A new sodium hydroxygallophosphate containing tetrameric gallium units: Na3[Ga4O(OH)(H2O)(PO4)4]·H2O

A new sodium hydroxygallophosphate, Na₃Ga₄O(OH)(H₂O)(PO₄)₄·H₂O, has been prepared by hydrothermal synthesis. Its structure has been determined from a single-crystal X-ray diffraction study. It crystallizes in the P2₁/c space group with the cell parameters a=9.445(2) Å, b=9.028(1) Å, c=19.209(3) Å, β=102.08(2), V=1603.4(4) Å³. Its three-dimensional framework can be described from PO₄ monophosphate groups sharing their apices with original Ga₄O₁₆(OH)(H₂O) tetrameric building units, which result from the assembly of one GaO₄ tetrahedron, one GaO₅ trigonal bipyramid and two octahedra: GaO₅(OH) and GaO₄(OH)(H₂O). The sodium cations and one water molecule are located in tunnels running along b.     

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.     

Solvothermal synthesis, crystal structure, magnetic and luminescent properties of (H3O)6·[Co4(H2O)4(HPMIDA)2(PMIDA)2)]·2H2O

A cobalt phosphonate (H₃O)₆·[Co₄(H₂O)₄(HPMIDA)₂(PMIDA)₂)]·2H₂O, 1, has been synthesized from a mild solvothermal reaction of Co(II) ion with N-(phosphonomethyl)iminodiacetic acid (H₄PMIDA). Compound 1 crystallizes in the triclinic space group with cell parameters of , , , α=93.06(3)°, β=99.66(3)°, γ=90.34(3)° and Z=1. Compound 1 shows a novel tetra-nuclear molecular structure. In the crystal lattice, molecules of 1 hydrogen bond to each other to form two-dimensional (2D) layers, which are further linked together by the co-crystallized H₂O molecules and H₃O⁺ counter ions through hydrogen bonding to form the 3D supramolecular network. Thermogravimetric analysis, IR spectrum, magnetic susceptibility and luminescent spectra are given.     

Hydrothermal synthesis, crystal structure, and magnetic properties of a novel organo-templated iron(III) borophosphate: (C3H12N2)Fe 6(H2O)4[B4P8O32(OH)8]

The organo-templated iron(III) borophosphate (C₃H₁₂N₂)Fe^III ₆(H₂O)₄[B₄P₈O₃₂(OH)₈] was prepared under mild hydrothermal conditions (at 443 K) and the crystal structure was determined from single crystal X-ray data at 295 K (monoclinic, P2₁/c (No. 14), a=5.014(2) Å, b=9.309(2) Å, c=20.923(7) Å, β=110.29(2)°, V=915.9(5) Å³, Z=2, R1=0.049, wR2=0.107 for all data, 2234 observed reflections with I>2σ(I)). The title compound contains a complex inorganic framework of borophosphate trimers [BP₂O₈(OH)₂]⁵⁻ together with FeO₄(OH)(H₂O)- and FeO₄(OH)₂-octahedra forming channels with ten-membered ring apertures in which the diaminopropane cations are located. The magnetization measurements confirm the Fe(III)-state and show an antiferromagnetic ordering at T_N≈14.0(1) K.     

Synthesis, structure, and properties of the first trimetallic phosphate [Ni(H2O)4]Cd(VO)(PO4)2 with neutral 3-D pillared-layer framework

Hydrothermal reactions of VOSO₄·3H₂O, CdAc₂·2H₂O, NiCl₂·6H₂O, H₃PO₄, and H₂O yield the first example of trimetallic phosphate materials, [Ni(H₂O)₄]Cd(VO)(PO₄)₂1. The single-crystal X-ray diffraction shows that its structure consists of Cd/V/O binary metal oxide lamellas decorated by PO₄ tetrahedra, which are further pillared by NiO₂(H₂O)₄ octahedra to generate a neutral 3-D framework containing two intercrossing 8-MR channels where the coordinated water molecules protrude into. Thermal and magnetic behaviors of this material were also measured. Crystal data: CdNiVP₂O₁₃H₈, orthorhombic Ibca (No.73), a=7.1307(2) Å, b=18.6248(3) Å, c=14.8046(2) Å, V=1966.17(7) Å³, Z=8.     

