Crystal Growth of A<Subscript>3</Subscript>A′MO<Subscript>6</Subscript> Oxides

Abstract  

Single crystals of two new oxides, Sr₃LiNbO₆ and Sr₃LiTaO₆, and the analogous antimonates, Ba₃NaSbO₆, Sr₃NaSbO₆ and Sr₃LiSbO₆, were grown out of hydroxide melts contained in silver/alumina crucibles. The crystal structures of all five oxides are isotypic with that of the 2H-hexagonal perovskite related A₃A′MO₆ family of oxides and consist of one-dimensional chains of face-shared MO₆ octahedra and A′O₆ trigonal prisms; infinite chains of distorted AO₈ square antiprisms separate these chains from one another.     

AErP<Subscript>2</Subscript>O<Subscript>7</Subscript> (A = Rb,Cs) and HEuP<Subscript>2</Subscript>O<Subscript>7</Subscript>·3H<Subscript>2</Subscript>O: Crystal Structures,Vibrational Studies and Thermal Behaviours

Abstract  

New diphosphates AErP₂O₇, A = Rb (1), Cs (2), and HEuP₂O₇·3H₂O (3) have been prepared via soft chemistry route from evaporation of aqueous solution. Their crystal structures have been solved by single crystal diffraction data. The compounds (1) and (2) crystallize in the monoclinic space group P2₁/c with the following unit cell dimensions: (1) a = 7.7248(4) ?, b = 10.9342(6) ?, c = 8.6716(3) ?, β = 105.434(4)° and Z = 4; (2) a = 7.9192(4) ?, b = 10.8606(4) ?, c = 8.7684(5) ?, β = 104.317(5)° and Z = 4. Compound (3) crystallises in the triclinic space group P − 1, with the unit cell parameters: a = 6.4036(5) ?, b = 6.8753(6) ?, c = 9.7964(8) ?, α = 81.706(7)°, β = 80.218(7)°, γ = 88.381(7)°. Crystal structure of (1) and (2) consists of 3D open framework built from [ErO₆] octahedra sharing corners with [P₂O₇] units, leading to the formation of channels running along c direction in which A⁺ [A = Rb(1), Cs(2)] ions are located. The compound (3), on the other hand, exhibits a lamellar structure, in which edge-sharing polyhedra of eightfold coordinated europium form chains along [010]. These chains are joined in turn to each others using diphosphates bridges. A network of O–H···O hydrogen bonds reinforces the cohesion of the structure of (3). The diphosphate groups in (1), (2) and (3) adopts an eclipsed configuration. IR and Raman spectra of the three new phosphates show usual signals related to the P₂O₇ diphosphate group and the water molecule. TG and DTA studies were carried out on crystals of (3). The data are correlated to the crystal structures ones.     

Electrical conductivity of γ-irradiated crystals of La<Subscript>0.95</Subscript>Ba<Subscript>0.05</Subscript>F<Subscript>2.95</Subscript> superionic conductor

The electrical conductivity of single crystals of the La_0.95Ba_0.05F_2.95 superionic conductor subjected to irradiation by γ quanta (source γ-⁶⁰Co, dose 2 × 10⁶ rad) has been investigated. It is shown that the radiation defects do not have a great effect on the ionic conductivity of nonstoichiometric La_0.95Ba_0.05F_2.95 crystals, which is caused by the heterovalent replacements of La³⁺ cations with Ba²⁺ cations.     

Synthesis and Crystal Structures of the Coordination Polymers Pb(PYTAC)<Subscript>2</Subscript> and Pb<Subscript>2</Subscript>(PYTAC)<Subscript>3</Subscript>(NO<Subscript>3</Subscript>) (PYTAC = 2-(pyridin-4-yl)thiazole-5-carboxylate)

