Crystal Structure and Properties of Rb4H2I2O10 · 4H2O

Single crystals of the Rb₄H₂I₂O₁₀· 4H₂O were synthesized for the first time and studied by X-ray diffraction analysis. The crystals are monoclinic, a = 7.321(6) Å, b = 12.599(8) Å, c = 8.198(8) Å, = 96.30(7)°, Z = 2, space group P2₁/c. The H₂I₂O₁₀ ^4– anion is formed by the edge-sharing IO₆ octahedra. The anions are united by hydrogen bonds into a chain running along the x axis. The chains are combined by water molecules into a three-dimensional structure through hydrogen bonds. The compound is a proton conductor. The conductivity values measured at 20–60°C vary within 10^–6 to 10^–4 ohm^–1 cm^–1.     

用醇还原VOPO4·2H2O制备的VOHPO4·0.5H2O的择优取向性能

 研究了用醇还原VOPO4·2H2O制备的VOHPO4·0．5H2O的晶面择优\r\n取向现象及其在正丁烷和空气混合气体中活化后,产物（VO）2P2O7的\r\n晶面择优暴露对正丁烷氧化制顺酐性能的影响．以伯醇还原VOPO4·2H\r\n2O制备的VOHPO4·0．5H2O晶体,晶面择优取向于（220）面,晶型为玫\r\n瑰状或扭曲的片状聚集体;活化后的产物仅含（VO）2P2O7相,其（02\r\n0）晶面择优暴露．以仲醇还原VOPO4·2H2O制备的VOHPO4·0．5H2O晶\r\n体,晶面择优取向于（001）面,晶型为平板片状体;活化后的产物由\r\n（VO）2P2O7,VOPO4和无定形相组成,其中（VO）2P2O7相含量低,其\r\n（020）晶面暴露少．由苄醇、环己醇和3－甲基－3庚醇还原VOPO4·2\r\nH2O制备的VOHPO4·0．5H2O的XRD谱与用仲醇制备的相似．用一般方法\r\n（V2O5／异丁醇／H3PO4）制备的VOHPO4·0．5H2O晶体不具有晶面择优\r\n取向性质,活化后得到的（VO）2P2O7的结晶度较低．由正辛醇还原VO\r\nPO4·2H2O制备的VOHPO4·0．5H2O经活化后,对正丁烷氧化制顺酐的催\r\n化性能优于用仲辛醇和一般方法制备的VOHPO4·0．5H2O．     

Thermochemistry of two lead borates; Pb(BO2)2·H2O and PbB4O7·4H2O

Two pure hydrated lead borates, Pb(BO₂)₂·H₂O and PbB₄O₇·4H₂O, have been characterized by XRD, FT-IR, DTA-TG techniques and chemical analysis. The molar enthalpies of solution of Pb(BO₂)₂·H₂O and PbB₄O₇·4H₂O in 1 mol dm^?3 HNO₃(aq) were measured to be (?35.00 ± 0.18) kJ mol^?1 and (35.37 ± 0.14) kJ mol^?1, respectively. The molar enthalpy of solution of H₃BO₃(s) in 1 mol dm^?3 HNO₃(aq) was measured to be (21.19 ± 0.18) kJ mol^?1. The molar enthalpy of solution of PbO(s) in (HNO₃ + H₃BO₃)(aq) was measured to be ?(61.84 ± 0.10) kJ mol^?1. From these data and with incorporation of the enthalpies of formation of PbO(s), H₃BO₃(s) and H₂O(l), the standard molar enthalpies of formation of ?(1820.5 ± 1.8) kJ mol^?1 for Pb(BO₂)₂·H₂O and ?(4038.1 ± 3.4) kJ mol^?1 for PbB₄O₇·4H₂O were obtained on the basis of the appropriate thermochemical cycles.     

