Two tetravalent uranium silicate and germanate crystals with three membered single-ring by molten salt method: K2USi3O9 and Cs2UGe3O9

Two tetravalent uranium silicate and germanate M₂U^IVT₃O₉ (M = K, Cs; T = Si, Ge) crystals were crystalized under inert gas by molten salt flux growth method. K₂USi₃O₉ (1) crystallizes in the monoclinic space group P1₂₁/n1 with lattice parameters a = 7.1076 Å, b = 10.4776 Å, c = 12.2957 Å, γ = 120° and V = 915.67 Å³. Cs₂UGe₃O₉ (2) crystallizes in a hexagonal space group P-6 with lattice constants of a = 7.5138 Å, b = 7.5138 Å, c = 11.0114 Å, γ = 120° and V = 538.38 ų. Bond valence calculations indicate tetravalent uranium in both structures, which contain three-membered single-ring T₃O₉^6? trimers. K₂USi₃O₉ is the first uranium silicate that contains the Si₃O₉^6? trimers.     

A calorimetric and thermodynamic investigation of A2[(UO2)2(MoO4)O2] compounds with A = K and Rb and calculated phase relations in the system (K2MoO4 + UO3 + H2O)

A calorimetric and thermodynamic investigation of two alkali-metal uranyl molybdates with general composition A₂[(UO₂)₂(MoO₄)O₂], where A = K and Rb, was performed. Both phases were synthesized by solid-state sintering of a mixture of potassium or rubidium nitrate, molybdenum (VI) oxide and gamma-uranium (VI) oxide at high temperatures. The synthetic products were characterised by X-ray powder diffraction and X-ray fluorescence methods. The enthalpy of formation of K₂[(UO₂)₂(MoO₄)O₂] was determined using HF-solution calorimetry giving Δ_fH° (T = 298 K, K₂[(UO₂)₂(MoO₄)O₂], cr) = −(4018 ± 8) kJ · mol⁻¹. The low-temperature heat capacity, С_р°, was measured using adiabatic calorimetry from T = (7 to 335) K for K₂[(UO₂)₂(MoO₄)O₂] and from T = (7 to 326) K for Rb₂[(UO₂)₂(MoO₄)O₂]. Using these С_р° values, the third law entropy at T = 298.15 K, S°, is calculated as (374 ± 1) J · K⁻¹ · mol⁻¹ for K₂[(UO₂)₂(MoO₄)O₂] and (390 ± 1) J · K⁻¹ · mol⁻¹ for Rb₂[(UO₂)₂(MoO₄)O₂]. These new experimental results, together with literature data, are used to calculate the Gibbs energy of formation, Δ_fG°, for both phases giving: Δ_fG° (T = 298 K, K₂[(UO₂)₂(MoO₄)O₂], cr) = (−3747 ± 8) kJ · mol⁻¹ and Δ_fG° (T = 298 K, Rb₂[(UO₂)₂(MoO₄)], cr) = −3736 ± 5 kJ · mol⁻¹. Smoothed С_р°(Т) values between 0 K and 320 K are presented, along with values for S° and the functions [H°(T) − H°(0)] and [G°(T) − H°(0)], for both phases. The stability behaviour of various solid phases and solution complexes in the (K₂MoO₄ + UO₃ + H₂O) system with and without CO₂ at T = 298 K was investigated by thermodynamic model calculations using the Gibbs energy minimisation approach.     

Real structure of SrSi2O2N2

SrSi₂O₂N₂ is an important host lattice for Eu²⁺ doped phosphors. Its crystal structure (space group P1, a = 7.0802(2) Å, b = 7.2306(2) Å, c = 7.2554(2) Å, α = 88.767(3)°, β = 84.733(2)°, γ = 75.905(2)° and V = 358.73(2) Å³, Z = 4) is isotypic with EuSi₂O₂N₂: highly condensed silicate layers are separated by Sr²⁺. The samples are characterized by pronounced real structure effects owing to pseudosymmetry of partial structures. Polysynthetic twinning with domains of various sizes is ubiquitous and oriented intergrowth of domains with different orientations has also been observed and analysed in detail by means of electron diffraction and high-resolution electron microscopy. These effects also affect the X-ray powder pattern and were taken into account in a Rietveld refinement.     