Abstract  

Two lead coordination compounds, Pb(PYTAC)₂ (1), and Pb(PYTAC)₂(NO₃) (2), were grown as single crystals via hydrothermal synthesis (PYTAC = 2-(4-pyridyl) thiazole-4-carboxylate). Both compounds have been identified via single crystal X-ray diffraction. Coordination polymer 1 crystallizes in a triclinic space group P-1 (a = 5.5097(4) ?, b = 7.2822(5) ?, c = 11.3134(8) ?, α = 103.5580(10)°, β = 99.4330(10)°, γ = 97.1050(10)°), and forms 2-D layers parallel to the crystallographic (ac) plane. Coordination polymer 2 crystallizes in a triclinic space group P-1 (a = 9.8102(5) ?, b = 10.5972(6) ?, c = 14.8076(8) ?, α = 91.9350(10)°, β = 100.8050(10)°, γ = 103.1350(10)°), and forms an infinite 1-D chains along the a axis.     

Synthesis,Crystal Structure,and Topology–Symmetry Analysis of a New Modification of NaIn[IO<Subscript>3</Subscript>]<Subscript>4</Subscript>

Crystals of new iodate NaIn[IO₃]₄ were prepared by the hydrothermal synthesis. The unit cell parameters are a = 7.2672(2) Å, b = 15.2572(6) Å, c = 15.0208(6) Å, β = 101.517(3)°, sp. gr. P2₁/c. The formula was determined during the structure determination and refinement of a twinned crystal based on a set of reflections from the atomic planes of the major individual. The refinement with anisotropic displacement parameters was performed for both twin components to the final R factor of 0.050. The In and Na atoms are in octahedral coordination formed by oxygen atoms. The oxygen octahedra are arranged into columns by sharing edges, and the columns are connected by isolated umbrella-like [IO₃]^– groups to form layers. The new structure is most similar to the isoformular iodate NaIn[IO₃]₄, which crystallizes in the same sp. gr. P2₁/c and is structurally similar, but has a twice smaller unit cell and is characterized by another direction of the monoclinic axis. The structural similarity and difference between the two phases were studied by topologysymmetry analysis. The formation of these phases is related to different combinations of identical one-dimensional infinite chains of octahedra.     

Structural Analysis of Sr<Subscript>3</Subscript>NbFe<Subscript>3</Subscript>Si<Subscript>2</Subscript>O<Subscript>14</Subscript> Single Crystal from the Langasite Family and Finding of Negative Thermal Expansion in the Range of 83–110 K

Iron-containing Sr₃NbFe₃Si₂O₁₄ single crystals from the langasite family, which are interesting for researchers due to their magnetic ordering at T _N = 26 K, have been grown by the floating zone melting method. Accurate X-ray diffraction analysis is performed at 293 and 90.5 K using the data collected on a CCD diffractometer. To compensate for systematic errors, two data sets are collected at each temperature. The structure is refined based on averaged data set: sp. gr. P321, Z = 1, sin θ/λ ≤ 1.35 Å^–1; a = 8.2609(4) Å, c = 5.1313(3) Å at 293 K and a = 8.2344(6) Å, c = 5.1243(6) Å at 90.5 K; the agreement factors are R/wR = 1.18/1.03% and Δρ_min/Δρ_max =–0.57/0.25 e/Å3 for 3583 independent reflections at 293 K and R/wR = 1.18/1.13% and Δρ_min/Δρ_max =–0.54/0.23 e/Å3 for 3638 reflections at 90.5 K. Negative thermal expansion in the direction of the cell c axis is revealed in the range of 83–110 K.     

Synthesis and Crystal Structure of [Na(H<Subscript>2</Subscript>O)<Subscript>1.5</Subscript>][Na(H<Subscript>2</Subscript>O)<Subscript>3.5</Subscript>] X<Subscript>2</Subscript>·2H<Subscript>2</Subscript>O (X = 4′-Methoxy-7-Hydroxyisoflavone-3′-Sulfonate)

