/O/(H), (M^II = Ca, Cd, Sr; X^VI = S, Se) were obtained under hydrothermal conditions (210 °C, one week). Crystal structure determinations based on single‐crystal X‐ray diffraction data revealed the compositions Ca₃(SeO₄)(TeO₃)₂, Ca₃(SeO₄)(Te₃O₈), Cd₃(SeO₄)(Te₃O₈), Cd₃(H₂O)(SO₄)(Te₃O₈), Cd₄(SO₄)(TeO₃)₃, Cd₅(SO₄)₂(TeO₃)₂(OH)₂, and Sr₃(H₂O)₂(SeO₄)(TeO₃)₂ for these phases. Peculiar features of the crystal structures of Ca₃(SeO₄)(TeO₃)₂, Ca₃(SeO₄)(Te₃O₈), Cd₃(SeO₄)(Te₃O₈), Cd₃(H₂O)(SO₄)(Te₃O₈), and Sr₃(H₂O)₂(SeO₄)(TeO₃)₂ are metal‐oxotellurate(IV) layers connected by bridging XO₄ tetrahedra and/or by hydrogen‐bonding interactions involving hydroxyl or water groups, whereas Cd₄(SO₄)(TeO₃)₃ and Cd₅(SO₄)₂(TeO₃)₂(OH)₂ crystallize as framework structures. Common to all crystal structures is the stereoactivity of the Te^IV electron lone pair for each oxotellurate(IV) unit, pointing either into the inter‐layer space, or into channels and cavities in the crystal structures.     

Herstellung keramischer Pulver. IX. Zur Bildung von NiMn2 O4 und ZnMn2O4 durch Zersetzung von [Ni(H2O)6] (MnO4)2 und [Zn(H2O)6] (MnO4)2

Preparation of Ceramic Powders. IX. NiMn₂O₄ and ZnMn₂O₄ Formation by Decomposition of [Ni(H₂O)₆] (MnO₄)₂ and [Zn(H₂O)₆] (MnO₄)₂ Improved preparation of Ba(MnO₄)₂ from BaMnO₄ is reported. Thermal or hydrothermal decomposition of [Ni(H₂O)₆] (MnO₄)₂ yields intermediately an amorphous manganate(IV) which forms crystalline NiMnO₃ and α-Mn₂O₃ in the range T > 400°C. NiMn₂O₄ is formed above 730°C in accordance with the phase diagram. On the other hand, ZnMn₂O₄ is already at 300°C obtained from [Zn(H₂O)₆](MnO₄)₂ at hydrothermal conditions.     

Syntheses, crystal structures and optical properties of the first strontium selenium(IV) and tellurium(IV) oxychlorides: Sr3(SeO3)(Se2O5)Cl2 and Sr4(Te3O8)Cl4

Two new quaternary strontium selenium(IV) and tellurium(IV) oxychlorides, namely, Sr₃(SeO₃)(Se₂O₅)Cl₂ and Sr₄(Te₃O₈)Cl₄, have been prepared by solid-state reaction. Sr₃(SeO₃)(Se₂O₅)Cl₂ features a three-dimensional (3D) network structure constructed from strontium(II) interconnected by Cl⁻, SeO₃²⁻ as well as Se₂O₅²⁻ anions. The structure of Sr₄(Te₃O₈)Cl₄ features a 3D network in which the strontium tellurium oxide slabs are interconnected by bridging Cl⁻ anions. The diffuse reflectance spectrum measurements and results of the electronic band structure calculations indicate that both compounds are wide band-gap semiconductors.     

Syntheses, crystal structures and characterizations of BaZn(SeO3)2 and BaZn(TeO3)Cl2

Two new barium zinc selenite and tellurite, namely, BaZn(SeO₃)₂ and BaZn(TeO₃)Cl₂, have been synthesized by the solid state reaction. The structure of BaZn(SeO₃)₂ features double chains of [Zn(SeO₃)₂]²⁻ anions composed of four- and eight-member rings which are alternatively along a-axis. The double chains of [Zn₂(TeO₃)₂Cl₃]³⁻ anions in BaZn(TeO₃)Cl₂ are formed by Zn₃Te₃ rings in which each tellurite group connects with three ZnO₃Cl tetrahedra. BaZn(SeO₃)₂ and BaZn(TeO₃)Cl₂ are wide bandgap semiconductors based on optical diffuse reflectance spectrum measurements.     