Synthesis and Crystal Structure of [Cu(phen)2(SO4)(H2O)]·0.5C4H4O4·7H2O

The title compound, [Cu(phen)2(SO4)(H2O)]·0.5C4H4O4·7H2O (phen = 1,10-phe-nanthroline and C4H4O4 = fumaric acid), has been synthesized and characterized by single-crystal X-ray diffraction. The crystal is of triclinic, space group P with a = 11.4827(2), b = 11.9086(2), c = 13.77350(10)(A), α = 80.6830(10), β = 66.6480(10), γ = 64.0480(10)o, V = 1554.63(4) (A)3, Mr = 722.17, Z = 2, Dc = 1.543 g/cm3, μ = 0.845 mm-1, F(000) = 750, R = 0.0349 and wR = 0.0837 for 4754 observed reflections (I > 2σ(I)). The compound contains a six-coordinated copper(II) center, which is surround by four N atoms of two phen ligands (Cu-N distances in the range of 1.997(2)～2.225(2)(A)), one sulfate O atom (Cu-O = 2.0037(17) (A)) and one water O atom (Cu-O(5w) = 2.719(2) (A)) in a distorted octahedral geometry. Extensive hydrogen-bonding interactions are involved in water molecules, ligated sulfate anions and fumaric acid molecules. In addition, π-π interactions via aromatic nitrogen-containing ligands are also discussed. The combination of non-covalent interactions leads to the formation of a 3-D network structure.     

Synthesis and Crystal Structure of [Ni(H2O)6][Ni(H2O)2(C4H2O4)]·4H2O

Reaction of a freshly prepared Ni(OH)_{2?2 x} (CO₃) _x ·yH₂O with maleic acid in H₂O at room temperature afforded [Ni(H₂O)₆][Ni(H₂O)₂(C₄H₂O₄)]·4H₂O, which consists of [Ni(H₂O)₆]²⁺ cations, [Ni(H₂O)₂(C₄H₂O₄)]^2? anions and lattice H₂O molecules. Ni atoms in cations are octahedrally coordinated and Ni atoms in anions are each octahedrally coordinated by bidentate chelating maleato ligands and two water molecules at trans positions. Cations and anions are interlinked by hydrogen bonds to form 1D chains, which are hexagonally arranged and connected by the lattice water molecules. When heated in a flowing argon stream, the compound decomposes, with complete dehydration being followed by dissociation of nickel maleate into NiO and maleic anhydride.     

ZnSO4·CO(NH2)2·2H2O和MgCl2·NH4Cl·6H2O的热分解动力学研究

采用TG-DSC研究了ZnSO4·CO(NH2)2·2H2O和MgCl2·NH4Cl·6H2O的热分解反应,并对其中的脱水过程及部分分解过程进行了动力学计算,由Fridman、Ozawa-Flynn-Wall、ASTME698三种方法得出峰温时的活化能值与指前因子值,通过优化选择出了热分解过程最佳机理函数.     

NaHSO4·H2O催化合成苯甲酸甲酯

以 Na HSO4 · H2 O催化苯甲酸与甲醇的酯化反应 ,合成了苯甲酸甲酯。研究结果表明 ,Na HSO4 · H2 O具有较高的催化活性。考察了苯甲酸 /甲醇摩尔比、催化剂用量及反应时间对酯产率的影响。在优化反应条件 [n(苯甲酸 )∶n(甲醇 )∶n( Na HSO4 ·H2 O) =1∶ 2∶ 0 .2 9,回流8h]下 ,苯甲酸甲酯产率达 85.3 %。     

New 1D and 2D metal oxygen connectivities in Cu(II) succinato and glutarato coordination polymers: [Cu3(H2O)2(OH)2(C4H4O4)2] · 4H2O, [Cu4(H2O)2(OH)4(C4H4O4)2] · 5H2O and [Cu5(OH)6(C5H6O4)2] · 4H2O

