Syntheses and crystal structures of two new hydrated borates, Zn8[(BO3)3O2(OH)3] and Pb[B5O8(OH)]·1.5H2O

Two new hydrated borates, Zn₈[(BO₃)₃O₂(OH)₃] and Pb[B₅O₈(OH)]·1.5H₂O, have been prepared by hydrothermal reactions at 170 °C. Single-crystal X-ray structural analyses showed that Zn₈[(BO₃)₃O₂(OH)₃] crystallizes in a non-centrosymmetric space group R32 with a=8.006(2) Å, c=17.751(2) Å, Z=3 and Pb[B₅O₈(OH)]·1.5H₂O in a triclinic space group P1¯ with a=6.656(2) Å, b=6.714(2) Å, c=10.701(2) Å, α=99.07(2)°, β=93.67(2)°, γ=118.87(1)°, Z=2. Zn₈[(BO₃)₃O₂(OH)₃] represents a new structure type in which Zn-centered tetrahedra are connected via common vertices leading to helical ribbons _∞¹[Zn₈O₁₅(OH)₃]¹⁷⁻ that pack side by side and are further condensed through sharing oxygen atoms to form a three-dimensional _∞³[Zn₈O₁₁(OH)₃]⁹⁻ framework. The boron atoms are incorporated into the channels in the framework to complete the final structure. Pb[B₅O₈(OH)]·1.5H₂O is a layered compound containing double ring [B₅O₈(OH)]²⁻ building units that share exocyclic oxygen atoms to form a two-dimensional layer. Symmetry-center-related layers are stacked along the c-axis and held together by interlayer Pb²⁺ ions and water molecules via electrostatic and hydrogen bonding interactions. The IR spectra further confirmed the existence of both triangular BO₃ and OH groups in Zn₈[(BO₃)₃O₂(OH)₃], and BO₃, BO₄, OH groups as well as guest water molecules in Pb[B₅O₈(OH)]·1.5H₂O.     

Phase transitions in Ca3(BN2)2 and Sr3(BN2)2

α-Ca₃(BN₂)₂ crystallizes in the cubic system (space group: ) with one type of calcium ions disordered over of equivalent (8c) positions. An ordered low-temperature phase (β-Ca₃(BN₂)₂) was prepared and found to crystallize in the orthorhombic system (space group: Cmca) with lattice parameters: , , and . Structure refinements on the basis of X-ray powder data have revealed that orthorhombic β-Ca₃(BN₂)₂ corresponds to an ordered super-structure of cubic α-Ca₃(BN₂)₂. The space group Cmca assigned for β-Ca₃(BN₂)₂ is derived from by a group-subgroup relationship.DSC measurements and temperature-dependent in situ X-ray powder diffraction studies showed reversible phase transitions between β- and α-Ca₃(BN₂)₂ with transition temperatures between 215 and 240 °C.The structure Sr₃(BN₂)₂ was reported isotypic with α-Ca₃(BN₂)₂ () with one type of strontium ions being disordered over of equivalent (2c) positions. In addition, a primitive () structure has been reported for Sr₃(BN₂)₂. Phase stability studies on Sr₃(BN₂)₂ revealed a phase transition between a primitive and a body-centred lattice around 820 °C. The experiments showed that both previously published structures are correct and can be assigned as α-Sr₃(BN₂)₂ (, high-temperature phase), and β-Sr₃(BN₂)₂ (, low-temperature phase).A comparison of Ca₃(BN₂)₂ and Sr₃(BN₂)₂ phases reveals that the different types of cation disordering present in both of the cubic α-phases () have a directing influence on the formation of two distinct (orthorhombic and cubic) low-temperature phases.     

[Hg5O2(OH)4][(UO2)2(AsO4)2]: A complex mercury(II) uranyl arsenate

Under mild hydrothermal conditions UO₂(NO₃)₂·6H₂O, Hg₂(NO₃)₂·2H₂O, and Na₂HAsO₄·7H₂O react to form [Hg₅O₂(OH)₄][(UO₂)₂(AsO₄)₂] (HgUAs-1). Single crystal X-ray diffraction experiments reveal that HgUAs-1 possesses a pseudo-layered structure consisting of two types of layers: and . The layers are complex, and contain three crystallographically unique Hg centers. The coordination environments and bond-valence sum calculations indicate that the Hg centers are divalent. The layers belong to the Johannite topological family. The and layers are linked to each other through μ₂-O bridges that include Hg?O=U=O interactions.     