Crystal chemistry of M[PO2(OH)2]2·2H2O compounds (M=Mg, Mn, Fe, Co, Ni, Zn, Cd): Structural investigation of the Ni, Zn and Cd salts

The compounds M[PO₂(OH)₂]₂·2H₂O (M=Mg, Mn, Fe, Co, Ni, Zn, Cd) were prepared from super-saturated aqueous solutions at room temperature. Single-crystal X-ray structure investigations of members with M=Ni, Zn, Cd were performed at 295 and 120 K. The space-group symmetry is P2₁/n, Z=2. The unit-cell parameters are at 295/120 K for M=Ni: a=7.240(2)/7.202(2), b=9.794(2)/9.799(2), c=5.313(1)/5.285(1) Å, β=94.81(1)/94.38(1)°, V=375.4/371.9 Å³; M=Zn: a=7.263(2)/7.221(2), b=9.893(2)/9.899(3), c=5.328(1)/5.296(2) Å, β=94.79(1)/94.31(2)°, V=381.5/377.5 Å³; M=Cd: a=7.356(2)/7.319(2), b=10.416(2)/10.423(3), c=5.407(1)/5.371(2) Å, β=93.85(1)/93.30(2)°, V=413.4/409.1 Å³. Layers of corner-shared MO₆ octahedra and phosphate tetrahedra are linked by three of the four crystallographically different hydrogen bonds. The fourth hydrogen bond (located within the layer) is worth mentioning because of the short O_h?O bond distance of 2.57-2.61 Å at room temperature (2.56-2.57 Å at 120 K); only for M=Mg it is increased to 2.65 Å. Any marked temperature-dependent variation of the unit-cell dimension is observed only vertical to the layers. The analysis of the infrared (IR) spectroscopy data evidences that the internal PO₄ vibrations are insensitive to the size and the electronic configuration of the M²⁺ ions. The slight strengthening of the intra-molecular P-O bonds in the Mg salt is caused by the more ionic character of the Mg-O bonds. All IR spectra exhibit the characteristic “ABC trio” for acidic salts: 2900-3180 cm⁻¹ (A band), 2000-2450 cm⁻¹ (B band) and 1550-1750 cm⁻¹ (C band). Both the frequency and the intensity of the A band provide an evidence that the PO₂(OH)₂ groups in M[PO₂(OH)₂]₂·2H₂O compounds form weaker hydrogen bonds as compared with other acidic salts with comparable O?O bond distances of about 2.60 Å. The observed shift of the O-H stretching vibrations of the water molecule in the order M=Mg>Mn≈Fe≈Co>Ni>Zn≈Cd has been discussed with respect to the influence of both the character and the strength of M↔H₂O interactions.     

Two layered gallophosphates assembled about the chiral metal complexes: Co(en)3·Ga3P4O16·5H2O and trans−Co(dien)2·Ga3P4O16·3H2O

Two new layered gallophosphates Co(en)₃·Ga₃P₄O₁₆·5H₂O (1) and trans-Co(dien)₂·Ga₃P₄O₁₆·3H₂O (2) have been hydrothermally synthesized using the racemic mixture of chiral metal complex Co(en)₃Cl₃ and Co(dien)₂Cl₃ as the structure-directing agent, respectively. Their structures are determined by single-crystal X-ray diffraction analysis and further characterized by X-ray power diffraction, ICP, elemental, and TG analyses. The structures of 1 and 2 consist of vertex-linking GaO₄ and PO₃(=O) tetrahedral units forming macroanionic [Ga₃P₄O₁₆]³⁻ sheets with a 4.6-net. The 4.6-net is characteristic of chiral [3.3.3] propellane-like structural motifs. The sheets of 1 stack in an ABAB sequence, with a pair of enantiomers of chiral Co(en)₃³⁺ cations residing in the interlayer region. The sheets of 2 array in a helical fashion with an ABCDEF stacking sequence, with only one enantiomer of chiral Co(dien)₂³⁺ cations residing in the interlayer region. Structural elucidation of 1 and 2 reveals that there exist stereo-specific correspondence between the metal complex template and the structure of the inorganic host. Crystal data: 1, Co(en)₃·Ga₃P₄O₁₆·5H₂O, orthorhombic, Pnna (No. 52), a=8.6618(2) Å, b=21.6071(5) Å, c=13.7426(4) Å, Z=4, R₁=0.0337 (I>2σ(I)), wR₂=0.0985 (all data); 2, Co(dien)₂·Ga₃P₄O₁₆·3H₂O, hexagonal, P6₅22 (No. 179), a=8.5152(7) Å, b=8.5152(7) Å, c=63.278(8) Å, R₁=0.1183 (I>2σ(I)), wR₂=0.2864 (all data) and Z=6.     

