Synthese und Kristallstruktur von K2(HSO4)(H2PO4), K4(HSO4)3(H2PO4) und Na(HSO4)(H3PO4)

Synthesis and Crystal Structure of K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄), and Na(HSO₄)(H₃PO₄) Mixed hydrogen sulfate phosphates K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄) and Na(HSO₄)(H₃PO₄) were synthesized and characterized by X‐ray single crystal analysis. In case of K₂(HSO₄)(H₂PO₄) neutron powder diffraction was used additionally. For this compound an unknown supercell was found. According to X‐ray crystal structure analysis, the compounds have the following crystal data: K₂(HSO₄)(H₂PO₄) (T = 298 K), monoclinic, space group P 2₁/c, a = 11.150(4) Å, b = 7.371(2) Å, c = 9.436(3) Å, β = 92.29(3)°, V = 774.9(4) ų, Z = 4, R₁ = 0.039; K₄(HSO₄)₃(H₂PO₄) (T = 298 K), triclinic, space group P 1, a = 7.217(8) Å, b = 7.521(9) Å, c = 7.574(8) Å, α = 71.52(1)°, β = 88.28(1)°, γ = 86.20(1)°, V = 389.1(8)ų, Z = 1, R₁ = 0.031; Na(HSO₄)(H₃PO₄) (T = 298 K), monoclinic, space group P 2₁, a = 5.449(1) Å, b = 6.832(1) Å, c = 8.718(2) Å, β = 95.88(3)°, V = 322.8(1) ų, Z = 2, R₁ = 0,032. The metal atoms are coordinated by 8 or 9 oxygen atoms. The structure of K₂(HSO₄)(H₂PO₄) is characterized by hydrogen bonded chains of mixed H_nS/PO₄^– tetrahedra. In the structure of K₄(HSO₄)₃(H₂PO₄), there are dimers of H_nS/PO₄^– tetrahedra, which are further connected to chains. Additional HSO₄^– tetrahedra are linked to these chains. In the structure of Na(HSO₄)(H₃PO₄) the HSO₄^– tetrahedra and H₃PO₄ molecules form layers by hydrogen bonds.     

Synthese und Kristallstruktur von Hydrogensulfaten einwertiger Metalle – Ag(H3O)(HSO4)2, Ag2(HSO4)2(H2SO4), AgHSO4 und Hg2(HSO4)2

Synthesis and Crystal Structure of Metal(I) Hydrogen Sulfates – Ag(H₃O)(HSO₄)₂, Ag₂(HSO₄)₂(H₂SO₄), AgHSO₄, and Hg₂(HSO₄)₂ Hydrogen sulfates Ag(H₃O)(HSO₄)₂, Ag₂(HSO₄)₂ · (H₂SO₄), and AgHSO₄ have been synthesized from Ag₂SO₄ and sulfuric acid. Hg₂(HSO₄)₂ was obtained from metallic mercury and 96% sulfuric acid as starting materials. The compounds were characterized by X‐ray single crystal structure determination. Ag(H₃O)(HSO₄)₂ belongs to the structure type of Na(H₃O)(HSO₄). The silver atom is coordinated by 6 + 2 oxygen atoms. In the structure, there are dimers and chains of hydrogen bonded HSO₄^– tetrahedra. Dimers and chains are connected by the H₃O⁺ ion to form a three dimensional hydrogen network. Ag₂(HSO₄)₂(H₂SO₄) crystallizes isotypic to Na₂(HSO₄)₂(H₂SO₄). The coordination number of silver is 6 + 1. The structure of Ag₂(HSO₄)₂(H₂SO₄) is characterized by hydrogen bonded trimers of HSO₄^– tetrahedra, which are further connected to chains. For the recently published structure of AgHSO₄ the hydrogen bonding system was discussed. There are tetrameres and chains, connected by bifurcated hydrogen bonds. The structure of Hg₂(HSO₄)₂ contains Hg₂²⁺ cations with Hg–Hg distance of 2.509 Å. Every mercury atom is coordinated by one oxygen atom at shorter distance (2.18 Å) and three ones at longer distances (2.57 to 3.08 Å). The HSO₄^– tetrahedra form zigzag chains by hydrogen bonds.     

Molecular structure of tris(acetylacetonato)scandium Sc(C5H7O2)3

Molecular structure of tris(acetylacetonato)scandium, Sc(C₅H₇O₂)₃, is investigated by gas-phase electron diffractometry. The main structural parameters of the molecule are evaluated. The average internuclear distances and angles correspond to C₃ symmetry. The chief structural motif is trigonal antiprisms of six oxygen, carbon, and hydrogen atoms with a scandium atom at the center. It is found that r_g(Sc-O) = 204.1(8) pm and r_g(C-O) = 124.7(4) pm. Translated fromZhumal Strukturnoi Khimii, Vol. 39, No. 4, pp. 633–639, July–August, 1998.     