Two Cu(II) hydroxo succinates [Cu₃(H₂O)₂(OH)₂(C₄H₄O₄)₂]?·?4H₂O (1) and [Cu₄(H₂O)₂(OH)₄(C₄H₄O₄)₂]?·?5H₂O (2) and one Cu(II) hydroxo glutarate [Cu₅(OH)₆(C₅H₆O₄)₂]?·?4H₂O (3) have been prepared and structurally characterized by single crystal X-ray diffraction methods. They feature 1D and 2D copper oxygen connectivity of elongated {CuO₆} octahedra in “4?+?1?+?1” and “4?+?2” coordination geometries. Within 1, linear trimers of three edge-sharing {CuO₆} octahedra are connected into copper oxygen chains, which are bridged by the anti conformational succinate anions to generate 2D layers with mono terminally coordinating gauche succinate anions on both sides. The layers are assembled into a 3D framework by interlayer hydrogen bonds with lattice H₂O molecules distributed in channels. Different from 1, the principal building units in 2 are linear tetramers of four edge-sharing {CuO₆} octahedra. The tetramers are condensed into copper oxygen chains and the succinate anions interlink them into a 3D framework with triangular channels filled by lattice H₂O molecules. The {CuO₆} octahedra in 3 are edge-shared to form unprecedented 2D inorganic layers with mono terminally coordinating glutarate anions on both sides. Interlayer hydrogen bonding interactions are responsible for supramolecular assembly of the layers into a 3D framework with lattice H₂O molecules in the channels. The inorganic layers in 3 can be described as hexagonal close packing of oxygen atoms with the Cu atoms in the octahedral cavities. The title compounds were further characterized by elemental analyses, IR spectra and thermal analyses.     

Syntheses and structures of p-HOOCC6F4COOH · H2O (H2L · H2O) and luminescent coordination polymers [Tb2(H2O)4(L)3 · 2H2O] n and Tb2(Phen)2(L)3 · 2H2O

Compounds p-HOOCC₆F₄COOH · H₂O (H₂L · H₂O), [Tb₂(H₂O)₄(L)₃ · 2H₂O] _n (I), and Tb₂(Phen)₂(L)₃ · 2H₂O (II) are synthesized. According to the X-ray structure analysis data, the crystal structure of H₂L · H₂O is built of centrosymmetric molecules H₂L and molecules of water of crystallization. The crystal structure of compound I is built of layers of coordination 2D polymer [Tb₂(H₂O)₄(L)₃] _n and molecules of water of crystallization. The ligands are the L^2? anions performing both the tetradentate bridging and pentadentate bridging-chelating functions. The coordination polyhedron TbO₉ is a distorted three-capped trigonal prism. Acid H₂L manifests photoluminescence in the UV region (??_max = 368 nm). Compounds I and II have the green luminescence characteristic of the Tb³⁺ ions, and the band with ??_max = 545 nm (transition ⁵ D ₄?? ⁷ F ₅) is maximum in intensity. The photoluminescence intensity of compound II is higher than that for compound I.     

Two binuclear complexes containing the enrofloxacinate anion: Cd2(C19H21N3O3F)4(H2O)2 · 4H2O and Pb2(C19H21N3O3F)4 · 4H2O

The syntheses and crystal structures of the closely related but non-isostructural Cd₂(C₁₉H₂₁N₃O₃F)₄(H₂O)₂?·?4H₂O (1) and Pb₂(C₁₉H₂₁N₃O₃F)₄?·?4H₂O (2) are described, where C₁₉H₂₁N₃O₃F^? is enrofloxacinate (enro). Both compounds contain centrosymmetric, binuclear, neutral complexes incorporating a central diamond-shaped M₂O₂ (M?=?Cd, Pb) structural unit. The Cd²⁺ coordination polyhedron in 1 is a CdO₆ trigonal prism, including one coordinated water. The Pb²⁺ coordination polyhedron in 2 can be described as a very distorted square-based PbO₅ pyramid, although two additional short Pb?···?O (<3.1?Å) contacts are also present. In the crystal of the cadmium complex, O–H?···?O hydrogen bonds lead to a layered structure. In the lead compound, O–H?···?O and O–H?···?N interactions lead to chains in the crystal. Crystal data: 1: C₇₆H₉₆Cd₂F₄N₁₂O₁₈, M _r?=?1766.45, triclinic, P 1, a?=?12.185(2)?Å, b?=?12.306(3)?Å, c?=?14.826(3)?Å, α?=?68.15(3)°, β?=?70.28(3)°, γ?=?86.11(3)°, V?=?1938.2(7)?ų, Z?=?1, T?=?298 K, R(F)?=?0.030, wR(F ²)?=?0.079. 2: C₇₆H₈₈F₄N₁₂O₁₆Pb₂, M _r?=?1920.00, triclinic, P 1, a?=?12.0283(4)?Å, b?=?12.7465(4)?Å, c?=?13.0585(4)?Å, α?=?83.751(1)°, β?=?74.635(1)°, γ?=?81.502(1)°, V?=?1904.3(1)?ų, Z?=?1, T?=?298?K, R(F)?=?0.021, wR(F ²)?=?0.049.     