(NH3CH2CH2NH3)B6O9(OH)2: Synthesis and crystal structure of a novel layered borate templated by ethylenediamine

A novel intercalated borate compound (NH₃CH₂CH₂NH₃)B₆O₉(OH)₂, has been solvothermally synthesized, and structurally characterized by single crystal X-ray diffraction. Compound crystallizes in the monoclinic, space group P2(1)/c, , , , β=93.32(3)°, , Z=4. Its oxoborate structure is built up from 1-D polyborate chains with 3, 11-membered boron rings bonded diamine molecules through electrostatic attraction and hydrogen bond interactions to construct 2-D layered compound. Other characterizations by IR, element analysis, thermal analysis and specific surface area are also discussed.     

A novel cesium hydroxygallophosphate with a layered structure built up of rutile ribbons: CsGa2(OH)2[(PO4)H(PO4)]

A new cesium gallophosphate, CsGa₂(OH)₂[(PO₄)H(PO₄)], with an original layer structure has been synthesized by hydrothermal route and characterized by single-crystal X-ray diffraction (R=0.0344, R_w=0.0319). Its structure crystallizes in the monoclinic space group P2₁/a with cell parameters , , , β=93.36(4)° and Z=2. It consists of [Ga(OH)PO₄]_∞ layers built up of rutile ribbons interconnected through PO₄ tetrahedra. The structure of CsGa₂(OH)₂[(PO₄)H(PO₄)] is closely related to those of (NH₄)Ga(OH)PO₄ and (en)Ga₂(OH)₂(PO₄)₂ (en=ethylenediamine [H₃N(CH₂)₂NH₃]²⁺). The three structures differ mainly from each other by the relative positions and the spacing of the successive layers, which are governed by different hydrogen bonding modes between [Ga(OH)PO₄]_∞ layers and the interleaved species. The title compound presents strong symmetric hydrogen bonds O---H---O which bridge two PO₄ tetrahedra of two successive layers. As a consequence, the distance between the layers is significantly shorter than in the two other amine compounds.     

Crystal structure and characterization of Rb2Ca[B4O5(OH)4]2·8H2O

Dirubidium calcium tetraborate octahydrate, Rb₂Ca[B₄O₅(OH)₄]₂·8H₂O, was prepared by reaction of Rb-borate aqueous solution with CaCl₂ and it's structure has been determined by single-crystal X-ray diffraction data. It crystallizes in the orthorhombic system, space group P2₁2₁2₁ with unit cell parameters, Z=4, The structure contains alternate layers of [B₄O₅(OH)₄]²⁻ polyanions separated by water molecules and Rb, Ca cations. The isolated [B₄O₅(OH)₄]²⁻ is constructed from two BO₃(OH) tetrahedron groups and two BO₂(OH) triangular groups joined at common oxygen atoms. The two BO₃(OH) tetrahedron groups are further linked by means of an oxygen bridge across the ring. The Ca²⁺ ion displays seven coordination, while the two non-equivalent Rb⁺ ions display nine and seven coordination, respectively. Infrared and Raman (4000-400 cm⁻¹) spectra of Rb₂Ca[B₄O₅(OH)₄]₂·8H₂O were recorded at room temperature and analyzed. Fundamental vibrational modes were identified and band assignments were made. The dehydration of this hydrated mixed borate occurs in one step and leads to an amorphous phase which undergoes a crystallization.     

A sodium gallophosphate with an original tunnel structure: NaGa2(OH)(PO4)2

A new sodium gallophosphate, NaGa₂(OH)(PO₄)₂, has been obtained by hydrothermal synthesis under autogeneous pressure at 473 K. It crystallizes in the P2₁/n space group with the cell parameters a=8.9675(8) Å, b=8.9732(5) Å, c=9.2855(7) Å, β=114.812(6)°, V=678.2 Å³ (Z=4). In its original three-dimensional framework, monophosphate groups share their apices with [Ga₄O₁₆(OH)₂] tetrameric units, which are built from two GaO₅(OH) octahedra and two GaO₄(OH) trigonal bipyramids. The sodium cations are located in tunnels running along a, whereas the tunnels running along b are empty.     