A new paratungstate-A-based organic–inorganic hybrid compound: Synthesis,structure and photocatalytic property of [Co(en)3]2[H2W7O24]·8H2O

A new paratungstate-A-based organic–inorganic hybrid compound with the chemical formula of [Co(en)₃]₂[H₂W₇O₂₄]·8H₂O (en = ethylenediamine) (1) has been hydrothermally synthesized and structurally characterized by the elemental analysis, IR, TG, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space group P2₁/c with a = 17.216(3) Å, b = 14.986(3) Å, c = 23.088(8) Å, β = 128.151(2)°, V = 4684.2 Å³, Z = 1, R₁ = 0.0484, and wR₂ = 0.1087. The structure of 1 consists of the [H₂W₇O₂₄]⁴⁻ building blocks and [Co(en)₃]²⁺ metal-organic cationic moieties, which are packed together via the electrostatic forces and extensive hydrogen-bonding interactions to form a three-dimensional supramolecular framework. Interestingly, compound 1 represents the first structurally-defined hybrid compound based on the metastable paratungstate-A polyoxoanions and metal–organic units. The degradation of Rhodamine-B (RhB) under UV irradiation with 1 as the heterogeneous photocatalyst has been investigated, showing a good photocatalytic property of 1 for RhB degradation.     

K2[Te4O8(OH)10]: synthesis,crystal structure and thermal behavior

Dipotassium octaoxodecahydroxotetratellurate, K₂[Te₄O₈(OH)₁₀], has been prepared hydrothermally in acidic medium under autogenous pressure. It crystallizes in space group P2₁/c of the monoclinic system with Z=2 in a cell of dimensions a=5.592(1) Å, b=8.283(2) Å, c=16.255(3) Å, and β=99.62(3)°. The outstanding feature of the structure is a tetrameric [Te₄O₈(OH)₁₀]^2– anion built up from edge and corner sharing TeO₆ octahedra. These anions and K⁺ cations are held together by electrostatic interactions and by hydrogen bonds. The compound decomposes in two steps at 350 and 420 °C, corresponding to a water and an oxygen loss, respectively, and affording the mixed valence oxide K₂Te^VI₃Te^IVO₁₂.     

Identification of a new family of phosphate compounds,AIBII6(P2O7)2P3O10: structures of KMn6(P2O7)2P3O10 and AgMn6(P2O7)2P3O10

Two members of a new family of inorganic phosphates of general formula A^IB^II₆(P₂O₇)₂P₃O₁₀; KMn₆(P₂O₇)₂P₃O₁₀ (a=5.405(2), b=26.918(11), c=6.660(5), β=107.31(3)°, V=925.1(9) Å³, space group P2₁/m, Z=2, D_calc=3.481 Mg m⁻³, R=0.0377 for 2235 observed reflections) and AgMn₆(P₂O₇)₂P₃O₁₀ (a=5.424(7), b=26.97(4), c=6.627(9), β=106.81(7)°, V=928(2) Å³, space group P2₁/m, Z=2, D_calc=3.716 Mg m⁻³, R=0.0594 for 1577 observed reflections) have been synthesized and identified by single crystal X-ray diffraction. The isostructural complexes present an interesting comparison of silver and potassium bonding.     

Non-centrosymmetric sodium borate: Crystal growth,characterization and properties on Na2B4O12H10

In this study, both solvent evaporation and hydrothermal methods were employed to grow hydrated sodium borate crystals using NaOH and H₃BO₃ as reagents, and transparent and colorless single-crystals were successfully obtained with sizes up to 12 × 6 × 6 mm³ and 6 × 5 × 4 mm³, respectively. The structure is determined by single-crystal X-ray diffraction techniques. The title compound crystallizes in the trigonal space group R32, with a = 11.1042(16) Å, b = 11.1042(16) Å, c = 21.131(4) Å, Z = 9 and R₁ = 0.0322, wR₂ = 0.0840. Infrared and transmission spectra are presented for the reported material. The powder second-harmonic generation (SHG) intensity measured by the Kurtz-Perry method indicates that the SHG effect of Na₂B₄O₁₂H₁₀ is about one-third times that of KH₂PO₄ (KDP).     

Crystal Structure and Thermal Behaviour of K2[CrF5·H2O]

K₂[CrF₅·H₂O] is monoclinic: a = 9.6835(3) Å, b = 7.7359(2) Å, c = 7.9564(3) Å, β = 95.94(1)°, Z = 4, space group C2/c (n^o 15). Its crystal structure was solved from its X‐ray powder pattern recorded on a powder diffractometer, using for the refinement the Rietveld method. It is built up from isolated octahedral [CrF₅·OH₂]^2? anions separated by potassium cations. The dehydration of K₂[CrF₅·H₂O] leads to anhydrous orthorhombic K₂CrF₅: a = 7.334(2) Å, b = 12.804(4) Å, c = 20.151(5) Å, Z = 16, space group Pbcn (n^o 60), isostructural with K₂FeF₅.     