Saure Sulfate des Neodyms: Synthese und Kristallstruktur von (H5O2)(H3O)2Nd(SO4)3 und (H3O)2Nd(HSO4)3SO4

Acidic Sulfates of Neodymium: Synthesis and Crystal Structure of (H₅O₂)(H₃O)₂Nd(SO₄)₃ and (H₃O)₂Nd(HSO₄)₃SO₄ Light violett single crystals of (H₅O₂)(H₃O)₂ · Nd(SO₄)₃ are obtained by cooling of a solution prepared by dissolving neodymium oxalate in sulfuric acid (80%). According to X‐ray single crystal investigations there are H₃O⁺ ions and H₅O₂⁺ ions present in the monoclinic structure (P2₁/n, Z = 4, a = 1159.9(4), b = 710.9(3), c = 1594.7(6) pm, β = 96.75(4)°, R_all = 0.0260). Nd³⁺ is nine‐coordinate by oxygen atoms. The same coordination number is found for Nd³⁺ in the crystal structure of (H₃O)₂Nd(HSO₄)₃SO₄ (triclinic, P1, Z = 2, a = 910.0(1), b = 940.3(1), c = 952.6(1) pm, α = 100.14(1)°, β = 112.35(1)°, γ = 105.01(1)°, R_all = 0.0283). The compound has been prepared by the reaction of Nd₂O₃ with chlorosulfonic acid in the presence of air. In the crystal structure both sulfate and hydrogensulfate groups occur. In both compounds pronounced hydrogen bonding is observed.     

Peroxofluorokomplexe der Übergangsmetalle. VII. Peroxofluorokryolithe A3Ti(O2)F5 (A = K,Na) und K2NaTi(O2)F5 Kristallstruktur von K3Ti(O2)F5

Transition Metal Peroxofluoro Complexes. VII. Peroxofluorokryolithes A₃Ti(O₂)F₅ (A = K, Na) and K₂NaTi(O₂)F₅. Crystal Structure of K₃Ti(O₂)F₅ Peroxofluorokryolithes A₃Ti(O₂)F₅ (A = K, Na) and K₂NaTi(O₂)F₅ were prepared at pH 4.5–6 by adding H₂O₂ and AOH/AF to solutions of TiO₂ in hydrofluoric acid or aqueous solutions of TiF₄. In the range of pH 3–4.5 exist phases of peroxofluoro-kryolithes with variations in stoichiometrie. A single crystall X-ray structure analysis of K₃Ti(O₂)F₅ (Fm3m, a = 883.6(1) pm) yielded a disordered kryolithstructure (R = 0.020, R_W = 0.017). Na₃Ti(O₂)F₅ was found to crystallize in two monoclinic low-temperature – and one cubic high-temperature modifications. K₂NaTi(O₂)F₅ crystallizes cubic (Fm3m) with a = 847.8(1) pm. Vibrational spectra have been measured and thermal behavior was studied by DTA/DTG and high-temperature guinier. At pH 9.5 K₃Ti(O₂)₂F₃ has been synthesized     

Small gas-phase dianions of Zn3O(4)(2-), Zn4O(5)(2-), CuZn2O(4)(2-), Si2GeO(6)(2-), Ti2O(5)(2-) and Ti3O(7)(2-)

We have searched for new species of small oxygen-containing gas-phase dianions produced in a secondary ion mass spectrometer by Cs+ ion bombardment of solid samples with simultaneous exposure of their surfaces to O2 gas. The targets were a pure zinc metal foil, a copper-contaminated zinc-based coin, two silicon-germanium samples (Si(1-x)Ge(x)(with x= 6.5% or 27%)) and a piece of titanium metal. The novel dianions Zn3O(4)(2-), Zn4O(5)(2-), CuZn2O(4)(2-), Si2GeO(6)(2-), Ti2O(5)(2-) and Ti3O(7)(2-) have been observed at half-integer m/z values in the negative ion mass spectra. The heptamer dianions Zn3O(4)(2-) and Ti2O(5)(2-) have been unambiguously identified by their isotopic abundances. Their flight times through the mass spectrometer are approximately 20 micros and approximately 17 micros, respectively. The geometrical structures of the two heptamer dianions Ti2O(5)(2-), and Zn3O(4)(2-) are investigated using ab initio methods, and the identified isomers are compared to those of the novel Ge2O(5)(2-) and the known Si2O(5)(2-) and Be3O(4)(2-) dianions.     

A direct method for the preparation of tris(2,4-pentanedionato) chromium(III), Cr(C5H7O2)3

A novel and direct method for the preparation of tris(2,4-pentanedionato) chromium(III) in excellent yield is reported.     