Synthesis, crystal structure and thermal behavior of a novel oxoborate SrBi2B4O10

A new compound, SrBi₂B₄O₁₀, has been grown by cooling a melt with the stoichiometric composition. It is triclinic, P−1, a=6.819(1), b=6.856(1), c=9.812(2) Å, α=96.09(1), β=109.11(1), γ=101.94(1)°, V=416.5(1) Å³, Z=2. The crystal structure of the compound has been solved by direct methods and refined to R₁=0.050 (wR₂=0.128). The structure contains Bi-O pseudolayers build up from Bi-O chains involving oxocentred OBi₃ triangles. Sr atoms and [B₄O₉]⁶⁻ isolated anions (4B:3Δ□:<2Δ□>Δ) are located between the Bi-O packages.The thermal treatment as well as DSC experiment showed that the compound melts above 800 °C presumably according to the peritectic reaction: SrBi₂B₄O₁₀ ↔ SrB₂O₄+SrB₄O₇+ Liquid. According to high-temperature X-ray powder diffraction study thermal expansion of SrBi₂B₄O₁₀ structure is anisotropic (α₁₁=13, α₂₂=9, α₃₃=2, α_V=24×10⁻⁶ °C⁻¹).     

Synthesis, characterization and thermochemistry of K2B5O8(OH)·2H2O

A pure hydrated potassium borate K₂B₅O₈(OH)·2H₂O has been synthesized under mild hydrothermal conditions and characterized by single-crystal X-ray diffraction, XRD, FT-IR, Raman spectra and DTA-TG. The crystal structure consists of two K-O polyhedra and [B₅O₈(OH)]²⁻ polyborate anion. The enthalpy of formation was determined to be −4772.6 ± 4.0 kJ mol⁻¹ by solution calorimetry.     

镧系稀土四元配合物Ln(NO_3)_2(phen)_2(CH_3COCHCOCH_3)的合成及晶体结构表征

以乙酰丙酮(Hacac)、邻菲咯啉(phen)、硝酸根为配体,8-羟基喹啉为酸度调节剂合成出一个系列的镧系轻稀土四元配合物Ln(NO3)2(phen)2(CH3COCHCOCH3)(Ln=La,Ce,Pr,Nd,Sm)。配合物的结构与性质由元素分析,IR,1HNMR和TGA等表征。单晶Ce(NO3)2(phen)2(CH3COCHCOCH3)·H2O结构经由X射线衍射仪分析表明,晶体属单斜晶系,空间群P21/n,晶胞参数为a=1.11017(8)nm,b=0.98401(7)nm,c=1.34453(10)nm,β=102.0530(10)°,V=1.43641(18)nm3,Dc=1.715g·cm-3,Z=2,F(000)=742。配合物呈单核结构,中心离子Ce髥配位数为10。     

Zn3(HPO3)4·Zn(H2O)6: a purely inorganic open-framework zincophosphite with octahedral zinc complex [Zn(H2O)6] encapsulating in the channels

The hydrothermal synthesis and single crystal structure of Zn₃(HPO₃)₄·Zn(H₂O)₆ are reported. The structure is built-up from vertex linking ZnO₄ tetrahedral and HPO₃ pseudo-pyramids units, giving rise to a three-dimensional framework with large 8, 16-membered ring channels. The zincophosphite is purly inorganic with the octahedral zinc complex filled in the channel. The synthesis of system required the presence of the organic amine which is not incorporated into the structure of the product. The framework-metal complex encapsulating in the channel is the first time appeared in open-framework zincophospates and zincophosphites. Crystal data: Zn₃(HPO₃)₄·Zn(H₂O)₆, M=689.52, orthorhombic, Fddd (No. 70), , , , , Z=8, , , R=0.0265, R_w=0.0406.     

Extended networks, porous sheets, and chiral frameworks. Thorium materials containing mixed geometry anions: Structures and properties of Th(SeO3)(SeO4), Th(IO3)2(SeO4)(H2O)3·H2O, and Th(CrO4)(IO3)2