Abstract  

Water-soluble derivative of formononetin, [Na(H₂O)_1.5][Na(H₂O)_3.5] X₂·2H₂O(X = 4′-methoxy-7-hydroxyisoflavone-3′-sulfonate) was synthesized by sulfonation reaction. It was characterized by IR, ¹H NMR and single-crystal X-ray diffraction analysis. Single-crystal X-ray diffraction analysis showed that the title compound crystallized in a triclinic space group P-1 with cell parameters a = 6.9642(15) ?, b = 13.343(3) ?, c = 20.634(5) ?, α = 107.115(3)˚, β = 93.121(4)˚, γ = 91.911(3)˚, V = 1827.3(7) ?⁻³, D _c  = 1.575 Mg m ⁻³, Z = 2. There are two conformers of 4′-methoxy-7-hydroxyisoflavone-3′-sulfonate anions, two kinds of sodium cations, five coordinated water molecules and two lattice water molecules in the crystal structure. The sodium atoms coordinated with the oxygen atoms from water molecules, hydroxyl groups and sulfo-groups to form a Na–O coordinated network. Aromatic π···π stacking interactions and hydrogen bonding existed in the crystal structure of title compound, which together with coordinated interactions and electrostatic interactions between sodium cations and anions sulfonates C₁₆H₁₀O₄SO₃ ⁻ lead to the moieties into a three-dimensional network.     

Synthesis,Crystal Structure and NLO Properties of a Mixed Crystal K<Subscript>1−x</Subscript>(NH<Subscript>4</Subscript>)<Subscript>x</Subscript>H<Subscript>2</Subscript>PO<Subscript>4</Subscript> (x = 0.5)

Abstract  

A new mixed crystal K_1−x(NH₄)_xH₂PO₄ (KADP) of ammonium dihydrogen phosphate (ADP) of ADP–KCl system has been synthesized with x = 0.5 by slow evaporation of the mixture of equimolar aqueous solution at room temperature. Crystal composition determined by single crystal X-ray diffraction analysis reveals that it belongs to the tetragonal system with noncentrosymmetric space group I-42d and it is structurally similar to ADP crystals with the following parameters: a = 7.418(3) ?; c = 7.2284(6) ?; v = 404.63(4) ?³; z = 4. The substitution results in defect centers which influence the physical properties. Mixed crystal has a superior NLO activity, twice that of KH₂PO₄ (KDP), a well known NLO material and the enhanced NLO activity is rationalized. The structural analysis of KADP and the influence of partial cationic substitution in ADP by K⁺ ions on the NLO properties are reported.     

Synthesis and Crystal Structure of (PzCH<Subscript>2</Subscript>CHOHCH<Subscript>2</Subscript>PzH)·(Ph<Subscript>2</Subscript>SnCl<Subscript>3</Subscript>) (Pz = 3,5-dimethylpyrazol-1-yl)

Abstract  

Reaction of Ph₂SnCl₂ with 1,3-bis(3,5-dimethylpyrazol-1-yl)-2-propanol (L) in a 1:1 ratio yields L(SnPh₂Cl₂)₂ adduct, which partly hydrolyzes to the title complex (C₂₅H₃₁Cl₃N₄OSn, Mr = 628.58) during crystal growing in the air. The title complex is of monoclinic, space group P2₁/n with a = 9.0338(9), b = 17.890(1), c = 17.340(1) ?, β = 95.533(1)^o, V = 2798.9(5) ?³, Z = 4, Dc = 1.492 Mg/m³, λ(MoKα) = 0.71073 ?, μ = 1.224 mm⁻¹, F(000) = 1272, R = 0.023, wR = 0.054 for 4212 observed reflections with I ≥ 2σ(I). The crystal structure indicates that there is no direct interaction between the pyrazolyl ligand and the tin atom, but this complex forms a supramolecular structure through weak intermolecular C–H⋯Cl and O–H⋯Cl hydrogen bonds.     