Single crystal growth and structural characterization of ternary transition-metal uranium oxides: MnUO4, FeUO4, and NiU2O6

Single crystals of MnUO₄, FeUO₄, and NiU₂O₆ were grown for the first time. The use of chloride fluxes facilitated the crystal growth. MnUO₄, a hexavalent uranium compound, crystallizes in the orthorhombic space group, Imma, with a = 6.6421(19) Å, b = 6.978(2) Å, and c = 6.748(2) Å, and exhibits typical uranyl, UO₂²⁺, coordination. FeUO₄ and NiU₂O₆ contain pentavalent uranium and are structurally related, exhibiting three-dimensional connectivity. FeUO₄ crystallizes in the orthorhombic space group, Pbcn, with a = 4.8844(2) Å, b = 11.9328(5) Å, c = 5.1070(2) Å. NiU₂O₆ crystallizes in the trigonal space group, P321, with a = 9.0148(3) Å, c = 5.0144(3) Å.     

Crystal structure,physical properties and bond valence analysis of NaLuP2O7

Single crystals of a diphosphate NaLuP₂O₇ have been synthesized by the flux method and characterized by single-crystal X-Ray diffraction. NaLuP₂O₇ crystallizes in the monoclinic system with P2₁/n space group with cell parameters: a = 8.9985(8) Å, b = 5.3473(5) Å, c = 12.756(1) Å, β = 103.174° (1), V = 597.67 (9) Å³, Z = 4. Its structure consists of a three-dimensional framework of P₂O₇ units that are corner-shared by LuO₆ octahedra, forming tunnels running parallel to [010] which are occupied by Na atoms. NaLuP₂O₇ powder was characterized by XRD, SEM, FTIR and Raman spectroscopy. The activation energy of (1.49 eV) obtained by electrical measurements suggests the charge carriers to be the sodium cations. The activation energies obtained from impedance and loss spectra were analyzed in order to explain the mechanism of conduction. The correlation between ionic conductivity of NaLuP₂O₇ and its crystallographic structure was investigated and the most probable transport pathway model was determined.     

Synthesis,structure, physical properties,and electronic structure of KGaSe2

The ternary gallium selenide KGaSe₂ has been synthesized by solid-state reactions and good quality crystal has been obtained. KGaSe₂ crystallizes in the monoclinic space group C2/c with cell dimensions of a = 10.878(2) Å, b = 10.872(2) Å, c = 15.380(3) Å, and β = 100.18(3)°. In the structure, adamantane like [Ga₄Se₁₀]⁸⁻ units are connected by common corners forming two-dimensional [GaSe₂]⁻ layers which are separated by K⁺ cations. KGaSe₂ exhibits congruent-melting behavior at around 965 °C. It is transparent in the range of 0.47–20.0 μm and has a band gap of 2.60(2) eV. From a band structure calculation, KGaSe₂ is a direct-gap semiconductor. The band gap is mainly determined by the [GaSe₂]⁻ layer.     

Synthesis,crystal structure,and magnetic properties of the oxometallates KBaMnO4 and KBaAsO4

Single crystals of KBaMnO₄ and KBaAsO₄ were grown using the hydroflux method and characterized by single crystal X-ray diffraction. Both compounds crystallize in the orthorhombic space group Pnma with a = 7.7795(4) Å, b = 5.8263(3) Å, and c = 10.2851(5) Å for the manganate and a = 7.7773(10) Å, b = 5.8891(8) Å, and c = 10.3104(13) Å for the arsenate. The materials exhibit a three-dimensional crystal structure consisting of isolated MnO₄³⁻ or AsO₄³⁻ tetrahedra, with the charge balance maintained by K⁺ and Ba²⁺. Each tetrahedron is surrounded by six K⁺ and five Ba²⁺, and shares its corner/edge with KO₁₀ polyhedra and corner/edge/face with BaO₉ polyhedra, respectively. The crystal growth, crystal structure and magnetic properties are discussed.     

