Synthesis and Properties of Inorganic Triphosphate Crystal Hydrates

Abstract

The polycrystalline samples and single crystals of crystal hydrates of inorganic triphosphates with ring-like and chain-like anion structured were synthesized: lithium and sodium cyclotriphosphates, sodium and ammonium chain triphosphates, and double salts of chain triphosphoric acid (ammonium-potassium, ammonium-magnesium, ammonium-manganese). The crystallization field of the double salt of variable composition (NH₄,K)₃H₂P₃O₁₀ ·xH₂O (NH₄ :K=0.23–3.60; x=0.8–1.5) from aqueous solutions was established. Synthesis of Na₅P₃O₁₀ · 6D₂O crystals has been performed by the interaction of the high temperature form Na₅P₃O₁₀ (I) with D₂0. At 20°C and relative humidity RH < 70–80% the (NH₄) ₅P₃O₁₀·2H₂O crystals lose their transparency and generate different crystalline products depending on RH value: (NH₄)₅P₃O₁₀ at RH=0% or (NH₄)₅P_{3 10} · H₂O at RH=32%. The (NH₄) ₅P₃ O₁₀ · H₂O crystals are stable at RH < 60–70%, at RH=80% they absorb water and transform into (NH₄) ₅P₃O₁₀ · 2H₂0. In the latter case a characteristic picture is registered: on active sites situated on the (NH₄) ₅P₃O₁₀ · H₂O crystal face the appearance and epitaxial growth of (NH₄) ₅P₃O₁₀ · H₂O crystals is observed. For some single crystals the character of dehydration localization has been shown to correlate with space arrangement of phosphate groups in crystal structure. On the basis of the obtained results a model of dehydration front propagation in crystals has been suggested.     

含质子柠檬酸氧钒（V）配合物中间体的合成和晶体结构

合成了含质子柠檬酸氧钒（Ｖ）配合物中间体ＮａＫ３［ＶＯ２（Ｈｃｉｔ）］２·７Ｈ２Ｏ，用红外光谱和Ｘ射线衍射进行了结构表征。结果表明：晶体属单斜晶系，Ｐ２１／ｎ空间群。晶胞参数ａ＝１．１２５８（２）ｎｍ，ｂ＝１．５７７４（３）ｎｍ，ｃ＝１６５５９（１）ｎｍ，β＝９８．５６８（９）°，Ｖ＝２．９０８（１）ｎｍ＾３，Ｚ＝４，Ｄｃ＝１．８５１ｇ·ｃｍ＾－３，Ｆ（０００）＝１６４０，μ（Ｃｕ Ｋα）＝１０４     

Hetero‐metallic Lanthanide CPs Involving Sodium: Synthesis,Crystal Structure,and Luminescence Properties

[TbNa(4‐msal)₄(phen)₂]_n ( 1 ) (4‐msal = 4‐methyl salicylic acid), a new hetero‐metallic lanthanide coordination polymer (CP) involving sodium was synthesized. It crystallizes in the monoclinic space group P2₁/n, with a = 20.4809(9) Å, b = 9.8183(2) Å, c = 26.1987(11) Å, α = 90.00°, β = 112.922(5)°, γ = 90.00°, V = 4852.2(3) ų, and Z = 4. The complex was characterized by single crystal and powder X‐ray diffraction, elemental analysis (EA), and Fourier transform infrared (FT‐IR) and luminescence spectroscopy. The luminescence properties of a powder sample of 1 were studied at room temperature and the luminescence lifetime and total quantum yield (QY) were determined.     

Preparation and Crystal Structure of Sodium Hydrogen Epoxysuccinate

1 INTRODUCTION In recent years, sodium hydrogen epoxysuccinatehas gained special attention as a raw material of po-lyepoxysuccinic acid (PESA)[1～3]. We have synthes-ized sodium hydrogen epoxysuccinate by the reac-tion of H2O2 and maleic anhydride in water ca-talyzed by tungstate and obtained its single crystal[1].Its structure was determined by X-ray Nonius CAD4diffractometer. Up to now some crystal structures oforganic carboxyl sodium have been determined[4～6].In this paper we …     

Temperature Dependence of Transport Properties of Liquid Sodium and Potassium

The electrical and thermal resistivities of liquid Na and K are calculated over a range of temperature at and above the melting point using the solutions of the Boltzmann equation, the form factors constructed using the Dagens-Rasolt-Taylor (DRT) model potential, the screening function of Geldart and Taylor and the X-ray structure factors of Waseda. The ratio of the electrical and the thermal resistivities is compared with the Wiedemann-Franz law and with experiment. We show that the deviation from the Lorenz number can be explained by the inelastic part of the electron-phonon scattering and the electron-electron scattering.     

