Two polymorphs of Ba3Sn2P4: Single crystal and electronic structures

Two polymorphs (I and II) of Ba₃Sn₂P₄ have been found in the same preparative batch. Both compounds crystallize in the centrosymmetric monoclinic space group P2₁/c (#14, a = 7.8669(2) Å, b = 19.2378(5) Å, c = 7.8472(2) Å, β = 112.77(1)°, V = 1095.06(5) Å³, Z = 4, and R/wR = 0.0303/0.0710 for I; a = 7.8771(3) Å, b = 19.4099(7) Å, c = 7.7040(3) Å, β = 112.44(1)°, V = 1088.67(7) Å³, Z = 4, and R/wR = 0.0224/0.0415 for II). Both structures consist of one-dimensional chains separated by Ba²⁺ cations. The isolated chain consists of condensed ethane-like [Sn₂P₆] units. In polymorphs I and II, the condensation and connectivity of the [Sn₂P₆] units are quite different. While [Sn₂P₆] units form four- and six-membered rings in I, they form the five-membered rings in II. The electronic structure calculations indicate that semiconducting behavior is expected for both compounds.     

On the crystal structure of new series of compounds, RPt2+xSb2−y (x = 0.125, y = 0.25; R = La, Ce, Pr)

A new compound CePt_2+xSb_2−y (x = 0.125, y = 0.25) was synthesized by arc-melting of the elements. The chemical and structural characterizations were carried out at room temperature on as-cast samples using X-ray diffractometry, metallographic analysis and EDS-microanalysis. According to the results of X-ray single crystal diffraction this antimonide crystallizes in I4cm space group (no. 108), Z = 32, ρ = 12.19 Mg/m³, μ = 89.05 mm⁻¹ (a = 12.5386(3) Å, c = 21.4692(6) Å (crystal I) and a = 12.5455(2) Å, c = 21.4791(5) Å (crystal II)). The structure and composition were confirmed by powder X-ray diffraction (a = 12.4901(2) Å, c = 21.3620(4) Å) and EDS-microanalysis respectively. Isotypic compounds were observed with La and Pr from X-ray powder diffraction of as-cast alloys at room temperature (a = 12.6266(4) Å, c = 21.4589(6) Å for LaPt_2+xSb_2−y and a = 12.5184(5) Å, c = 21.4178(7) Å for PrPt_2+xSb_2−y). The CePt_2+xSb_2−y structure is derived from CaBe₂Ge₂ (a = 2a₀ − 2b₀, b = 2a₀ + 2b₀, c = 2c₀) and comprises a new atomic arrangement with both vacancy on 4(b) pyramidal site and substitution of antimony atoms (X) by platinum (B) in the B–XX–B layers (referring to the subcell structure) forming two B––1/2B1/2XX–3/4B and two X–BB–X layers per cell. The structure of CePt_2+xSb_2−y is compared with those reported before for URh_1.6As_1.9 and CeNi_1.91As_1.94.     

High-pressure synthesis and crystal structures of two new polyphosphides, NaP5 and CeP5

Two novel polyphosphides, NaP₅ and CeP₅, were prepared in a BN crucible by the reaction of elemental components under a high pressure of 3 GPa at 800–950 °C. The X-ray structural analysis showed that NaP₅ crystallizes in an orthorhombic space group Pnma with a=10.993(2) Å, b=6.524(1) Å, c=6.903(1) Å, Z=4 and CeP₅ in the monoclinic group P2₁/m with a=4.9143(5) Å, b=9.6226(8) Å, c=5.5152(4) Å, β=104.303(6)°, Z=2. The crystal structure of NaP₅ consists of a three-dimensional framework _∞³[P₅]¹⁻ constructed by P---P bonds among four crystallographically inequivalent phosphorus sites, with large channels hosting the sodium cations, while CeP₅ is a layered compound containing _∞²[P₅]³⁻ polyanionic layers that are separated by Ce³⁺ ions. NaP₅ exhibits the diamagnetic behavior, while the temperature-dependent magnetic susceptibility of CeP₅ essentially follows the Curie–Weiss law.     