Two novel Keggin tungstocobaltates grafted by cobaltII complex group(s): K[Co(phen)2(H2O)]2[HCoW12O40]·2H2O and [Co(2,2′-bipy)3]1.5{[Co(2,2′-bipy)2(H2O)][HCoW12O40]}·0.5H2O

Two novel inorganic–organic hybrid compounds composed of Keggin tungstocobaltate framework and cobalt(II)–N coordination complexes, K[Co(phen)₂(H₂O)]₂[HCoW₁₂O₄₀]·2H₂O (1) (phen = 1,10-phenanthroline) and [Co(2,2′-bipy)₃]_1.5{[Co(2,2′-bipy)₂(H₂O)][HCoW₁₂O₄₀]·0.5H₂O (2) (bipy = bipyridine), have been synthesized under hydrothermal conditions by directly using Keggin POMs as starting materials, which were characterized by elemental analyses, IR, TG analyses and X-ray single crystal diffraction. Crystal data for compound 1: C₄₈H₄₁Co₃KN₈O₄₄W_12, triclinic, space group P-1, a = 10.918(5) Å, b = 13.401(5) Å, c = 13.693(5) Å, α = 69.291(5)°, β = 71.568(5)°, γ = 78.421(5)°, V = 1768.9(12) Å³, Z = 1; for compound 2: C₁₃₀H₁₀₄Co₇N₂₆O₈₃W_24, orthorhombic, space group, C2/c, a = 46.839(9) Å, b = 14.347(3) Å, c = 26.147(5) Å, α = β = γ = 90°, V = 17,570(6) Å³, Z = 4. Compound 1 exhibits a pseudo-1D chainlike structure, in which potassium ions act as linkages of Keggin unit doubly grafted by [Co(phen)₂(H₂O)] complex. Compound 2 represents a [Co(2,2′-bipy)₂(H₂O)]²⁺ mono-grafted Keggin tungstocobaltate derivative with 1.5[Co(2,2′-bipy)₃]²⁺ countercations. The cyclic voltammetric behavior of 1-CPE is similar to the parent 3-CPE, but the cyclic voltammetric behavior of Co^II shows a little difference. Variable-temperature magnetic susceptibility measurement of compound 1 demonstrates the presence of antiferromagnetic interactions.     

(C5H6N)4[Be6(HPO3)8]·H2O: A low-density open-framework beryllium phosphite with multidirectional 12-ring channels

Employing the common pyridine (=py) solvent as the source of structure-directing agents (SDAs), a novel three-dimensional open-framework beryllium phosphite (Hpy)₄[Be₆(HPO₃)₈]·H₂O (1), has been solvothermally synthesized and structurally characterized by IR, elemental analysis, thermogravimetric analysis, powder and single-crystal X-ray diffractions. It crystallizes in the orthorhombic system, space group Pbca (No. 61), a = 20.0034(4) Å, b = 20.2188(4) Å, c = 20.9731(3) Å, V = 8482.5(3) Å³, and Z = 8. The alternating connection of BeO₄ tetrahedra and HPO₃ pseudopyramids give rise to a (3, 4)-connected network with multidirectional intersecting 12-ring channels. The compound possesses a low density and a new {4.8.10}{4².6.8.10.12}{4².6}₃{4².8.10².12}{4³.6².8} topology.     

Crystal structure and ionic conductivity of AgCr2(PO4)(P2O7)

Single crystals of a new phosphate AgCr₂(PO₄)(P₂O₇) have been prepared by the flux method and its structural and the infrared spectrum have been investigated. This compound crystallizes in the monoclinic system with the space group C2/c and the parameters are, a = 11.493 (3) Å, b = 8.486 (3) Å, c = 8.791 (2) Å, β = 114.56 (2)°, V = 779.8 (3) ųand Z = 4. Its structure consists of CrO₆ octahedra sharing corners with P₂O₇ units to form undulating chains extending infinitely along the [110] direction. These chains are connected by the phosphate tetrahedra giving rise to a 3D framework with six-sided tunnels parallel to the [101] direction, where the Ag⁺ ions are located. The infrared spectrum of this compound was interpreted on the basis of P₂O₇^4? and PO₄^3? vibrations. The appearance of ν_sP–O–P in the spectrum suggests a bent P–O–P bridge for the P₂O₇^4? ions in the compound, which is in agreement with the X-ray data. The electrical measurements allow us to obtain the activation energy of (1.36 eV) and the conductivity measurements suggest that the charge carriers through the structure are the silver captions.     

