Synthesis and crystal structure of novel Ruddlesden–Popper strontium niobium oxynitrides

Abstract The family (SrO)(SrNbO 2-x N) n is the first example of Ruddlesden-Popper strontium niobium oxynitrides and provides layered structures to obtain mixed valence niobium compounds with a variety of oxidation states and transport properties. We have prepared members with n =1 (Sr 2 NbO 3 N) and n =2 (Sr 3 Nb 2 O 5 N 2 ) by solid state reaction of Nb 2 O 5 and SrCO 3 at 900–1050 °C under ammonia flow. These compounds crystallize in the I4/mmm space group and show a range of anionic stoichiometry that together with the N/O ratio determines the formal oxidation state for niobium and therefore the resultant physical properties. Samples of the n =1 member show mixed valence Nb 5+ /Nb 4+ an…

Intercalation chemistry of superconducting zirconium and hafnium nitride halides

Abstract Lithium intercalation in MNX (M=Zr, Hf; X=Cl, Br) may lead to superconducting compounds with critical temperatures up to 24 K. Electrochemical lithiation experiments agree with the results obtained with chemical methods, as samples with larger capacity on discharge are also those having larger lithium contents after chemical lithiation. Variations exist in the electrochemical profiles of different batches for these compounds indicating differences in the intercalation reaction pathway. High-resolution electron microscopy images confirm the structural model isotypic to SmSI for β-MNX phases. The major part of crystals from ZrNX as well as from the HfNCl samples showing a high lithiu…

Crystal structures of superconducting sodium intercalates of hafnium nitride chloride

Sodium intercalation compounds of HfNCl have been prepared at room temperature in naphtyl sodium solutions in tetrahydrofuran and their crystal structure has been investigated by Rietveld refinement using X-ray powder diffraction data and high-resolution electron microscopy. The structure of two intercalates with space group Rm and lattice parameters a = 3.58131(6) A u , c = 57.752(6) A u , and a = 3.58791(8) A u , c = 29.6785(17) A u is reported, corresponding to the stages 2 and 1, respectively, of NaxHfNCl. For the stage 2 phase an ordered model is presented, showing two crystallographically independent (HfNCl) units with an alternation of the Hf-Hf interlayer distance along the c-axis, …

Synthesis and spectral studies ofN-2-pyridinylcarbonyl-2-pyridinecarxoximidate copper(II) complexes

Dimeric and polymeric copper(II) complexes containing BPCA (N-2-pyridinylcarbonyl-2-pyridinecarboximidate), having general formulae Cu(BPCA)X·nH2O (X=Cl, Br, NCS, NCO, N3, or CN) and Cu2(BPCA)2-X·nH2O [X=oxalate anion (OX), chloranilate anion (CA) or the dianion of 2,5-dihydroxy-1,4-benzoquinone (DHBQ)] have been synthesized by the copper(II)-assisted hydrolysis of 2, 4, 6-tris(2-pyridyl)-1, 3, 5-triazine. Spectroscopic results indicate five-coordinate, approximately square-pyramidal, geometry around the copper(II) ion. Half-field absorption in the ΔMs=±2 region of the X-band e.p.r. powder spectra has been observed for the dimeric species.

Crystal chemistry and redox behaviour of antimony strontium calcium perovskites

The compound Sr2Sb1.4Ca0.6O6 and their reduced forms Sr2Sb1.4Ca0.6O5.17 and Sr2Sb1.4Ca0.6O4.84 have been prepared and characterized by powder X-ray diffraction, electron diffraction, iodometric analyses and thermogravimetric analysis. The three phases with different oxygen stoichiometries are structurally related to the perovskite and show symmetry distortions from the ideal cubic structure (with cell parameter ap). The crystal structure of Sr2Sb1.4Ca0.6O6 may be refined by the Rietveld method from powder X-ray diffraction data using the space group P21/n, and the cell parameters a=5.776(2), b=5.7837(2), c=8.1718(3) A, β=90.039(3)° with the same structural model than for previously studied …

Very high titanium content mesoporous silicas

Titanium content in mesoporous titanosilicate catalysts has been modulated up to a minimum Si/Ti value of 1.9 by using complexing agents able to coordinate both Si and Ti atoms and harmonize the reactivity of the resulting precursors avoiding subsequent phase segregation and leading to chemically very homogeneous materials. El Haskouri, Jamal, Jamal.Haskouri@uv.es ; Beltran Porter, Aurelio, Aurelio.Beltran@uv.es ; Beltran Porter, Daniel, Daniel.Beltran@uv.es ; Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es