Two Metal Complexes Supported by {VO<Subscript>3</Subscript>}<Subscript>n</Subscript><Superscript>n−</Superscript> Chains: Hydrothermal Syntheses and Crystal Structures of [M(dpa)V<Subscript>2</Subscript>O<Subscript>6</Subscript>] (M = Zn(II) and Cu(II); dpa = 2,2′-dipyridylamine)

Abstract  

Two new metal complexes supported by {VO₃}_n ⁿ⁻ chains, [M(dpa)V₂O₆] (1, M = Zn²⁺; 2·H₂O, M = Cu²⁺; dpa = 2,2′-dipyridylamine), have been synthesized hydrothermally and characterized by elemental analysis, TG analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal data: [Zn(dpa)V₂O₆] 1, Triclinic, P-1, a = 9.663(7) ?, b = 10.617(7) ?, c = 15.114(10) ?, α = 105.678(10)°, β = 104.772(9)°, γ = 94.021(10)°, Z = 2; [Cu(dpa)V₂O₆]·H₂O 2·H₂O, Monoclinic, C2, a = 20.543(3) ?, b = 7.2460(9) ?, c = 10.4853(13) ?, β = 111.318(2)°, Z = 4. Complex 1 is constructed from sinusoidal {VO₃}_n ⁿ⁻ chains with {Zn(dpa)}²⁺ fragments spanning the adjacent troughs and crests into an 1D ribbon-like structure. Complex 2 is built up by linking {VO₃}_n ⁿ⁻ chains via pairs of symmetrical {Cu(dpa)}²⁺ fragments into a 2D layered structure. The Zn(II) and Cu(II) ions exhibit tetrahedral and square pyramidal coordination environments, respectively. The formation of the two isomers is attributed to the flexibility of {VO₃}_n ⁿ⁻ chains and the different coordination configurations of the two metal ions. There exist significant π–π stacking and hydrogen bonding interactions in complexes 1 and 2.     

Synthesis,Structure and Theoretical Research of a New Triaryl Phosphine Complex [HgCl<Subscript>2</Subscript>(PPh<Subscript>2</Subscript>Bz)<Subscript>2</Subscript>] (PPh<Subscript>2</Subscript>Bz = Benzyldiphenylphosphine)

Abstract  The solution-phase reaction of HgCl₂ with benzyldiphenylphosphine (PPh₂Bz) yields a new triaryl phosphine complex [HgCl₂(PPh₂Bz)₂] (1) with the bigger P–Hg–P angle, the longer Hg–Cl bond, and the shorter Hg–P bond. Comparison of the sensitive bond parameters with similar compounds and the theoretical calculation show that the σ-donating abilities of tertiaryl phosphine ligands toward HgCl₂ conforms to the following order: PEt₃ > PPh₂Bz > P(2-thienyl)₃ > dppf > PPh₃. Graphical Abstract  The solution-phase reaction of HgCl₂ with benzyldiphenylphosphine (PPh₂Bz) yields a new triaryl phosphine complex [HgCl₂(PPh₂Bz)₂] (1) with the bigger P–Hg–P angle. Comparison of the sensitive bond parameters with similar compounds shows that the σ-donating abilities of tertiaryl phosphine ligands toward HgCl₂ conforms to the following order: PEt₃ > PPh₂Bz > P(2-thienyl)₃ > dppf > PPh₃.      

Synthesis and crystal structure of Na<Subscript>3</Subscript>(H<Subscript>3</Subscript>O)[UO<Subscript>2</Subscript>(SeO<Subscript>3</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>· H<Subscript>2</Subscript>O

Single crystals of the compound Na₃(H₃O)[UO₂(SeO₃)₂]₂ · H₂O (I) have been synthesized, and their structure has been investigated using X-ray diffraction. Compound I crystallizes in the triclinic system with the unit cell parameters a = 9.543(6)Å, b = 9.602(7)Å, c = 11.742(8)Å, α = 66.693(16)°, β = 84.10(2)°, γ = 63.686(14)°, space group P \(\bar 1\), Z = 2, and R = 0.0734. The uranium-containing structural units of the crystals are [UO₂(SeO₃)₂]^2? chains, which belong to the crystal-chemical group AB ² B ¹¹ (A = UO ₂ ²⁺ , B ² = SeO ₃ ^2? , B ¹¹ = SeO ₃ ^2? ) of the uranyl complexes. The structures of the compounds containing the [UO₂(SeO₃)₂]^2? anionic complexes are compared.     