Syntheses and single-crystal structures of La3AgSnS7, Ln3MxMS7 (Ln = La, Ho, Er; M = Ge, Sn; 1/4 ≤ x ≤ 1/2)

In our investigation of non-centrosymmetric rare earth sulfides in the La₃AgSnS₇/KBr, LaAlGeS₅/NaBr, HoAlGeS₅/KBr, ErAlGeS₅/NaBr, Er₃AgGeS₇/KBr and La₃NaSnS₇/NaBr systems, five compounds belonging to the R₆B₂C₂Q₁₄ family have been obtained. These compounds crystallize in the P6₃ space group, and the crystal data are as follows—La₃AgSnS₇: a = 10.3780(15) Å, c = 5.9900(12) Å, Z = 2; La₃Ge_0.25GeS₇: a = 10.2970(15) Å, c = 5.8120(12) Å, Z = 2; Ho₃Ge_0.272(10)GeS₇: a = 9.6480(14) Å, c = 5.7920(12) Å, Z = 2; Er₃Ge_0.330(10)GeS₇: a = 9.5930(14) Å, c = 5.8490(12) Å, Z = 2; La₃Sn_0.25SnS₇: a = 10.2770(15) Å, c = 6.0030(12) Å, Z = 2. Single-crystal analysis indicated that the crystal structures consist of three types of building block: LnS_n, MS₄, and AgS₃ (for La₃AgSnS₇) or MS₆ units (for Ln₃M_xMS₇, Ln = La, Ho, Er; M = Ge, Sn; 1/4 ≤ x ≤ 1/2), as any other compounds belonging to the R₆B₂C₂Q₁₄ family. Ln₃M_xMS₇ (Ln = La, Ho, Er; M = Ge, Sn; 1/4 ≤ x ≤ 1/2) are deficient compounds with the B sites occupied partly by M(II), and/or M(IV).     

LaMg2NiH7, a novel quaternary metal hydride containing tetrahedral [NiH4] complexes and hydride anions

A new ternary compound of composition LaMg₂Ni has been found and investigated with respect to structure and hydrogenation properties. It crystallizes with the orthorhombic MgAl₂Cu type structure (space group Cmcm, a=4.2266(6), b=10.303(1), c=8.360(1) Å; V=364.0(1) ų; Z=4) and absorbs hydrogen near ambient conditions (<200 °C, <8 bar) thereby forming the quaternary metal hydride LaMg₂NiH₇. Neutron powder diffraction on the deuteride revealed a monoclinic distorted metal atom substructure (LaMg₂NiD₇: space group P2₁/c, a=13.9789(7), b=4.7026(2), c=16.0251(8) Å; β=125.240(3)°, V=860.39(8) ų; Z=8) that contains two symmetry independent tetrahedral [NiD₄]⁴⁻ complexes with Ni–D bond lengths in the range 1.49–1.64 Å, and six D⁻anions in tetrahedral metal configuration with bond distances in the ranges 1.82–2.65 Å (Mg) and 2.33–2.59 Å (La). The compound constitutes a link between metallic ‘interstitial’ hydrides and non-metallic ‘complex’ metal hydrides.     

An investigation of the structures of the compounds in the tin-rich part of the Dy–Sn system: Crystal structure of Dy5Sn11 and Dy5Sn13

The structural properties of the compounds in the tin-rich part of the dysprosium–tin system have been studied by X-ray powder diffraction. The crystal structures of six compounds DySn_2+x (0 < x < 1) have been characterized. There are four compounds with known structural types: DySn₂ with the ZrSi₂ structure, Dy₃Sn₇ with the Gd₃Sn₇ structure, Dy₂Sn₅ with the Er₂Ge₅ structure, DySn₃ with the DyGe₃ structure and two compounds characterized by new body-centred orthorhombic types (Immm): Dy₅Sn₁₁ (a = 4.411 Å, b = 42.50 Å and c = 4.328 Å) and Dy₅Sn₁₃ (a = 4.341 Å, b = 48.05 Å and c = 4.405 Å) which result from various insertions of AuCu₃ and Po slabs into the ZrSi₂ structure. The relationships and structural evolution are discussed.     