An analysis of the vibrational frequencies and amplitudes of the H5O+2 ion in H4SiW12O40·6H2O (TSA·6H2O) and H3PW12O40·6H2O (TPA·6H2O)

The infrared, Raman and inelastic neutron scattering (INS) spectra of TSA·6H₂O and TPA·6H₂O are in agreement with those expected for the presence of H₅O⁺₂ ions. Force fields for different assignment schemes are compared with the observed vibrational frequencies and the INS spectral profile. All but two schemes are eliminated. Whilst low-resolution INS spectroscopy cannot distinguish between these two schemes, the orientations of the vibrational ellipsoids for one scheme are in better agreement with those reported from low-temperature crystallographic studies of the H₅O⁺₂ ion.     

碱性水溶液中4Na2SO4·2H2O2·NaCl的分解动力学

以低浓度(30(wt)%)的双氧水制备了硫酸钠-过氧化氢-氯化钠加合物,各组分的含量均接近于理论值,其纯度为99.3%;在323K和333K下,研究了4Na2SO4*2H2O2*NaCl于碱性水溶液中的分解动力学.结果表明,在不同条件下,其分解均为一级反应;随着温度和pH的增加,其分解速率加快.置信水平为95%时k和C0的联合置信域均为椭圆形且面积较小,求得的参数精确度较高;优化出的模型能较准确地描述4Na2SO4*2H2O2*NaCl于碱性水溶液中的分解过程.     

[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O超分子化合物的晶体结构、荧光性质及热稳定性

在水-乙醇混合体系中,以2-羰基丙酸水杨酰腙(C10H10N2O4,简作H3L)、1,10-菲啰啉C12H8N2,简作phen)与Eu(NO3)3·4H2O反应,首次培养出黄色单晶[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O.该晶体属三斜晶系,P1空间群,晶胞参数a=1.378 6(12) nm,b=1.398 8(12) nm,c=1.759 7(16) nm,α=73.977(11)°,β=68.598(12)°,γ=71.224(12)°,V=29.42(4) nm3,Z=2,μ=2.208 mm-1,Dc=1.746 Mg/m3,F(000)=1 556,R=0.037 7,ωR=0.074 4,GOF=0.916.每个配合物晶体中均有两个相似的结构单元,每个结构单元中铕(Ⅲ)配位数为9,分别与两个2-羰基丙酸水杨酰腙和3个水分子配位; 每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和CN中的氮与Eu3+配位,形成两个共边的稳定的五元环,另3个配位原子则分别来自3个水分子中的氧原子,该结构单元在空间呈扭曲的单帽四方反棱柱,而在每两个铕的九配位单元周围还有一个游离的1,10-菲啰啉分子和4个水分子.IR,1H NMR及热分解结果佐证了配合物的组成.该配合物具有很好的荧光特性.     

Synthesis and properties of tetraalkylammonium chlorides peroxosolvates (CH3)4NCI·H2O2 and (C2H5)4NCl·H2O2

Tetraalkylammonium chlorides peroxosolvates (CH₃)₄NCl·H₂O₂ and (C₂H₅)₄NCl·H₂O₂ were synthesized. The composition of the solvates was proved by chemical analysis; their X-ray patterns, IR spectra, and thermograms were obtained. The solubility of the solvates in water and their stability in aqueous solutions were investigated.