水化锂蒙脱石层间结构和动力特征的分子模拟

利用分子力场和分子动力学(MD)的方法研究了Li-蒙脱石的结构构型, 层间阳离子的水化行为、水分子的结构特征以及它们的扩散性质. 分子力场构型优化结果表明: Li-蒙脱石的层间距、体积和密度与层间水含量有关; MD模拟的动画轨迹显示Li-蒙脱石层间Li^＋的位置与层间电荷位置有关. 均方根位移和自扩散系数的计算结果表明: 层间阳离子、水分子在Li-蒙脱石一、二层水合物中的扩散受到上下粘土片表面的限制, 在三层水合物中开始离开粘土层面向其它方向快速扩散. 径向分布函数及其结构因子的分析结果表明Li^＋在一、二、三层水合物中有不同的水合层; 层间水分子的结构特征说明其在蒙脱石层间有水合水分子和自由水分子之分, 且它们的比值在一、二和三层水合物中有所不同.     

The 1,4,7,10,13-Pentaoxacyclohexadecane-14,16-Dione Complex with Potassium Thiocyanate: Crystal Structure

The complex of 1,4,7,10,13-pentaoxacyclohexadecane-14,16-dione (L) with potassium thiocyanate, C₁₁H₁₈O₇· KNCS (I), is prepared and characterized by X-ray diffraction analysis: space group C2/c, a = 26.810 Å, b = 7.834 Å, c = 20.504 Å, = 129.19°, Z = 8. The crystal structure is solved by the direct method and refined anisotropically by the full-matrix least-squares method to R = 0.038 for all 2929 unique measured reflections (CAD4 automated diffractometer, MoK ). Structure I is built of [KL(NCS)] monomers of the host–guest type, which are united into [K₂L₂(NCS)₂] dimers containing four-membered KNKN cycles. In the crystal, the dimers are united into infinite polymeric double chains (along the b axis) by K···O=C outer bonds. The K⁺ cation (CN 8) does not lie in the plane of the L crown ligand but is located above it. The coordination polyhedron of the K⁺ cation is irregular; its vertices are occupied by five ether O atoms of one L ligand, two N atoms of two SCN ligands, and one carbonyl O atom of the adjacent L ligand.     

Crystal Structure and Properties of a Sodium Terbium Borate Na2.67Tb2.11B3O9

A new nonlinear optical crystal of sodium terbium borate (Na2.67Tb2.11B3O9, Mr=573.14) was synthesized by solid reaction method. The colorless transparent single crystals were grown from the high temperature solution by employing NaBO2 as flux. The structure was determined by single-crystal X-ray diffraction method. The compound crystallizes in the orthorhombic system, space group Amm2 with a=5.0744(10), b=10.990(2), c=6.9078(14) , V=385.24(13) ·3, Dc=4.941 g/cm3, F(000)=250, Z=2, μ=9.205 mm-1, the final R=0.0253 and wR=0.0610. Its three-dimensional network structure is constructed from isolated BO33-, Na(1)O8, Na(2)O6, Na(3)O6 and Tb(1)O9 polyhedra. Variable-temperature magnetic susceptibility measurements show the compound is paramagnetic (μj=7.04 μb). The intensity of the second harmonic generation of Na2.67Tb2.11B3O9 is 2.5 times that of KDP.     

Synthesis,Crystal Structure,and Properties of the Sodium Molybdate Fluoride Na3MoO4F

The compound Na₃MoO₄F was synthesized by high temperature solution methods. Single‐crystal X‐ray diffraction analysis reveals that Na₃MoO₄F crystallizes in the orthorhombic space group Pnma (No. 62) with lattice constants a = 5.588(2) Å, b = 7.515(3) Å, c = 12.876(5) Å, and Z = 4. The crystal structure consists of isolated MoO₄ groups and [FNa₃]_∞ chains, which are connected by Na–O bonds to form a three‐dimensional framework. A detailed structure comparison between Na₃MoO₄F and NaMoO₃F was carried out. IR spectroscopy and bond valence sum analysis of Na₃MoO₄F indicate that the structure is reasonable. In addition, the electronic structure was investigated by the first‐principles method.     