Three novel Th(IV) compounds containing heavy oxoanions, Th(SeO₃)(SeO₄) (1), Th(IO₃)₂(SeO₄)(H₂O)₃·H₂O (2), and Th(CrO₄)(IO₃)₂ (3), have been synthesized under mild hydrothermal conditions. Each of these three distinct structures contain trigonal pyramidal and tetrahedral oxoanions. Compound 1 adopts a three-dimensional structure formed from ThO₉ tricapped trigonal prisms, trigonal pyramidal selenite, SeO₃^2-, anions containing Se(IV), and tetrahedral selenate, SeO₄^2-, anions containing Se(VI). The structure of 2 contains two-dimensional porous sheets and occluded water molecules. The Th centers are found as isolated ThO₉ tricapped trigonal prisms and are bound by four trigonal pyramidal iodate anions, two tetrahedral selenate anions, and three coordinating water molecules. In the structure of 3, the Th(IV) cations are found as ThO₉ tricapped trigonal prisms. Each Th center is bound by six IO₃^1- anions and three CrO₄^2- anions forming a chiral three-dimensional structure. Second-harmonic generation of 532 nm light from 1064 nm radiation by a polycrystalline sample of 3 was observed. Crystallographic data (193 K, MoKα, λ=0.71073): 1; monoclinic, P2₁/c; , , , β=103.128(1), Z=4, R(F)=2.47% for 91 parameters with 1462 reflections with I>2σ(I); 2, monoclinic, P2₁/n, , , , β=100.142(2), Z=4, R(F)=4.71% for 158 parameters with 2934 reflections with I>2σ(I); 3, orthorhombic, P2₁2₁2₁, , , , Z=4, R(F)=2.04% for 129 parameters with 2035 reflections with I>2σ(I).     

铁氧簇合物[Fe11O6(OH)6(O2CCH3)15](C5H5N)6的结构和磁性质

通过三核铁盐[Fe₃O(O₂CCH₃)₆(H₂O)₃]C1在吡啶溶液中水解聚合得到铁氧簇合物[Fe₁₁O₆(OH)₆(O₂CCH₃)₁₅](C₅H₅N)₆。晶体结构表明11个铁离子(Ⅲ)中6个位于扭曲的三棱柱的顶点上，其余5个分别位于三棱柱的每个面之外。铁离子(Ⅲ)之间以氧桥或者羟基氧桥相连。变温磁化率证实铁离子(Ⅲ)之间是反铁磁耦合的。     

新型水合稀土多硼酸盐Ln[B5O8(OH)2](Ln=Pr，Nd)的合成与结构

采用熔融硼酸法在200 ℃下合成了一种具有层状结构的新型水合稀土多硼酸盐，Ln[B₅O₈(OH)₂](Ln=Pr，Nd)，并利用粉末X射线衍射技术确定了它的结构。Ln[B₅O₈(OH)₂]晶体属于单斜晶系、P2₁/c空间群，它的基本构建单元(FBB)是由3个BO₄和2个BO₃组成的双三元环，[B₅O₁₂](2Δ+3T)。每一个FBB和邻近的4个FBB通过共用氧原子相连，形成了具有九元环窗口的层状硼酸根基团，稀土离子位于九元环中心附近。CSD：391317。     

[Mo(C9H6NO)2O2]的合成和晶体结构

合成了标题化合物[Mo(C9H6NO)2(O)2](C9H6NO=8-羟基喹啉),测定了化合物的晶体结构.晶体属单斜晶系,空间群Cc,a=13.372(3),b=9.421(2),c=13.554(3)A,β=109.71(3)°,V=1607.6(8)A3.结构由直接法解出,最后可靠性因子R=0.0473,Rw=0.062.Mo原子为6配位,位于八面体的中心.两个配体氧相互处于邻位,分别与8-羟基喹啉中的N原子处于对位.     

Structure and microstructure of the high pressure synthesised misfit layer compound [Sr2O2][CrO2]1.85

The strontium chromium oxide [Sr₂O₂][CrO₂]_1.85 misfit layer compound has been synthesised at high-pressure and high-temperature conditions. Electron diffraction patterns and high-resolution transmission electron microscopy images along [001] show the misfit character of the different layers composing the structure with a supercell along the incommensurate parameter b≈7b₁≈13b₂. The modulated crystal structure has been refined within the superspace formalism against single-crystal X-ray diffraction data, employing the (3+1)-dimensional superspace group C′nmb(0σ₂0)0 0 s. The compound has a composite structure with lattice parameters a₁=5.182(1) Å, b₁=5.411(1) Å, c₁=18.194(3) Å for the first, SrO, subsystem and the same a and c, but with b₂=2.925(1) Å for the second, CrO₂, subsystem. The layer stacking is similar to that of orthorhombic PbS(TiS₂)_1.18, but with a much stronger intersubsytem bonding in the case of the oxide. The intersubsystem lattice mismatch is mainly handled by displacement modulations of the Sr atoms, correlated with modulations of the valence, the coordination and the anisotropic displacement parameters.     