The Synthesis and Crystal Structure of (Hpy)<Subscript>3</Subscript>[PMo<Subscript>12</Subscript>O<Subscript>40</Subscript>]·2(py)

Abstract  

The novel supramolecular networks based on Keggin-type polyoxoanion, formulated (Hpy)₃[PMo₁₂O₄₀]·2(py) has been synthesized hydrothermally and determined by X-ray diffraction. The compound crystallize in Monoclinic, system with space groups and cell parameters, P2 ₁ /n, a = 10.9370(2) ?, b = 19.586(3) ?, c = 12.5500(2) ?, β = 98.618(2)°, V = 2657.8(6) ?³. Organic fragments and Keggin anions are connected via N–H···N, N–H···O contacts to form interesting 1D zigzag chain. The molecule is stabilized in solid state by electrostatic forces and intermolecular hydrogen-bonding interactions to give the confirmation of guest [PMo₁₂O₄₀]³⁻ inserting in organic host.     

Hydrothermal Synthesis and Structure of the Solid Solution (Fe<Subscript>0.54</Subscript>Mn<Subscript>0.46</Subscript>)(PO<Subscript>4</Subscript>)⋅2H<Subscript>2</Subscript>O

Abstract  

The iron-manganese phosphate of composition (Fe_0.54Mn_0.46)(PO₄).2H₂O has been obtained as a single-phase product using hydrothermal methods and the structure has been determined by single crystal X-ray diffraction. The title compound is orthorhombic, Pbca, a = 8.720(1), b = 9.884(1), c = 10.114(2) ?, isostructural with strengite. The structure consists of a linkage of MO₆ octahedra and PO₄ ³⁻ tetrahedra. The octahedra are insular and are held together to form a three-dimensional structure by the tetrahedra. The crystal structure study revealed that (Fe_0.54Mn_0.46)(PO₄)⋅2H₂O exhibits a strong Jahn–Teller effect. The compound has been characterized by Raman and IR Spectroscopy, showing the bonds characteristic of the PO₄ ³⁻ polyanions. Measurements by the electric permittivity revealed a peak at 350 K.     

Nitrilotris(methylenephosphonato)potassium K[μ<Superscript>6</Superscript>-NH(CH<Subscript>2</Subscript>PO<Subscript>3</Subscript>)<Subscript>3</Subscript>H<Subscript>4</Subscript>]: Synthesis,structure, and the nature of the K–O chemical bond

The crystal structure of nitrilotris(methylenephosphonato)potassium K[μ⁶-NH(CH₂PO₃)₃H₄]—a three-dimensional coordination polymer—was determined. The potassium atom is coordinated by seven oxygen atoms belonging to the six nearest ligand molecules, resulting in distorted monocapped octahedral coordination geometry. The complex contains the four-membered chelate ring K–O–P–O. The K–O chemical bond is predominantly ionic. Meanwhile, the bonds of the potassium atom with some oxygen atoms have a noticeable covalent component. In addition to coordination bonds, the molecules in the crystal packing are linked by hydrogen bonds.     

Synthesis and Crystal Structure of a Novel Double-Chain Coordination Polymer [Zn<Subscript>2</Subscript>(bipy)<Subscript>2</Subscript>(btec)(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>]<Subscript>n</Subscript> (bipy = 2,2′-bipyridine; btec = 1,2,4,5-benzenetetracarboxylate)

Abstract  A novel aromatic polycarboxylate polymer, [Zn₂(bipy)₂(btec)(H₂O)₂]_n (1), has been synthesized and structurally characterized by the single crystal X-ray diffraction. Compound 1 belongs to the triclinic crystal system, space group P-1; a = 7.7449(6) ?, b = 8.9286(8) ?, c = 10.7422(8) ?, α = 80.95(1)°, β = 70.21(1)°, γ = 78.14(1)°, V = 680.93(10) ?³, Z = 2. The coordination geometry of Zn(II) atom is distorted trigonal bipyramidal with two nitrogen atoms of one 2,2′-bipy group, two oxygen atoms from two different btec ligands, and one water. The 16-membered rings are alternately arranged forming an infinite 1-D double-chain structure. A 3-D network was constructed by interlayer C···H–O, O···H–O hydrogen bonds and π–π stacking interactions. Compound 1 exhibits fluorescence at room temperature in the solid state. Graphical Abstract  A 1-D double-chain aromatic polycarboxylate polymer, [Zn₂(bipy)₂(btec)(H₂O)₂]_n (1), has been synthesized and structurally characterized by the single crystal X-ray diffraction. A 3-D network was constructed by intermolecular C···H–O, O···H–O hydrogen bonds and π–π stacking interactions. Compound 1 exhibits fluorescence at room temperature in the solid state.      