An open-framework three-dimensional indium oxalate: [In(OH)(C2O4)(H2O)]3·H2O

By hydrothermal reaction of In₂O₃ with H₂C₂O₄·2H₂O in the presence of H₃BO₃ at 155 °C, an open-framework three-dimensional indium oxalate of formula [In(OH)(C₂O₄)(H₂O)]₃·H₂O (1) has been obtained. The compound crystallizes in the trigonal system, space group R3c with , , , Z=6, R₁=0.0352 at 298 K. The small pores in 1 are filled with water molecules. It loses its filled water at about 180 °C without the change of structure, then the bounded water at 260 °C, and completely decompounds at 324 °C. The residue is confirmed to be In₂O₃.     

A simple solvothermal synthesis of MFe2O4 (M=Mn, Co and Ni) nanoparticles

Nanoparticles of MFe₂O₄ (M=Mn, Co and Ni), with diameters ranging from 5 to 10 nm, have been obtained through a solvothermal method. In this synthesis, an alcohol (benzyl alcohol or hexanol) is used as both a solvent and a ligand; it is not necessary, therefore, to add a surfactant, simplifying the preparation of the dispersed particles. We have studied the influence of the synthetic conditions (temperature, time of synthesis and nature of solvent) on the quality of the obtained ferrites and on their particle size. In this last aspect, we have to highlight that the solvent plays an important role on the particle size, obtaining the smallest diameters when hexanol was used as a solvent. In addition, the magnetic properties of the obtained compounds have been studied at room temperature (RT). These compounds show a superparamagnetic behaviour, as was expected for single domain nanoparticles, and good magnetization values. The maxima magnetization values of the MFe₂O₄ samples are quite high for such small nanoparticles; this is closely related to the high crystallinity of the particles obtained by the solvothermal method.     

新型微孔磷酸铝[C4N2H14]2+[H2Al3P3O14]2-的合成、结构及相转变

以3-甲氨基丙胺为结构导向剂,在水热条件下合成了1个具有三维开放骨架结构的微孔磷酸铝化合物[C4N2H14][H2Al3P3O14](1),并通过X射线单晶衍射确定了其结构,用粉末X射线衍射(PXRD)、热重(TG)、元素分析(ICP及CHN)和扫描电子显微镜(SEM)对其进行表征.结果表明,化合物1属正交晶系,Pbca空间群,晶胞参数a=1.59839(11)nm,b=0.99402(6)nm,c=1.82261(11)nm,V=2.8958(3)nm3.化合物1的无机骨架由铝氧多面体(AlO5/AlO6)和磷氧四面体(PO4)严格交替连接构筑而成,形成了在[010]方向上具有一维十元环孔道的三维阴离子开放骨架.每个P原子通过桥氧原子与相邻的4个Al原子相连,而Al原子除了通过桥氧原子与相邻的4个P原子相连之外,还通过羟基的桥氧原子与1个或2个Al原子相连,分别形成五配位和六配位的Al.化合物1在550℃空气或氧气气氛下灼烧5 h后转变为具有ATV分子筛结构的微孔磷酸铝分子筛AlPO4-25,且一直稳定到800℃.     

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.     

Hydrothermal synthesis, crystal structure, and magnetic property of a three-dimensional inorganic-organic hybrid material: Mn(H2O)[HO3PCH2NH(CH2CO2)2]

A novel three-dimensional inorganic-organic hybrid compound, Mn(H₂O)[HO₃PCH₂NH(CH₂CO₂)₂] from a hydrothermal reaction of Mn (II) ion with N-(phosphonomethyl)iminodiacetic acid (H₄PMIDA) was reported. The compound crystallizes in the monoclinic P2₁/n with cell dimensions of a=5.215(5) Å, b=14.111(15) Å, c=12.727(12) Å, β=93.646(16)°, V=934.6(16) Å³ and Z=4. In this structure each Mn atom is six-coordinated with the carboxylic groups and phosphonic groups to form layers along the bc plane. These layers are further connected with the organic moieties of H₂PMIDA, resulting in a complicated three-dimensional network structure. Thermogravimetric analysis, IR spectrum and magnetic susceptibility of this compound are given.     