ChemInform Abstract: Crystal Structure of the Novel Copper Phosphate Cu3(PO4)2·H2O.

The title compound, obtained in the ternary system CuO₂-P₃O₅-H₂O at 160°C, crystallizes in the monoclinic crystal system (C2/c, Z=8).     

ChemInform Abstract: Temperature Induced Phase Transition of CaMn0.5Zr1.5(PO4)3 Phosphate.

In view of a known structural phase transition at 800—875 °C and the by 10 times increased luminescence of Mn²⁺ in the high‐temperature phase, low‐ (LT) and high‐temperature (HT) polymorphs of CaMn_0.5Zr_1.5(PO₄)₃ are prepared by sol—gel reaction of Mn(O‐Ac)₂, Ca(NO₃)₂, ZrOCl₂, and NH₄H₂PO₄ in ethylene glycol followed by a final annealing (700 or 900 °C, 20 h, resp.).     

ChemInform Abstract: Intermetallic Compounds Ce4Ru3Ga3 and La3Ru2Ga2 with Crystal Structures of New Types.

Ce₄Ru₃Ga₃ (I) and La₃Ru₂Ga₂ (II) are synthesized by arc melting of the elements under Ar followed by annealing (873 K, 30 d).     

ChemInform Abstract: On Compound Formation of M′O:M2O3. Part 11. Crystal Structure of BaIn2O4.

Single crystals of the title compound, obtained from a melt after reacting intimate mixtures of BaCO₃ and In₂O₃ at 840 °C (12 h), belong to the monoclinic space group P2₁/a with Z=16.     

La4(Si5.2Ge2.8O18)(TeO3)4 and La2(Si6O13)(TeO3)2: Intergrowth of the lanthanum(III) tellurite layer with the XO4 (X=Si/Ge) tetrahedral layer

Two novel lanthanum(III) silicate tellurites, namely, La₄(Si_5.2Ge_2.8O₁₈)(TeO₃)₄ and La₂(Si₆O₁₃)(TeO₃)₂, have been synthesized by the solid state reactions and their structures determined by single crystal X-ray diffraction. The structure of La₄(Si_5.2Ge_2.8O₁₈)(TeO₃)₄ features a three-dimensional (3D) network composed of the [(Ge_2.82Si_5.18)O₁₈]⁴⁻ tetrahedral layers and the [La₄(TeO₃)₄]⁴⁺ layers that alternate along the b-axis. The germanate-silicate layer consists of corner-sharing XO₄ (X=Si/Ge) tetrahedra, forming four- and six-member rings. The structure of La₂(Si₆O₁₃)(TeO₃)₂ is a 3D network composed of the [Si₆O₁₃]²⁻ double layers and the [La₂(TeO₃)₂]²⁺ layers that alternate along the a-axis. The [Si₆O₁₃]²⁻ double layer is built by corner-sharing silicate tetrahedra, forming four-, five- and eight-member rings. The TeO₃²⁻ anions in both compounds are only involved in the coordination with La³⁺ ions to form a lanthanum(III) tellurite layer. La₄(Si_5.2Ge_2.8O₁₈)(TeO₃)₄ is a wide band-gap semiconductor.     

ChemInform Abstract: The First Boroselenates as New Silicate Analogues.

Single crystals of Rb₃[B(SeO₄)₃] (I) and Cs₃[B(SeO₄)₃] (II) are prepared by heating a 1.5:1:6.6 molar mixture of Rb₂CO₃ (Cs₂CO₃), H₃BO₃, and H₂SeO₄ in air (quartz crucible, 550 K, 2 d).     

ChemInform Abstract: YCa3(CrO)3(BO3)4: A Cr3+ Kagome Lattice Compound Showing No Magnetic Order Down to 2 K.

Polycrystalline gaudefroyite‐type YCa₃(CrO)₃(BO₃)₄ with Cr³⁺ ions (3d³, S = 3/2) forming an undistorted Kagome lattice is prepared by reaction of a stoichiometric mixture of Y₂O₃, CaCO₃, Cr₂O₃, H₃BO₃ in a KCl flux (Al₂O₃ crucible, 1000 °C, 1 d) followed by re‐grinding and further annealing (1000 °C, 2 d, 95% yield).     