Crystal and molecular structures of Ni[(iso-C4H9)2PS2]2 and Pd[(iso-C4H9)2PS2]2 chelates

Crystal structures of chelate compounds Ni[(iso-C₄H₉)₂PS₂]₂ (I) and Pd[(iso-C₄H₉)₂PS₂]₂ (II) have been determined by X-ray diffraction: diffractometer X8-APEX, MoK _α∔ -radiation, 1048 F _hkl , R = 0.0544 for I and CAD-4 diffractometer, MoK _α∔ -radiation, 1283 F _hkl , R = 0.0347 for II. The crystals are rhombic: a = 12.921(5) Å, b = 17.094(5) Å, c = 22.971(5) Å; V = 5074(3) ų, Z = 8, calc = 1.250 g/cm³, space group Pbca for I and a = 13.312(3) Å, b = 16.130(7) Å, c = 23.171(5) Å; V = 4975(3) ų, Z = 8, ρ_calc = 1. 208 g/cm³, space group Pbca for II. The structures of I and II are formed by discrete mononuclear molecules. Coordination cores MS₄ (M = Ni, Pd) approach planar square configurations. Original Russian Text Copyright ? 2005 by L. A. Glinskaya, T. G. Leonova, T. E. Kokina, R. F. Klevtsova, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 4, pp. 715–720, July–August, 2005.     

[{(NiOH)2Mo10O36(PO4)Ti2}n]: a novel chainlike trimetal heteropolyanion based on pseudo-keggin fragments

A new mixed Mo/Ni/Ti heteropoly compound [C₅H₅NH]₅ [(NiOH)₂Mo₁₀O₃₆(PO₄)Ti₂] has been hydrothermally synthesized and structurally determined by the single-crystal X-ray diffraction. Black prismatic crystals crystallize in the monoclinic system, space group P2(1)/n, a=11.2075(2), b=37.8328(5) c=13.0888(1) Å, β=101.4580(10)°, M=2276.13, V=5439.19(13) ų, Z=4. Data were collected on a Siemens SMART CCD diffractometer at 293(2) K in the range of 1.68<θ<25.09° using the ω-scan technique (λ=0.71073 Å R(F)=0.0872 for 9621 reflections). The title compound contains a trimetal heteropolyanion polymer and “trans-titanium”-bridging pseudo-Keggin fragments linked to a chain.     

Synthesis and structure of three manganese oxalates: MnC2O4·2H2O, [C4H8(NH2)2][Mn2(C2O4)3] and Mn2(C2O4)(OH)2

Three manganese oxalates have been hydrothermally synthesized, and their structures determined by single-crystal X-ray diffraction. MnC₂O₄·2H₂O (I) is orthorhombic, P2₁2₁2₁, , , , , Z=4, final R, R_w=0.0832, 0.1017 for 561 observed data (I>3σ(I)). The one-dimensional structure consists of chains of oxalate-bridged manganese centers. [C₄H₈(NH₂)₂][Mn₂(C₂O₄)₃] (II) is triclinic, , , , , α=81.489(2)°, β=81.045(2)°, γ=86.076(2)°, , Z=1, final R, R_w=0.0467, 0.0596 for 1773 observed data (I > 3σ (I)). The three-dimensional framework is constructed from seven coordinate manganese and oxalate anions. The material contains extra-framework diprotonated piperazine cations. Mn₂(C₂O₄)(OH)₂ (III) is monoclinic, P2₁/c, , , , β=91.10(3)°, , Z=1, final R₁, wR2=0.0710, 0.1378 for 268 observed data (I>2σ (I)). The structure is also three dimensional, with layers of MnO₆ octahedra pillared by oxalate anions. The hydroxide group is found bonded to three manganese centers resulting in a four coordinate oxygen.     

Heterometallic hafnocene(+4) aluminum hydride complex [(ηp5-C5H5)2Hf(H)(μ2-H)Al(H)Br(μ2-OC4H9)]2

The [Cp₂HfH₂Al(H)Br(OBu)]₂ complex (1) was prepared by the reaction of Cp₂HfBr₂ with AlH₃ in THF and characterized by X-ray crystallography. The formation of dinuclear complex 1 proceeds through the intermediate formation (as a result of cleavage of THF molecules) of the >Al(μ-OBu)₂Al< fragment. The latter is linked to two hafnocene dihydride molecules by the Hf-H-Al hydrogen bridges. The Hf atom in complex 1 has a 16-electron environment.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2082–2085, October, 2004.