奥扎格雷的晶体结构和酸碱性质

通过单晶X射线衍射测定了奥扎格雷的晶体结构. 晶体属正交晶系, 空间群为P212121, 晶胞参数为a=0.62522(6) nm, b=0.91897(8) nm, c=1.95789(18) nm, V=1.12492(18) nm3, Z=4. 通过紫外光谱和荧光光谱pH滴定研究了其基态和激发态酸碱性质, 测定了奥扎格雷的基态和激发态酸式电离常数. 结果表明奥扎格雷是一个pH诱导的荧光分子开关.     

Synthesis and Crystal Structure of Potassium Indium Tribromide,KInBr3

KInBr₃, the first ternary indium bromide containing divalent indium, is synthesized from InBr₃, KBr, and elemental In at 450 °C. Its trigonal crystal structure (a = b = 853.24(1) pm, c = 1077.76(2) pm; P3¯; Z = 4) has been solved and refined from X-ray powder data. Indium atoms of oxidation state two are found in an [In₂Br₆]^2– unit with ecliptic ethane structure while potassium ions are located in two different polyhedra. There is an octahedral coordination by bromine anions for half of the K⁺ whereas the other K⁺ cations are located in trigonal Br^– prisms, tricapped by three additional Br^– anions.     

Synthesis,Structure and Properties of Inverse-Keggin Potassium Tetraniobooctatungstosilicate

Ｓｙｎｔｈｅｓｉｓ，ＳｔｒｕｃｔｕｒｅａｎｄＰｒｏｐｅｒｔｉｅｓｏｆＩｎｖｅｒｓｅ－ＫｅｇｇｉｎＰｏｔａｓｓｉｕｍＴｅｔｒａｎｉｏｂｏｏｃｔａｔｕｎｇｓｔｏｓｉｌｉｃａｔｅＹＵＥＢｉｎ，ＴＡＮＧＬｉ－ｈａｏ，ＲＵＩＣｈｅｎｇ－ｇｕｏ，ＬＩＵＨｕｉ－ｚ...     

超分子碱金属膦酸盐——哌嗪双膦酸钠的合成及晶体结构

二维或三维金属膦酸盐聚合物作为功能材料在催化、离子交换和纳米材料等研究领域受到广泛关注 .最初的研究主要集中在四价金属盐 ,后来陆续报道了对于其它价态金属盐的研究 [1～ 3] ,但关于单一碱金属的研究报道较少 . 2 0 0 0年 ,Aranda等[4 ] 报道了首例 Na2 [( HO3PCH2 ) 3NH ]· 1 .5 H2 O( Na PP- 1 )晶体结构 .与其它膦酸盐的明显差别是 ,碱金属双膦酸盐是治疗骨质疏松症的药物 [5] .本文从重要的医药原料哌嗪 [6 ]出发 ,制备并测定了一种具有超分子特征的 α-氨基双膦酸钠Na2 [( HO3PCH2 ) NC4 H8N( CH2 PO3H) ]( H2 O)…     

Hydrothermal Synthesis and Crystal Structure of a Novel 3D Potassium Complex

N-m-cyanophenyl-o-aminobenzoato acid(C15H11N2O2,HNCAB) ligand was syn-thesized through the bromination and nucleophilic reactions.The compound [K(NCAB)]n(1) was synthesized via the hydrothermal reaction of CuSO4,KCO3 and HNCAB,and characterized by elemental analysis,infrared spectra,and X-ray diffraction.The complex crystallizes in orthorho-mbic,space group Iba2 with a = 26.422(2),b = 15.1060(2),c = 6.849(1) ,V = 2733.5(4) 3,Z = 8,C15H11KN2O2,Mr = 290.36,Dc = 1.411 g/cm3,F(000) = 1200 and μ(MoKα) = 0.390 mm-1.The final R = 0.0329 and wR = 0.0788 for 2644 observed reflections with Ⅰ 2σ(Ⅰ) and R = 0.0397 and wR = 0.0826 for all data.Each carboxylato of NCAB ligand is coordinated to four K ions in an unprecedented μ4-κ2,κ1,κ1,κ1 coordination mode to form a 1-D tube-chain along the c axis.These 1D tube-chains are assembled into an unprecedented 3D framework via K-N bonds.The network of compound 1 exhibits a relatively rare five-connected topology.     