CoSm(SeO3)2Cl,CuGd(SeO3)2Cl,MnSm(SeO3)2Cl,CuGd2(SeO3)4 und CuSm2(SeO3)4: Übergangsmetallhaltige Selenite von Samarium und Gadolinum

CoSm(SeO₃)₂Cl, CuGd(SeO₃)₂Cl, MnSm(SeO₃)₂Cl, CuGd₂(SeO₃)₄ and CuSm₂(SeO₃)₄: Transition Metal containing Selenites of Samarium and Gadolinum The reaction of CoCl₂, Sm₂O₃, and SeO₂ in evacuated silica ampoules lead to blue single crystals of CoSm(SeO₃)₂Cl (triclinic, , Z = 4, a = 712.3(1), b = 889.5(2), c = 1216.2(2) pm, α = 72.25(1)°, β = 71.27(1)°, γ = 72.08(1)°, R_all = 0.0586). If MnCl₂ is used in the reaction light pink single crystals of MnSm(SeO₃)₂Cl (triclinic, , Z = 2, a = 700.8(2), b = 724.1(2), c = 803.4(2) pm, α = 86.90(3)°, β = 71.57(3)°, γ = 64.33(3)°, R_all = 0.0875) are obtained. Green single crystals of CuGd₂(SeO₃)₂Cl (triclinic, , Z = 4, a = 704.3(4), b = 909.6(4), c = 1201.0(7) pm, α = 70.84(4)°, β = 73.01(4)°, γ = 70.69(4)°, R_all = 0.0450) form analogously in the reaction of CuCl₂ and Gd₂O₃ with SeO₂. CoSm(SeO₃)₂Cl contains [CoO₄Cl₂] octahedra, which are connected via one edge and one vertex to infinite chains. The Mn²⁺ ions in MnSm(SeO₃)₂Cl are also octahedrally coordinated by four oxygen and two chlorine ligands. The linkage of the polyhedra to chains occurs exclusively via edges. Both, the cobalt and the manganese compound show the Sm³⁺ ions in eight and ninefold coordination of oxygen atoms and chloride ions. In CuGd(SeO₃)₂Cl the Cu²⁺ ions are coordinated by three oxygen atoms and one Cl^— ion in a distorted square planar manner. One further Cl^— and one further oxygen ligand complete the [CuO₃Cl] units yielding significantly elongated octahedra. The latter are again connected to chains via two common edges. For the Gd³⁺ ions coordination numbers of ?8 + 1”? and nine were found. Single crystals of the deep blue selenites CuM₂(SeO₃)₄ (M = Sm/Gd, monoclinic, P2₁/c, a = 1050.4(3)/1051.0(2), b = 696.6(2)/693.5(1), c = 822.5(2)/818.5(2) pm, β = 110.48(2)°/110.53(2)°, R_all = 0.0341/0.0531) can be obtained from reactions of the oxides Sm₂O₃ and Gd₂O₃, respectively, with CuO and SeO₂. The crystal structure contains square planar [CuO₄] groups and irregular [MO₉] polyhedra.     

Incorporation of Sulfate or Selenate Groups into Oxotellurates(IV): II. Compounds with Divalent Lead

Four mixed oxochalcogenate compounds in the systems Pb^II/X^VI/Te^IV/O/(C), (X^VI = S and Se) were obtained as minority phases under hydrothermal conditions (210 °C, one week). Their compositions as determined on the basis of single‐crystal X‐ray diffraction data are Pb₃(SeO₄)(TeO₃)₂, Pb₇O₄(SeO₄)₂(TeO₃), Pb₅(SeO₄)₂(TeO₄)(CO₃), and Pb₂(SO₄)(TeO₃). All crystal structures are centrosymmetric, and in each case the oxochalcogenate anions are isolated from each other. The Pb²⁺ cations exhibit distorted coordination polyhedra with coordination numbers ranging from six to ten, in the majority of cases with a “one‐sided” coordination by oxygen atoms. The presence of the very rare square‐pyramidal Te^IVO₄^4– anion distinguishes the structure of Pb₅(SeO₄)₂(TeO₄)(CO₃) from the other structures, where the oxotellurate(IV) anions exist in the TeO₃^2– trigonal‐pyramidal configuration.     

