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.     

Synthesis and structural characterization of (H4APPIP)[V3(C2O4)2(HPO4)3(PO4)(H2O)]·6H2O (APPIP=1,4-bis(3-aminopropyl)piperazine), a layered vanadium oxalatophosphate containing double 6-ring units

A new vanadium(III) oxalatophosphate has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction and thermogravimetric analysis. It crystallizes in the triclinic space group with a=11.604(2) Å, b=12.391(2) Å, c=15.220(3) Å, α=71.090(3)°, β=82.630(3)°, γ=62.979(3)°, V=1843.8(5) Å³ and Z=2. The structure consists of V₆(HPO₄)₆ double 6-ring (D6R) units connected by coordinating C₂O₄²⁻ and PO₄³⁻ anions to form anionic sheets in the ab plane with charge-compensating quadruply protonated 1,4-bis(3-aminopropyl)piperazinium cations and water molecules between the sheets. It is one of the few compounds with 2D layer structures and the second example containing D6R units in the system of metal oxalatophosphates. The iron analogue was also synthesized.     

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.     

九配位钇(Ⅲ)-氨三乙酸配合物K3[Y(NTA)2(H2O)]·6H2O的合成及分子结构

In this paper we describe the molecular and crystal structures of the K₃[Y(NTA)₂(H₂O)]· 6H₂O(H₃NTA=nitrilotriacetic acid). The crystal data are as followsmonoclinic system, C2/c space group, a=1.5268(3)nm,b=1.2833(3)nm,c=2.6079(5)nm,β =96.03(3)°,V=5.0815(18)nm³,Z=8,M=708.68,Dc=1.852gcm^-3,μ =2.875mm^-1,F(000)=2880.The final R1 and wR2 are 0.0636 and 0.1523 for 4264 [I >2.0σ (I)] unique reflections and 0.1178 and 0.1651 for all 4364 reflections,respectively.In the title complex, the anion [Y(NTA)₂(H₂O)]^3- has a nine-coordination structure with distorted monocapped square antiprism. Each group acts as a tetradentate ligand with three Oatoms and one Natom and a H₂O molecule caps a quadrilateral face as a ligand.It can be known that the Y(Ⅲ) ion can form a high-coordinate compound with aminopolycarboxylic acid ligands because it has a larger ionic radius (0.104nm).     

Solid state photodecomposition studies of K4Ti(O2)4·2H2O, K3Ta(O2)2F4 and K2V2O3(O2)2F2

The compounds K₄Ti(O₂)₄·2H₂O, K₃Ta(O₂)₂F₄ and K₂V₂O₃(O₂)₂F₂ undergo photolysis in the solid state. The photolysis kinetics obey the parabolic rate equation p = kt^1/2 and indicate a monoexcitation process for the photolysis. These features are similar to those reported previously for peroxo complexes. The mechanism of evolution of oxygen reported earlier appears to be the same in all these solids.     

Syntheses and structural determination of nine-coordinate K3[Nd(nta)2(H2O)]·6H2O and K3[Er(nta)2(H2O)]·5H2O

The syntheses and structural determination of Nd^III and Er^III complexes with nitrilotriacetic acid (nta) were reported in this paper. Their crystal and molecular structures and compositions were determined by single-crystal X-ray structure analyses and elemental analyses, respectively. The crystal of K₃[Nd^III(nta)₂(H₂O)]·6H₂O complex belongs to monoclinic crystal system and C2/c space group. The crystal data are as follows: a=1.5490(11) nm, b=1.3028(9) nm, c=2.6237(18) nm, β=96.803(10)°, V=5.257(6) nm³, Z=8, M=763.89, D_c=1.930 g cm⁻³, μ=2.535 mm⁻¹ and F(000)=3048. The final R₁ and wR₁ are 0.0390 and 0.0703 for 4501 (I>2σ(I)) unique reflections, R₂ and wR₂ are 0.0758 and 0.0783 for all 10474 reflections, respectively. The Nd^IIIN₂O₇ part in the [Nd^III(nta)₂(H₂O)]³⁻ complex anion has a pseudo-monocapped square antiprismatic nine-coordinate structure in which the eight coordinate atoms (two N and six O) are from the two nta ligands and a water molecule coordinate to the central Nd^III ion directly. The crystal of the K₃[Er^III(nta)₂(H₂O)]·5H₂O complex also belongs to monoclinic crystal system and C2/c space group. The crystal data are as follows: a=1.5343(5) nm, b=1.2880(4) nm, c=2.6154(8) nm, b=96.033(5)°, V=5.140(3) nm³, Z=8, M=768.89, D_c=1.987 g cm⁻³, μ=3.833 mm⁻¹ and F(000)=3032. The final R₁ and wR₁ are 0.0321 and 0.0671 for 4445 (I>2σ(I)) unique reflections, R₂ and wR₂ are 0.0432 and 0.0699 for all 10207 reflections, respectively. The Er^IIIN₂O₇ part in the [Er^III(nta)₂(H₂O)]³⁻ complex anion has the same structure as Nd^IIIN₂O₇ part in which the eight coordinate atoms (two N and six O) are from the two nta ligands and a water molecule coordinate to the central Nd^III ion directly.     