Ce(Au,Sb)2 with UHg2 structure type, a new member of the AlB2 family

A new ternary compound Ce(Au,Sb)₂, with a homogeneity range has been observed from X-ray powder diffraction of as cast alloys, a = 4.743–4.712 Å, c = 3.567–3.768 Å. Its crystal structure was investigated by X-ray diffraction from Ce(Au_1−xSb_x)₂ (x = 0.266) single crystal: CAD-4 automatic diffractometer, Mo K radiation, a = 4.7256(6) Å, c = 3.6711(6) Å, P6/mmm space group, V = 70.997(17) Å³, Z = 1, ρ = 10.732 Mg/m³, μ = 76.369 mm⁻¹, R₁ = 0.0415, wR₂ = 0.0793 for 99 reflections with I > 2σ(I₀). The coordination polyhedron of X (X = 0.734Au + 0.266Sb) atom is a full-capped trigonal prism [XCe₆X₃X₂]. Ce atom is coordinated by 14 atoms: [CeX₁₂Ce₂]. The compound is isotypic with UHg₂ structure, a deformation derivative of AlB₂ structure type. It forms isostructural compounds with La and Pr.     

Structural investigation of the alluaudite-like mixed-valence iron phosphate: Na1.25Mg1.10Fe1.90(PO4)3

A new mixed-valence iron phosphate Na_1.25Mg_1.10Fe_1.90(PO₄)₃ has been synthesized as single crystals by a flux technique and its structure has been refined from X-ray data to a residual R₁ = 0.032. The compound crystallizes in the monoclinic space group C2/c with the parameters: a = 11.7831(3) Å, b = 12.4740(3) Å, c = 6.3761(2) Å, β = 113.643(2)° and Z = 4. The structure belongs to the alluaudite structural type, and thus it obeys to the X(2)X(1)M(1)M(2)₂(PO₄)₃ general formula. The X(2) and X(1) sites are occupied by sodium while the M(1) and M(2) sites feature a statistical distribution of iron and magnesium.

Additional information about the cation distribution has been extracted from a Mössbauer spectroscopy study which confirmed the mixed valency of the compound. A magnetic susceptibility study has also been undertaken and has shown the compound to be antiferromagnetic with a Neel temperature of about 35 K.     

Synthesis, structure and fluorescence properties of a highly stable indium(III)-2,5-pyridinedicarboxylate coordination polymer

The hydrothermal reaction of 2,5-pyridinedicarboxylic acid (H₂PDC), diethylene triamine and In(NO₃)₃·4.5H₂O gave rise to a two-dimensional (2D) coordination polymer In(OH)(2,5-PDC). This compound crystallizes in the orthorhombic space group Iba2, with cell parameters, a = 12.656(3) Å, b = 20.114(4) Å, c = 6.2216(1) Å, V = 1583.9(5) Å³ and Z = 8. Its structure contains one-dimensional In–O–In–O– chains, which are further linked by 2,5-PDC ligands into a 2D supramolecular neutral framework. The adjacent 2D layers are parallel with each other and construct a three-dimensional framework via hydrogen bands. At room temperature, the compound exhibits intense photoluminescence. On the basis of the results of TG/DTA analyses, the structure is thermally stable up to 390 °C.     

Nd11Pd4In9 compound – A new member of the homological series based on AlB2 and CsCl types

The Nd₁₁Pd₄In₉ compound was prepared by arc melting of pure metals under an argon atmosphere. Crystal structure was refined from X-ray single crystal diffractometer data (space group Cmmm, a = 14.843(3), b = 22.284(3), c = 3.7857(6) Å, Z = 2, R_I = 0.0584, 653 F₂ values). It has own structure type and together with Mn₂AlB₂, Cr₃AlB₄, Mo₂FeB₂ and Lu₅Ni₂In₄ structure types belongs to homological series based on AlB₂ and CsCl structure types with common formula R_m+nM_2nX_m.     

Synthese und kristallstruktur von KCr0,8Al0,2Mo2O8

Single crystals of KCr_0.8Al_0.2Mo₂O₈ were prepared and investigated by the X-ray diffractometer technique. It shows a structure type related to trigonal KAIMo₂O₈, monoclinic NaCrMo₂O₈ or orthorhombic KInMo₂O₈, space group C_2h⁶—C2/c; a=17.445 Å, b=5.649 Å, c=8.997 Å, β=119.37°; Z=4. KCr_0.8Al_0.2Mo₂O₈ is characterized by isolated MoO₄ tetrahedra, isolated (Cr/Al)O₆ octahedra and a distorted square antiprism around K⁺. The crystal structure is discussed with respect to those of related compounds.