A synthetic zinc tellurium oxochloride,Zn2(TeO3)Cl2

Single crystals of dizinc tellurium dichloride trioxide, Zn₂(TeO₃)Cl₂, were synthesized via a transport reaction in sealed evacuated glass tubes. The compound has a layered structure in which the building units are [ZnO₄Cl] square pyramids, distorted [ZnO₂Cl₂] tetrahedra and [TeO₃E] tetrahedra (E is the 5s² lone pair of the Te^IV atom), joined through shared edges and corners to form charge‐neutral layers. Cl atoms and Te‐atom lone pairs protrude from the surfaces of each layer towards adjacent layers, and the layers are held together by dispersion forces only. The compound is isostructural with the synthetic compound CuZn(TeO₃)Cl₂ and the mineral sophiite, Zn₂(SeO₃)Cl₂.     

Ag2Hg2(TeO4)3

Red single crystals of disilver(I) dimercury(II) tris­[tetra­oxo­tellurate(VI)], Ag₂Hg₂(TeO₄)₃, were obtained under hydro­thermal conditions at 523 K. The structure is built up of _∞¹[(TeO_2/1O_4/2)({TeO_2/1O_2/2}₂O_4/2)] chains, with an overall composition [TeO₄]²⁻, that run parallel to the crystallographic a axis. Distorted AgO₆ and HgO₆ polyhedra (the latter with two short and nearly collinear Hg—O bonds) link the tellurate chains into a three‐dimensional network. Except for one Te atom situated on an inversion center, all atoms occupy general positions.     

ChemInform Abstract: Syntheses,Structures, Physical Properties,and Electronic Structures of Ba2MLnTe5 (M: Ga and Ln: Sm,Gd, Dy,Er, Y; M: In and Ln: Ce,Nd, Sm,Gd, Dy,Er, Y).

The title compounds are synthesized by solid state reactions of BaTe, Ga₂Te₃ or In₂Te₃, Ln, and Te (1273—1323 K, 20—48 h) and characterized by single crystal XRD, diffuse reflectance spectroscopy, magnetic susceptibility measurements, second harmonic generation measurements, and DFT electronic structure calculations.     

Neue Phosphido-verbrückte Mehrkernkomplexe des Ag,Cd und Zn Die Kristallstrukturen von [Ag4(PPh2)4(PMe3)4], [Ag6(PPh2)6(PtBu3)2] und [M4Cl4(PPh2)4(PnPr3)2] (M = Zn,Cd)

New Phosphido-bridged Multinuclear Complexes of Ag, Cd and Zn. The Crystal Structures of [Ag₄(PPh₂)₄(PMe₃)₄], [Ag₆(PPh₂)₆(P^tBu₃)₂] and [M₄Cl₄(PPh₂)₄(PⁿPr₃)₂] (M = Zn, Cd) AgCl reacts with Ph₂PSiMe₃ in the presence of a tertiary Phosphine PMe₃ or P^tBu₃ to form the multinuclear complexes [Ag₄(PPh₂)₄(PMe₃)₄] ( 1 ) and [Ag₆(PPh₂)₆(P^tBu₃)₂] ( 2 ). In analogy to that MCl₂ reacts with Ph₂PSiMe₃ in the presence of PⁿPr₃ to form the two multinuclear complexes [M₄Cl₄(PPh₂)₄(PⁿPr₃)₂] (M = Zn ( 3 ), Cd ( 4 )). The structures were characterized by X-ray single crystal structure analysis ( 1 : space group Pna2₁ (Nr. 33), Z = 4, a = 1 313.8(11) pm, b = 1 511.1(6) pm, c = 4 126.0(18) pm, 2 : space group P–1 (Nr. 2), Z = 2, a = 1 559.0(4) pm, b = 1 885.9(7) pm, c = 2 112.4(8) pm, α = 104.93(3)°, β = 94.48(3)°, γ = 104.41(3)°; 3 : space group C2/c (Nr. 15), Z = 4, a = 2 228.6(6) pm, b = 1 847.6(6) pm, c = 1 827.3(6) pm, β = 110.86(2); 4 : space group C2/c (Nr. 15), Z = 4, a = 1 894.2(9) pm, b = 1 867.9(7) pm, c = 2 264.8(6) pm, β = 111.77(3)°). 3 and 4 may be considered as intermediates on the route towards polymeric [M(PPh₂)₂]_n (M = Zn, Cd).