Synthesis, Crystal Structure, Fluorescent and Thermal Properties of Sodium Tridecafluorodizirconate Na5Zr2F13 Compound

1 INTRODUCTION Considerable research effort on the heavy metal fluoride glasses like barium, zirconium fluoride and a series of rare-earth fluorozirconate compounds du- ring the last two decades was initiated by the broad optical transmission window of these glasses and thereby the potential for ultralow-loss optical fi- bers[1~10]. The fluorozirconate of alkali metals was first reported in 1938[11], and most of the sodium and potassium fluorozirconates were reported amongthe 1940s and 19…     

Concomitant Polymorphism in an Organic Solid: Molecular and Crystal Structure and Intra- and Intermolecular Potential Contributions to tert-Butyl and Methyl Group Rotation

We investigate the relationship between structure (crystal and molecular) and tert-butyl and methyl group dynamics in 2-(tert-butyl)-9-(4-(tert-butyl)phenyl)anthracene. Powder and single-crystal X-ray diffraction, taken together, show that different polycrystalline samples recrystallized from different solvents have different amounts of at least four polymorphs (crystallites having different crystal structures), of which we have identified three by single crystal X-ray diffraction. The molecules in the asymmetric units of the different crystal structures differ by the dihedral angle the tert-butylphenyl group makes with the anthracene moiety. Ab initio electronic structure calculations on the isolated molecule show that very little intramolecular energy is required to change this angle over a range of about 60° which is probably the origin of the concomitant polymorphism (crystals of more than one polymorph in a polycrystalline sample). Solid state ¹H nuclear magnetic resonance (NMR) spin-lattice relaxation experiments support the powder and single-crystal X-ray results and provide average NMR activation energies (closely related to rotational barriers) for the rotation of the tert-butyl groups and their constituent methyl groups. These barriers have both an intramolecular and an intermolecular component. The latter is sensitive to the crystal structure. The intramolecular components of the rotational barriers of the two tert-butyl groups in the isolated molecule are investigated with ab initio electronic structure calculations.     

Crystal Structure Refinement for Potassium(2.2.2-cryptand)thiocyanate Monohydrate

The crystal structure of potassium(2.2.2-cryptand)thiocyanate monohydrate, [K⁺(2.2.2-Crypt)]·SCN^- ·H₂O, has been refined by XRD analysis: space group P2/c, a=11.290(2), b=8.308(2), c=14.360(2) , =109.97(2)°, Z=2; 3680 unique reflections, R=0.051. Using a different structural model with a twice shorter crystallographic a axis compared to the original work gave much more precise structural data.     

Eu4Bi3: Crystal Structure,Magnetic and Electronic Properties

The Eu? Bi system contains the phases Eu₅Bi₃, Eu₄Bi₃ and Eu₁₁Bi₁₀. The structure types of these phases have been determined by powder X-ray diffraction. Crystals of Eu₄Bi₃ (cubic, space group I4 3d; a = 9.920 Å, Z = 4, T = 130 K, R1/wR2 = 4.86/10.84%) were obtained in low yield by reaction of Eu, Mn, and Bi in the ratio 14:1:11 in a closed niobium tube (heating rate 30°C/h; reaction at 1050°C for 300 h, cooling rate 100°C/h). The crystal structure consists of distorted octahedra made up of six Bi coordinated to a central Eu atom. Eu is also coordinated to a three other Eu atoms and forms a three-dimensional network composed of interconnected rings. The Bi atoms are coordinated to eight Eu atoms. High yields of Eu₄Bi₃ can be prepared by reacting stoichiometric amount of the elements in a sealed tantalum tube at 1100°C for 24 h. Temperature dependent magnetic susceptibility is consistent with antiferromagnetic behavior with an ordering temperature of 18 K. The data could be fit with the Curie-Weiss law and a moment of 7.38 μ_B/Eu is obtained, consistent with all Eu atoms being Eu¹¹. Temperature dependent resistivity indicates that Eu₄Bi₃ is a metal with a room temperature resistance of 1.3 Ωcm.