Crystal chemistry of MSeO3 and MTeO3 (M = Mg,Mn, Co,Ni, Cu,and Zn)

New selenites and tellurites MgSeO₃, MnSeO₃, CoSeO₃, NiSeO₃, CuSeO₃, MnTeO₃, CoTeO₃, and NiTeO₃ were synthesized under high pressures and temperatures. All the compounds are isomorphous and their crystal system is orthorhombic. Structure analyses were carried out for all the selenites and CoTeO₃. The structure is described as a salt of M²⁺ and SeO₃^2? or TeO₃^2? ions or as a distorted perovskite. In these compounds an Se or Te atom is closely linked to three oxygen atoms to form a flattened trigonal pyramid. The features of this coordination are discussed. At low temperature, magnetic order appears in all the compounds containing iron group ions, among which CuSeO₃ is a ferromagnet with the Curie temperature of 26°K.     

Etude à haute pression des tétramétaphosphates du type M2P4O12 (M = Ni,Mg, Cu,Co, Fe,Mn, Cd). Données cristallographiques sur tous les composés M2P4O12

Fe₂P₄O₁₂ has been prepared and identified as an isotype of the other M^II₂P₄O₁₂ tetrametaphosphates (M^II = Ni, Mg, Cu, Co, Mn, Cd). Its monoclinic unit cell:

$\text{a=11.952,b=8.359,c=9.932}\text{A}\text{?}$

$\text{β=118°76}$

contains 4 formula units. The space group is $\text{C2}\text{c}$. For tetrametaphosphates with M^II = Ni, Mg, Cu, Co, and Mn we found a new denser phase induced at 80 kbar and 1000°C. In the case of Fe₂P₄O₁₂ the unit cell of this new form is

$\text{a=9.777,b=8.994,c=4.968}\text{A}\text{?}$

$\text{β=107°22}$

with Z = 2 and two possible space groups Cc or $\text{2C}\text{c}$. This dense phase exists at ordinary pressure for the zinc salt.     

Hydrothermal synthesis, crystal structure and characterization of [Zn(H2O)4]2 [H2As6V15O42(H2O)]·2H2O

The compound [Zn(H₂O)₄]₂[H₂As₆V₁₅O₄₂(H₂O)]·2H₂O (1) has been synthesized and characterized by elemental analysis, IR, ESR, magnetic measurement, third-order nonlinear property study and single crystal X-ray diffraction analysis. The compound 1 crystallizes in trigonal space group R3, a=b=12.0601(17) Å, c=33.970(7) Å, γ=120°, V=4278.8(12) Å³, Z=3 and R1(wR2)=0.0512 (0.1171). The crystal structure is constructed from [H₂As₆V₁₅O₄₂(H₂O)]⁴⁻ anions and [Zn(H₂O)₄]²⁺ cations linked through hydrogen bonds into a network. The [H₂As₆V₁₅O₄₂(H₂O)]⁶⁻ cluster consists of 15 VO₅ square pyramids linked by three As₂O₅ handle-like units.     

Hydrothermal synthesis and characterization of layered vanadium phosphite: [HN(C2H4)3N][(VO)2(HPO3)2(OH)(H2O)]·H2O

A novel compound, [HN(C₂H₄)₃N][(VO)₂(HPO₃)₂(OH)(H₂O)]·H₂O, was hydrothermally synthesized and characterized by single crystal X-ray diffraction. This compound crystallizes in the monoclinic system with the space group C2/c and cell parameters a=11.0753(3) Å, b=17.8265(6) Å, c=16.5229(5) Å, and β=92.362(2)°. The structure of the compound consists of vanadium phosphite layers which are built up from the infinite one-dimensional chains of [(VO)(H₂O)(HPO₃)₂]²⁻ of octahedral VO₅(H₂O) and pseudo pyramidal [HPO₃], and bridging binuclear fragments of [VO(OH)]₂. Thermogravimetric analysis and magnetic susceptibility data for this compound are given.     