Synthesis and structure of [C6H14N2][(UO2)4(HPO4)2(PO4)2(H2O)]·H2O: An expanded open-framework amine-bearing uranyl phosphate

A new open-framework compound, [C₆H₁₄N₂][(UO₂)₄(HPO₄)₂(PO₄)₂(H₂O)]·H₂O, (DUP-1) has been synthesized under mild hydrothermal conditions. The resulting structure consists of diprotonated DABCOH₂²⁺ (C₆H₁₄N₂²⁺) cations and occluded water molecules occupying the channels of a complex uranyl phosphate three-dimensional framework. The anionic lattice contains uranophane-like sheets connected by hydrated pentagonal bipyramidal UO₇ units. [C₆H₁₄N₂][(UO₂)₄(HPO₄)₂(PO₄)₂(H₂O)]·H₂O possesses five crystallographically unique U centers. U(VI) is present here in both six- and seven-coordinate environments. The DABCOH₂²⁺ cations are held within the channels by hydrogen bonds to both two uranyl oxygen atoms and a μ₂-O atom. Crystallographic data (193 K, Mo Kα, λ=0.71073 Å): DUP-1, monoclinic, P2₁/n, a=7.017(1) Å, b=21.966(4) Å, c=17.619(3) Å, β=90.198(3)°, Z=4, R(F)=4.76% for 382 parameters with 6615 reflections with I>2σ(I).     

Hydrothermal synthesis and characterization of (enH2)3.5[As8V14O42(PO4)]·2H2O

The compound (enH₂)_3.5[As₈V₁₄O₄₂(PO₄)]·2H₂O 1 (en=ethylenediamine) has been synthesized and characterized by means of elemental analysis, IR spectrum, ESR spectrum, XPS spectrum, TG analysis and single crystal X-ray diffraction analysis. The compound 1 crystallizes in monoclinic system, space group C2/c, β=105.59(3), Z=8 and R₁(wR₂)=0.0398(0.0885). The compound 1 is constructed from [As₈V₁₄O₄₂(PO₄)]⁷⁻ anions and H₂en cations linked through hydrogen bonds into a network. The [As₈V₁₄O₄₂(PO₄)]⁷⁻ cluster consists of 14 VO₅ square pyramids linked by 4 As₂O₅ handle-like units, and includes at its center an ordered PO₄³⁻ anion.     

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.     

The crystal structure of Cu4(PO4)2O

Cu₄(PO₄)₂O crystallizes in the space group $\text{P}\text{1}$ with a = 7.5393(8) Å, b = 8.1021(9) Å, c = 6.2764(8) Å, α = 113.65(1)°, β = 98.42(1)° and γ = 74.19(1)°. The structure was refined by full-matrix least-squares techniques using automatic diffractometer data to R = 0.046 (R_w = 0.056). Four unique copper atoms are in six, five-, and four-coordinated polyhedra which are linked together to form a three-dimensional network. The structure is best described in terms of a cubic close-packed array of oxygen atoms with one-tenth of the possible anion sites vacant.     

The actual structure of K6(VO)2(V2O3)2(PO4)4(P2O7): Ordered distribution of P2O7 groups and charge ordering of vanadium

The actual structure of the vanadium phosphate K₆(VO)₂(V₂O₃)₂(PO₄)₄(P₂O₇) has been determined, using a much larger single crystal than previously used for the isostructural Rb-phase. The actual supercell is four times larger than the corresponding orthorhombic subcell with , , , α=β=γ=90°. The structure resolution, performed in the triclinic space group C-1, shows that the P₂O₇ groups alone are responsible for the superstructure, all the other atoms keeping the atomic positions of the orthorhombic subcell. This structural study shows a perfect ordering of the P₂O₇ groups in the actual structure, in contrast to the results obtained from the subcell. Concomitantly, the V⁴⁺ and V⁵⁺ are found to be ordered in the form of [110] stripes.     