Thermodynamic properties of Na2Ti6O13 and Na2Ti3O7: electrochemical and calorimetric determination

Standard values of Gibbs free energy, entropy, and enthalpy of Na₂Ti₆O₁₃ and Na₂Ti₃O₇ were determined by evaluating emf-measurements of thermodynamically defined solid state electrochemical cells based on a Na–β″-alumina electrolyte. The central part of the anodic half cell consisted of Na₂CO₃, while two appropriate coexisting phases of the ternary system Na–Ti–O are used as cathodic materials. The cell was placed in an atmosphere containing CO₂ and O₂. By combining the results of emf-measurements in the temperature range of 573⩽T/K⩽1023 and of adiabatic calorimetric measurements of the heat capacities in the low-temperature region 15⩽T/K⩽300, the thermodynamic data were determined for a wide temperature range of 15⩽T/K⩽1100. The standard molar enthalpy of formation and standard molar entropy at T=298.15 K as determined by emf-measurements are Δ_fH_m⁰=(−6277.9±6.5) kJ · mol⁻¹ and S_m⁰=(404.6±5.3) J · mol⁻¹ · K⁻¹ for Na₂Ti₆O₁₃ and Δ_fH_m⁰=(−3459.2±3.8) kJ · mol⁻¹ and S_m⁰=(227.8±3.7) J · mol⁻¹ · K⁻¹ for Na₂Ti₃O₇. The standard molar entropy at T=298.15 K obtained from low-temperature calorimetry is S_m⁰=399.7 J · mol⁻¹ · K⁻¹ and S_m⁰=229.4 J · mol⁻¹ · K⁻¹ for Na₂Ti₆O₁₃ and Na₂Ti₃O₇, respectively. The phase widths with respect to Na₂O content were studied by using a Na₂O-titration technique.     

A new potassium rare earth oxyborate K2La2(BO3)2O

A series of potassium rare earth oxyborates, K₂RE₂(BO₃)₂O (RE = La, Nd, Sm and Eu), have been synthesized. Single crystal of the first member of the series, K₂La₂(BO₃)₂O, has been grown by the flux method. Its structure, determined by single crystal X-ray diffraction, shows that it belongs to the monoclinic system, space group P2₁/c with unit cell parameters of a = 11.422(2) Å, b = 6.6803(13) Å, c = 10.813(2) Å, β = 17.23(3)° and Z = 4. Optical transmission spectrum shows that the K₂La₂(BO₃)₂O crystal is highly transparent from 215 nm to 2750 nm.     

New gallium pentaphosphates: AGa2P5O16 (A=Rb,Cs)

Gallium pentaphosphates have been synthesized for the first time. These compounds, RbGa₂P₅O₁₆ and CsGa₂P₅O₁₆, are isotypic to the cesium pentaphosphates CsM₂P₅O₁₆ (M=Fe, V). They crystallize in the noncentrosymmetric Pn space group with a=7.4058(3) Å, b=9.2151(2) Å, c=10.0912(11) Å, β=110.768(8)°, V=643.9(1) Å³ (Z=2) and a=7.462(2) Å, b=9.241(3) Å, c=10.103(2) Å, β=110.731(16)°, V=651.5(3) Å³ (Z=2) for the rubidium and cesium compounds, respectively. The single crystal structure determination shows that the 3D [Ga₂P₅O₁₆]_∞ framework is rather rigid and does not vary significantly whatever M=Fe, V, Ga and A=Rb, Cs. The strongly distorted character of the pentaphosphate unit may be at the origin of strains along the P₅O₁₆ group, which explains the difficulty to stabilize pentaphosphates.     

Heat capacities,third-law entropies and thermodynamic functions of the geometrically frustrated antiferromagnetic spinels GeCo2O4 and GeNi2O4 from T=(0 to 400) K

The molar heat capacities of GeCo₂O₄ and GeNi₂O₄, two geometrically frustrated spinels, have been measured in the temperature range from T=(0.5 to 400) K. Anomalies associated with magnetic ordering occur in the heat capacities of both compounds. The transition in GeCo₂O₄ occurs at T=20.6 K while two peaks are found in the heat capacity of GeNi₂O₄, both within the narrow temperature range between 11.4<(T/K)<12.2. Thermodynamic functions have been generated from smoothed fits of the experimental results. At T=298.15 K the standard molar heat capacities are (143.44 ± 0.14) J · K⁻¹ · mol⁻¹ for GeCo₂O₄ and (130.76 ± 0.13) J · K⁻¹ · mol⁻¹ for GeNi₂O₄. The standard molar entropies at T=298.15 K for GeCo₂O₄ and GeNi₂O₄ are (149.20 ± 0.60) J · K⁻¹ · mol⁻¹ and (131.80 ± 0.53) J · K⁻¹ · mol⁻¹ respectively. Above 100 K, the heat capacity of the cobalt compound is significantly higher than that of the nickel compound. The excess heat capacity can be reasonably modeled by the assumption of a Schottky contribution arising from the thermal excitation of electronic states associated with the CO²⁺ ion in a cubic crystal field. The splittings obtained, 230 cm⁻¹ for the four-fold-degenerate first excited state and 610 cm⁻¹ for the six-fold degenerate second excited state, are significantly lower than those observed in pure CoO.