New binuclear vanadium(III) and (IV) squarate species: synthesis, structure and characterization of [V(OH)(H2O)2(C4O4)]2·2H2O and (NH4)[(VO)2(OH)(C4O4)2(H2O)3]·3H2O

Two new vanadium squarates have been synthesized, characterized by infrared and thermal behavior and their structures determined by single crystal X-ray diffraction. Both structures are made of discrete, binuclear vanadium entity but in 1, [V(OH)(H₂O)₂(C₄O₄)]₂·2H₂O the vanadium atom is trivalent and the entity is neutral while in 2, (NH₄)[(VO)₂(OH)(C₄O₄)₂(H₂O)₃]·3H₂O, the vanadium atom is tetravalent and the entity is negatively charged, balanced by the presence of one ammonium ion. Both molecular anions are bridged by two terminal μ₂ squarate ligands. 1 crystallizes in the triclinic system, space group P-1, with lattice constants a=7.5112(10) Å, b=7.5603(8) Å, c=8.2185(8) Å, α=106.904(8)°, β=94.510(10)°, γ=113.984(9)° while 2 crystallizes in the monoclinic system, space group C2/c, with a=14.9340(15) Å, b=6.4900(9) Å, c=17.9590(19) Å and β=97.927(12)°. From the magnetic point of view, V(III) binuclear species show ferromagnetic interactions at low temperatures. However, no anomalies pointing to magnetic ordering are observed down to 2 K.     

[Ni(C6N2H14)2][Zn4(H2O)(HPO3)5]: A new open-framework zinc phosphite with intersecting 8-, 12- and 16-ring channels

A new three-dimensional (3-D) zinc phosphite with Zn/P ratio of 4/5, [Ni(C₆N₂H₁₄)₂][Zn₄(H₂O)(HPO₃)₅] (1), has been prepared by using self-assembled nickel complexes as the structure-directing agents. Its structure is built up from strict alternation of ZnO₄ tetrahedra and HPO₃ pseudo-pyramids, resulting in an open framework with multi-directional intersecting 8-, 12- and 16-ring channels. The unique nickel complexes Ni(DACH)₂ (DACH=1,2-diaminocyclohexane) only involving the cis-DACH acting as ligands are self-assembled under hydrothermal conditions, and act as the structure-directing agents (SDAs) to direct the formation of compound 1. Nickel complexes reside in the channels in a manner that the hydrophobic ends of the cis-DACH molecules exclusively protrude into the 16-ring pores and the amino groups closely interact with the charged inorganic framework through weak H-bonds. The interesting arrangements of nickel complexes imply a feasible approach to the design and synthesis of extra-large pore materials.     

Synthesis, structure of [H3dien]·(MF6)·H2O (M=Cr, Fe) and Fe Mössbauer study of [H3dien]·(FeF6)·H2O

Single crystals of [H₃dien]·(FeF₆)·H₂O (I) and [H₃dien]·(CrF₆)·H₂O (II) are obtained by solvothermal synthesis under microwave heating. I is orthorhombic (Pna2₁) with a=11.530(2) Å, b=6.6446(8) Å, c=13.787(3) Å, V=1056.3(2) Å³ and Z=4. II is monoclinic (P2₁/c) with a=13.706(1) Å, b=6.7606(6) Å, c=11.3181(9) Å, β=99.38(1)°, V=1034.7(1) Å³ and Z=4. The structure determinations, performed from single crystal X-ray diffraction data, lead to the R₁/wR₂ reliability factors 0.028/0.066 for I and 0.035/0.102 for II. The structures of I and II are built up from isolated FeF₆ or CrF₆ octahedra, water molecules and triprotonated amines. In both structures, each octahedron is connected by hydrogen bonds to six organic cations and two water molecules. The iron-based compound is also characterized by ⁵⁷Fe Mössbauer spectrometry: the hyperfine structure confirms the presence of Fe³⁺ in octahedral coordination and reveals the existence of paramagnetic spin fluctuations.     

[C2N2H10]1.5[Nd(SO4)3(H2O)]·2H2O: The first organically templated neodymium sulfate with a layer structure

The first organically templated neodymium sulfate has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction analysis. [C₂N₂H₁₀]_1.5[Nd(SO₄)₃(H₂O)]·2H₂O crystallizes in the monoclinic space group P2₁/c with crystal data , , , β=104.399(5)°, , Z=4. Refinement gave R₁[I>2σ(I)]=0.0471, and wR₂[I>2σ(I)]=0.0899. The compound exhibits an infinite zigzag anionic layer structure, which consists of {Nd(SO₄)₃(H₂O)}³⁻ structural units connected together to form interesting eight-membered rings via corner-sharing and edge-sharing modes. The compound has the antiferromagnetic behavior and exhibits intense photoluminescence upon photo-excitation at 450 nm.