Low-temperature heat capacity of triangle antiferromagnetic molecular clusters K12[(VO)3(SbW9O33)2]·15H2O and K12[(VO)3(BiW9O33)2]·29H2O

Energy level diagrams have been determined for two molecular clusters, K₁₂[(VO)₃(SbW₉O₃₃)₂]·15H₂O and K₁₂[(VO)₃(BiW₉O₃₃)₂]·29H₂O, by low-temperature heat capacity measurements down to 85 mK under magnetic field strengths up to 9 T. Both compounds exhibit a broad heat capacity peak dependent upon the magnetic field, which can be explained by the thermal excitation in the magnetic energy levels. A detailed analysis based on the numerical calculation reveals that the spin-spin interaction between the V⁴⁺ ions includes a Dzyaloshinskii-Moriya interaction.     

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.     

Thermochemistry of NaRb[B4O5(OH)4]·4H2O

The enthalpies of solution of NaRb[B₄O₅(OH)₄]·4H₂O in approximately 1 mol dm⁻³ aqueous hydrochloric acid and of RbCl in aqueous (hydrochloric acid + boric acid + sodium chloride) were determined. From these results and the enthalpy of solution of H₃BO₃ in approximately 1 mol dm⁻³ HCl(aq) and of sodium chloride in aqueous (hydrochloric acid + boric acid), the standard molar enthalpy of formation of −(5128.02 ± 1.94) kJ mol⁻¹ for NaRb[B₄O₅(OH)₄]·4H₂O was obtained from the standard molar enthalpies of formation of NaCl(s), RbCl(s), H₃BO₃(s) and H₂O(l). The standard molar entropy of formation of NaRb[B₄O₅(OH)₄]·4H₂O was calculated from the Gibbs free energy of formation of NaRb[B₄O₅(OH)₄]·4H₂O computed from a group contribution method.     

[H3N(CH2)4NH3]2[Al4(C2O4)(H2PO4)2(PO4)4]·4[H2O]: A new layered aluminum phosphate-oxalate

A new layered inorganic-organic hybrid aluminum phosphate-oxalate [H₃N(CH₂)₄NH₃]₂[Al₄(C₂O₄)(H₂PO₄)₂(PO₄)₄]·4[H₂O](AlPO-CJ25) has been synthesized hydrothermally, by using 1,4-diaminobutane (DAB) as structure-directing agent. The structure has been solved by single-crystal X-ray diffraction analysis and further characterized by IR, ³¹P MAS NMR, TG-DTA as well as compositional analyses. Crystal data: the triclinic space group P-1, a=8.0484(7) Å, b=8.8608(8) Å, c=13.2224(11) Å, α=80.830(6)°, β=74.965(5)°, γ=78.782(6)°, Z=2, R_1[I>2σ(I)]=0.0511 and wR_{2(all data)}=0.1423. The alternation of AlO₄ tetrahedra and PO₄ tetrahedra gives rise to the four-membered corner-sharing chains, which are interconnected through AlO₆ octahedra to form the layered structure with 4,6-net sheet. Interestingly, oxalate ions are bis-bidentately bonded by participating in the coordination of AlO₆, and bridging the adjacent AlO₆ octahedra. The layers are held with each other through strong H-bondings between the terminal oxygens. The organic ammonium cations and water molecules are located in the large cavities between the interlayer regions.     

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.     

Hydrothermal Syntheses, Structures, and Properties of Two New Potassium Vanadium Phosphates: K3(VO) (V2O3) (PO4)2(HPO4) and K3 (VO) (HV2O3) (PO4)2(HPO4)

Two new potassium vanadium phosphates have been prepared and their structures have been determined from analysis of single crystal X-ray data. The two compounds, K₃(VO)(V₂O₃) (PO₄)₂(HPO₄) and K₃(VO)(HV₂O₃)(PO₄)₂(HPO₄), are isostructural, except for the incorporation of an extra hydrogen atom into the nearly identical frameworks. The structures consist of a three-dimensional network of [VO]_n chains connected through phosphate groups to a [V₂O₃] moiety. Magnetic susceptibility experiments indicate that in the case of the di-hydrogen compound, there are no significant magnetic interactions between the three independent vanadium (IV) centers. Crystal data: for K₃(VO)(V₂O₃)(PO₄)₂ (HPO₄), M_r = 620.02, orthorhombic space group Pnma (No. 62), a = 7.023(4) Å, b = 13.309(7) Å, c = 14.294(7) Å, V = 1336(2) ų, Z = 4, R = 5.02%, and R_w = 5.24% for 1238 observed reflections [I > 3σ(I)]; for K₃(VO)(HV₂O₃)(PO₄)₂(HPO₄), M_r = 621.04, orthorhombic space group Pnma (No. 62), a = 6.975(3) Å, b = 13.559(7) Å, c = 14.130(7) Å, V = 1336(1) ų, Z = 4, R = 6.02%, and R_w = 6.34% for 1465 observed reflections [I > 3σ(I)].     