Zusammenfassung

Einkristalle von KCr_0.8Al_0.2Mo₂O₈ wurden synthetisiert und mit Vierkreisdiffraktometertechnik röntgenographisch untersucht. Sie zeigen einen mit trigonal-KA1Mo₂O₈, monoklin-NaCrMo₂O₈ oder orthorhombisch-KlnMo₂O₈ verwandten Strukturtyp, Raumgruppe C_2h⁶—C2/c; a=17,445 Å, b=5,649 Å, c=8,997 Å, β=119,37°; Z=4. KCr_0.8Al_0.2Mo₂O₈ zeichnet sich durch isolierte MoO₄-Tetraeder, isolierte (Cr/Al)O₆-Oktaeder und ein verzerrtes quadratisches Antiprisma um K⁺ aus. Die Kristallstruktur wird mit solchen verwandter Verbindungen diskutiert.     

Crystal growth of MgAlB14-type compounds using metal salts and some properties

LEAlB₁₄ (orthorhombic, Imam) (LE = Li, Mg) crystals were grown using metal salts (Li₂CO₃, LiF, LiI, MgO, MgF₂, MgI₂) and crystalline boron from a high-temperature aluminium metal flux. The growth conditions for growing LEAlB₁₄ were established using the starting mixtures of B/LE = 2.0, and Al metal was added to each mixture at a mass ratio of 1:15–20. LEAlB₁₄ crystals from the Al-self flux using metal salts could be obtained from all the different salts. The maximum dimensions of LiAlB₁₄ and MgAlB₁₄ crystals were approximately 18 and 12 mm for the crystals obtained from LiF and MgF₂. The unit-cell parameters of as-grown LEAlB₁₄ are as follows: for LiAlB₁₄, obtained from LiF, a = 0.5846 (2) nm, b = 0.8144 (2) nm, c = 1.0355 (3) nm, V = 0.4930 (2) nm³: for MgAlB₁₄, obtained from MgF₂, a = 0.5845 (2) nm, b = 0.8114 (2) nm, c = 1.0330 (3) nm, V = 0.4899 (3) nm³. Microhardness, oxidation resistance and magnetic susceptibility of these materials are described in detail.     

Subsolidus phase relation in the system ZnO–Li2O–MoO3

The subsolidus phase relation of the system ZnO–Li₂O–MoO₃ has been investigated by X-ray diffraction (XRD) analyses. The phase diagram has been constructed. There are six binary compounds and one ternary compound in this system. The phase diagram comprises nine three-phase regions. The ternary compound Li₂Zn₂(MoO₄)₃ is refined by the Rietveld method. It belongs to an orthorhombic system with space group Pnma and lattice constants a = 5.1114 Å, b = 10.4906 Å, c = 17.6172 Å.     

Crystal structure of La5Ti4GaO17

The crystal structure of La₅Ti₄GaO₁₇ compound synthesized by heat-treatment of the co-precipitated hydroxy-oxalates has been determined by the X-ray powder diffraction. It was found that crystal structure of La₅Ti₄GaO₁₇ belongs to the CaLa₄Ti₅O₁₇-type structure (space group Pmnn, a = 0.3912(1) nm, b = 3.128(1) nm, c = 0.5523(1) nm, Z = 2). The final R_W value is equal to 0.081 for 169 independent reflections.     

Structural investigation of ternary RIr3B2 compounds (R=Ce and Pr)

Structural studies were performed for the ternary RIr₃B₂ compounds (R=Ce and Pr) from as cast samples. The crystal structure of the ternary boride CeIr₃B₂ (CeCo₃B₂ structure type, space group P6/mmm, a=5.520(3) Å, c=3.066(2) Å, Z=1, V=80.91 ų, ρ_x=15.154 g cm⁻³) was refined to R₁=0.0470, wR₂=0.1240 from single-crystal X-ray diffraction data. The new ternary boride PrIr₃B₂ was found to be isostructural with the CeIr₃B₂ compound. Its lattice parameters a=5.5105(2) Å, c=3.1031(1) Å were obtained from a Rietveld refinement of X-ray powder diffraction data.     