Synthese und Struktur neuer Natriumhydrogensulfate Na(H3O)(HSO4)2; Na2(HSO4)2(H2SO4) und Na(HSO4)(H2SO4)2

Synthesis and Structure of New Sodium Hydrogen Sulfates Na(H₃O)(HSO₄)₂, Na₂(HSO₄)₂(H₂SO₄), and Na(HSO₄)(H₂SO₄)₂ Three acidic sodium sulfates have been synthesized from the system sodium sulfate/sulfuric acid and have been crystallographically characterized. Na(H₃O)(HSO₄)₂ ( A ) crystallizes in the space group P2₁/c with the unit cell parameters a = 6.974(2), b = 13.086(2), c = 8.080(3) Å, α = 105.90(4)°, V = 709.1 Å3, Z = 4. Na₂(HSO₄)₂(H₂SO₄) ( B ) is orthorhombic (space group Pna2₁) with the unit cell parameters a = 9.970(2), b = 6.951(1), c = 13.949(3) Å, V = 966.7 ų and Z = 4. Na(HSO₄)(H₂SO₄)₂ ( C ) crystallizes in the triclinic space group P1 with the unit cell parameters a = 5.084(1), b = 8.746(1), c = 11.765(3) Å, α = 68.86(2)°, β = 88.44(2)°, γ = 88.97(2)°, V = 487.8 Å3 and Z = 2. All three compounds contain SO₄ tetrahedra as HSO₄^? anions and additionally in B and C in form of H₂SO₄ molecules. The ratio H:SO₄ determines the connectivity degree in the hydrogen bond system. In A , there are zigzag chains and dimers additionally connected via oxonium ions. Complex chains consisting of cyclic trimers (two HSO₄^? and one H₂SO₄) are present in B . In structure C , several parallel chains are connected to columns due to the greater content of H₂SO₄. Sodium cations show a distorted octahedral coordination by oxygen in all three structures, the NaO₆ octahedra being “isolated” (connected via SO₄ tetrahedra only) in A . Pairs of octahedra with common edge form Na₂O₁₀ dimeric units in C . Such double octahedra are connected via common corners forming zigzag chains in B .     

Solvothermal and surfactant-free synthesis of crystalline Nb(2)O(5), Ta(2)O(5), HfO(2), and Co-doped HfO(2) nanoparticles

A simple route to niobium, hafnium and tantalum oxide nanocrystals using a nonaqueous sol-gel route based on the solvothermal reaction of the corresponding metal chlorides with benzyl alcohol is presented. This approach can easily be extended to the preparation of high quality Co-doped HfO(2) nanoparticles of uniform size and shape and with a homogenous distribution of the magnetic ions. The structural characterization of all these nanomaterials as well as the magnetic properties of pure and doped hafnia, with special attention to the doping efficiency, are discussed. The obtained Co-doped hafnia exhibits paramagnetic properties with very weak antiferromagnetic interactions between Co ions moments.     

Ein neues Kaliumhydrogensulfat,K(H3O)(HSO4)2 — Synthese und Struktur

A New Potassium Hydrogensulfate, K(H₃O)(HSO₄)₂ — Synthesis and Structure Single crystals of the new compound K(H₃O)(SO₄)₂ are synthesized from the system potassium sulfate/sulfuric acid. The up to day not described compound crystallizes in the monoclinic space group P2₁/c with the unit cell parameters a = 7.203(1) b = 13.585(2) and c = 8.434(1) Å, β = 105.54(1)°, V = 795.1 ų, Z = 4 and D_x = 2.107 g · cm^?3. There are two crystallographically different tetrahedral SO₃(OH) anions. The first kind S1 tetrahedra forms dimers, whereas the second kind S2 forms infinite chains bonded via hydrogen bridges. The S1 dimers are linked to the S2 chains via oxonium ions (hydrogen bonds). Potassium is coordinated by 8 oxygen atoms which belong to four different SO₃(OH) tetrahedra. These potassium oxygen polyhedra are connected by common edges forming chains running parallel z.     

Exploratory synthesis in molten salts: role of flux basicity in the stabilization of the complex thiogermanates Cs(4)Pb(4)Ge(5)S(16), K(2)PbGe(2)S(6), and K(4)Sn(3)Ge(3)S(14)

The influence of the Lewis basicity of alkali polysulfide fluxes (A(2)S(x)) (A = alkali) as a function of x on the respective reactivities of Pb and Sn with Ge was studied and found to be strong. Cs(4)Pb(4)Ge(5)S(16), K(2)PbGe(2)S(6), and K(4)Sn(3)Ge(3)S(14) could be prepared only under low basicity with S/A(2)S ratios of > or =11. These compounds display complex frameworks and are semiconductors. Cs(4)Pb(4)Ge(5)S(16) is luminescent with red emission.