X-ray diffraction study of Ba<Subscript>3</Subscript>TaFe<Subscript>3</Subscript>Si<Subscript>2</Subscript>O<Subscript>14</Subscript> single crystal—a promising langasite-type multiferroic

Ba₃TaFe₃Si₂O₁₄ single crystals (sp. gr. P321, Z = 1), promising langasite-type multiferroics, have been grown by floating zone melting. An accurate X-ray diffraction study of Ba₃TaFe₃Si₂O₁₄ single crystal has been performed using two datasets, obtained independently for two different orientations of the same sample on a diffractometer equipped with a CCD area detector at 295 K. Structure refinement is performed based on an averaged dataset: a = 8.5355(1) Å, c = 5.2332(1) Å, sp. gr. P321, Z = 1; the R factors of model structure refinement were found to be R/wR = 1.02/1.23% for 4552 independent reflections. Disordering asymmetry is revealed for the magnetic Fe ion in the 3f site and the Ba cation in the 3e site.     

Synthesis,Crystal Structure and Spectral Properties of [Fe<Subscript>3</Subscript>(2,2′-bipy)<Subscript>6</Subscript>(ox)<Subscript>3</Subscript>]·12.25H<Subscript>2</Subscript>O Complex

A novel iron (II) complex of formula [Fe₃(2,2′-bipy)₆(ox)₃]·12.25H₂O (2,2′-bipy = 2,2′-bipyridine, ox = oxalate) has been prepared and structurally characterized by X-ray crystallography. In the complex, the metal atoms are six-coordinated in distorted octahedral environment. In the complex [Fe(ox)₃]^4? anions and water molecules are linked together into 1D chain structure by hydrogen interaction. The red crystal of the complex is monoclinic, space group P2₁/c, with a = 22.932(6) Å, b = 13.715(4) Å, c = 22.493(6) Å, β = 93.177(5)°, and V = 7063(3) Å³ with Z = 4.     

A Sodium Supported Borate Ester: Synthesis,Spectral Characterization and Crystal Structure of dimeric Sodium Organoborate Complex [Na(py)][B(hyncaH<Subscript>−2</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>

Abstract  A dimeric sodium supported borate complex, [Na(py)][B(hyncaH₋₂)₂]₂ (1) (py = pyridine, hynca = 1-hydroxynaphthalene-2-carboxylic acid), has been synthesised by the reaction of NaBH₄ with two equivalents of hynca in anhydrous THF and following crystallization from py/H₂O solution afforded borate ester derivative. The complex has been fully characterized by FT-IR in the solid state and by NMR (¹H and ¹³C) spectroscopy and electrospray ionization mass spectrometry in solution. The molecular structure of the title compound was determined by single crystal X-ray diffraction. Structure analysis of complex 1 confirmed the presence of an anionic complex [B(hyncaH₋₂)₂]⁻ in which boron atom is coordinated simultaneously by two hynca ligands utilising both alkoxide and carboxylate groups for bonding. The Na atom is six- coordinate to five O atoms of hydroxy carboxylic acid and one pyridine N atom. Crystal data: crystal system, monoclinic, a = 10.971(3) Å, b = 6.839(3) Å, c = 30.545(5) Å, β = 92.20(2)°, space group P2₁/c (#14), V = 2,290(1) Å³, Z = 4. Index Abstract  There are limited examples of alkali metal supported borate ester complexes.