Synthesis and structure of a potassium nitridoditungstenate (K6W2N4O3), a potassium digermanate (K6Ge2O7) and a rubidium digermanate (Rb6Ge2O7)

Light yellow single crystals of potassium nitridoditungstate (K₆W₂N₄O₃) and pale single crystals of potassium digermanate (K₆Ge₂O₇) were obtained by the reaction of the metal oxides WO₃ (molar ratio, 1 : 15.7) or GeO₂ (molar ratio, 1 : 2) in alkali metal amide melts in an autoclave at 530–600 °C for 6–8 days. Colourless single crystals of rubidium digermanate (Rb₆Ge₂O₇) were prepared by the reaction of GeO₂ with rubidium amide (molar ratio, 1 : 2) in ammonia at 350 °C in a high-pressure autoclave (H. Jacobs and D. Schmidt, in E. Kaldis (ed.), High-pressure Ammonolysis in Solid State Chemistry, Current Topics in Materials Science, Vol. 8, North Holland, Amsterdam, 1981, p. 379) (p(NH₃) = 5.5 kbar) for 10 days. In all three cases other nitrogen-containing products were present.

The structures of the title compounds were determined on the basis of single-crystal data. They are isotypic or structurally closely related to each other: K₆W₂N₄O₃: P2₁/n, a = 6.720(2) Å, b = 9.473(1) Å, c = 9.581(2) Å, β = 91.99(2)°, Z = 2, R/R_w = 0.040/0.048, N(I) > 3σ(I) 2057, N(Var.) = 71. K₆Ge₂O₇: Pn, a = 6.529(2) Å, b = 9.079(4) Å, c = 9.162(6)Å, β = 91.85(4)°, Z = 2, R/R_w = 0.022/0.024, N(I) 3σ(I) = 1486, N(Var.) = 135. Rb₆Ge₂O₇: P2₁/n, a = 6.839(4) Å, b = 9.437(6) Å, c = 9.460(6) Å, β = 91.53(5)°, Z = 2, R/R_w = 0.061/0.074, N(I) 3σ(I) = 1055, N(Var.) = 71.     

Hydrothermal synthesis and characterization of a new layered compound Li2VGeO5

The new compound Li₂VGeO₅ with a layered structure has been synthesized at 580 °C via the hydrothermal method. The compound crystallizes in the space group P4/n of the tetragonal system with two formula units in a cell of dimensions a=6.5187(9) Å, c=4.5092(9) Å (T=298 K), V=191.61(5) Å³. The structure is composed of layers made of repeating [(VO₅)(GeO₄)]¹⁻ units. Li⁺ ions reside between the layers. The magnetic susceptibility data show an antiferromagnetic coupling below 5 K with C=0.47 emu K mol⁻¹, and θ=−13 K with μ_eff=1.89μ_B for each Li₂VGeO₅ unit.     

The ternary system Na2O–ZnO–WO3: Compounds and phase relationships

The subsolidus phase relationships of ternary system Na₂O–ZnO–WO₃ have been investigated by X-ray diffraction (XRD) and differential thermal analyzer (DTA). All the samples were synthesized in the temperature range from 530 to 850 °C in air. There are one ternary compound and five binary compounds in the Na₂O–ZnO–WO₃ system, which can be divided into eight three-phase regions. The crystal structure of the ternary compound Na_3.6Zn_1.2(WO₄)₃ is determined by single-crystal structure analysis method. It belongs to triclinic system with space group and lattice constants a = 7.237 (5) Å, b = 9.172 (6) Å, c = 9.339 (6) Å and  = 94.920 (4)°, β = 105.772 (9)°, γ = 103.531 (8)°, Z = 2. DTA analyses indicate that the compound Na₂WO₄ is not suitable to be the flux for ZnO crystal growth below 1250 °C, since no liquidus was observed in the system before 1250 °C.     

Sr3GeMgN4: new quaternary nitride containing Mg

A new Mg-containing quaternary nitride, Sr₃GeMgN₄, was obtained as single crystals from constituent elements in molten Na. It crystallizes in space group Pnna (No. 52) with a=5.939(1) Å, b=10.320(2) Å, c=9.618(2) Å, and Z=6. It is isostructural with Sr₃Ga₂N₄, both of which contain one-dimensional chains of edge-sharing tetrahedra.