The synthesis and crystal structure of vanadium complexes: [VO2(phen)2]·6H2O and [2,2′-(bipy)2VO2](H2BO3)·3H2O

The organic-inorganic hybrid materials vanadium oxide [V^IVO₂(phen)₂]·6H₂O (1) and [(2,2′-bipy)₂V^VO₂](H₂BO₃)·3H₂O (2) have been conventional and hydrothermal synthesized and characterized by single crystal X-ray diffraction, elemental analyses, respectively. Although the method and the ligand had been used in the syntheses of the compounds (1) and (2) are different, they almost possess similar structure. They all exhibit the distorted octahedral [VO₂N₄] unit with organonitrogen donors of the phen and 2,2′-bipy ligands, respectively, which coordinated directly to the vanadium oxide framework. And they are both non-mixed-valence complexes. But the compound (1) is isolated, and the compound (2) consists of a cation of [(2,2′-bipy)₂V^VO₂]⁺ and an anion of (H₂BO₃)⁻. So the valence of vanadium of (1) and (2) are tetravalence and pentavalence, respectively. Meanwhile it is noteworthy that π-π stacking interaction between adjacent phen and 2,2′-bipy groups in compounds 1 and 2 also play a significant role in stabilization of the structure. Thus, the structure of [V^IVO₂(phen)₂]·6H₂O and [(2,2′-bipy)₂V^VO₂](H₂BO₃)·3H₂O are both further extended into interesting three-dimensional supramolecular. Crystal data: (1) Triclinic, a=8.481(4), b=12.097(5), and α=66.32(2), β=82.97(3), and γ=82.59(4)°, Z=2, R₁=0.0685, wR₂=0.1522. (2) Triclinic, a=6.643(13), b=11.794(2), and α=101.39(3), β=101.59(3), and γ=97.15(3)°, Z=2, R₁=0.0736, wR₂=0.1998.     

Synthesis, structure, and characterization of hybrid materials: [Ce(H2O)]2[O2C(CH2)2CO2]3 and [Sm(H2O)]2[O2C(CH2)2CO2]3·H2O

The rare-earth dicarboxylate hybrid materials [Ce(H₂O)]₂[O₂C(CH₂)₂CO₂]₃ ([Ce(Suc)]) and [Sm(H₂O)]₂[O₂C(CH₂)₂CO₂]₃·H₂O ([Sm(Suc)]) have been hydrothermally synthesized (200°C, 3 days) under autogenus pressure. [Ce(Suc)] is triclinic, a=7.961 (3) Å, b=8.176 (5) Å, c=14.32 (2) Å, α=97.07° (7), β=96.75° (8), γ=103.73° (6), and z=2. The crystal structure of this compound has been determined using 3120 unique single crystal data. The final refinements let the agreement factors R₁ and wR₂(F²) converge to 0.0138 and 0.0363, respectively. [Ce(Suc)] is built up from infinite chains of edge-sharing nine-fold coordinated cerium atoms running along [100]. These chains are interconnected by the carbon atoms of the succinate anions, leading to a three-dimensional hybrid framework. The cell constants of [Sm(Suc)], isotypic with monoclinic C2/c [Pr(H₂O)]₂[O₂C(CH₂)₂CO₂]₃·H₂O ([Pr(Suc)]), were refined starting from X-ray powder data: a=20.275 (3) Å, b=7.919 (6) Å, c=14.130 (3) Å, and β=121.45° (1). Despite its lower symmetry, [Ce(Suc)] presents an important structural filiation with [Sm(Suc)]     

Single-Crystal Neutron Structure Analysis of (NH4)21[H3Mo57V6(NO)6O183(H2O)18]·53 H2O

The crystal structure of (NH₄)₂₁[H₃Mo₅₇V₆(NO)₆O₁₈₃ (H₂O)₁₈]·53 H₂O a supramolecular heteropoly cluster compound (space group P6₃/mmcZ=2 final R1=0.1302 (I>2σ(I)) for 1745 unique reflections) was redetermined by single-crystal neutron diffraction studies at 20 K. The X-ray diffraction results reported in 1994 by Müller et al. (Z. Anorg. Allg. Chem. 620 599) are confirmed. Additionally we could localize many hydrogen positions not found so far and establish a phase transition near 240 K. Many of the ammonium ions the ligand and hydrate H₂O molecules and the hydroxy group are orientationally disordered even at 20 K. The central cavity of the structure is built up by two twelve-membered rings consisting of six O-H·sdot;·O hydrogen bonds each. These strong hydrogen bonds are obviously decisive for the stability of the cluster. The hydrate H₂O molecules are stronger-hydrogen-bond acceptor groups than the oxoligands of the cluster.