Synthesis and Crystal Structure of a Novel Lamellar Barium Derivative:  Ba(VOPO4)2·4H2O. Synthetic Pathways for Layered Oxovanadium Phosphate Hydrates M(VOPO4)2·nH2O

A unified synthetic strategy has allowed us to rationalize the preparative chemistry of the layered oxovanadium phosphates M(VOPO4)2·nH2O. Thus, we have been able to isolate as single phases with reasonable yields both all the previously characterized phosphates and a new solid containing Ba2+ cations as guest species as well as to prepare new related derivatives involving arsenate anions. In order to organize the experimental results, we have used two complementary models:  a simple restatement of the partial charge model (PCM), and the valence matching principle (VMP) (derived from the bond valence method). The crystal structure of the new barium lamellar derivative, Ba(VOPO4)2·4H2O, has …

Study of the thermal behaviour of ordered bimetallic EDTA complexes

Abstract The study of the thermal behaviour of a family of isostructural ordered bimetallic MM'(EDTA)·6H 2 O complexes has been performed using TG and DTA. Formal kinetic analysis of the dehydration step has been approached using non-isothermal procedures. The resulting correlation among the calculated E a values and the cationic sizes implies a common dehydration mechanism. Copper-containing complexes show distinctive behaviour during the ligand pyrolysis processes. A mechanistic interpretation involving formation of Cu(I) and Cu(0) intermediates is furnished. The evolution of the inorganic residues in systems containing both Co and Ni is especially considered given the interest in the (Co…

Synthetic Pathways for New Tubular Transition Metal Hydroxo- and Fluoro-Selenites: Crystal Structures ofM12(X)2(SeO3)8(OH)6(M=Co2+,Ni2+;X= OH−)

The dumortierite-family structuresM12X2(SeO3)8(OH)6(M= Co2+and Ni2+;X= OH−and F−) have been synthesized. The crystal structures of the hydroxo-derivatives have been refined from X?ray powder diffraction data in the space groupP63mc(Z= 1) witha= 12.887(3) A andc= 4.981(4) A (M= Co2+,X= OH−or F−) anda= 12.704(5) A andc= 4.925(6) A (M= Ni2+,X= OH−or F−). Application of the Partial Charge Transference Model allows the understanding of the selenite derivatives crystal chemistry.

Mono and dinuclear copper(II) complexes of 2,4,6-tris(2-pyridyl)-1, 3,5-triazine and halide or pseudohalide ions: Synthesis and spectral studies

By inhibiting the copper(II) assisted TPT (TPT = 2,4,6-tris(2-pyridyl)-1,3,5-triazine) hydrolysis, monomeric and dimeric copper(II) complexes having as general formulae Cu(TPT)X, · nH2O (X = Cl, Br, NCS, NCO or N3) and [Cu(TPT)X]2(PF6)2 · nH2O (X = Cl, Br, NCS or N3) have been synthesized and characterized by i.r., electronic and e.p.r. spectra, x-ray powder diffraction and analytical data. Spectroscopic results indicate five-coordinate geometry around the copper(II) ion, intermediate between trigonal-bipyramid and square-pyramid structures. The half-field absorption in the ΔMS = 2 region of powdered X-band e.p.r. spectra has been observed for the dimeric species.

Lithium intercalation chemistry, microstructure and superconductivity in zirconium and hafnium nitride halides

Abstract Lithium intercalation in β-MNX (M=Zr, Hf; X=Cl, Br) leads to superconducting compounds with critical temperatures between 12 and 24 K. The lithium uptakes after treatment of the host materials with n-butyllithium/hexane solutions are ca. 0.2 atoms per formula for β-ZrNCl and β-ZrNBr, and between 0.07 and 0.67 for β-HfNCl. Electrochemical lithiation experiments agree with the results obtained with chemical methods, as samples with larger capacity on discharge are also those having larger lithium contents after chemical lithiation. Variations exist in the electrochemical profiles of different batches for the three compounds indicating differences in the intercalation reaction pathway…

Amorphous Complexes MM (EDTA) (H2O)4 · 2H2O . LAXS and XPS Investigation of the Local Structure

Abstract The amorphous MM (EDTA)(H2O)4·2 H2O (M = Ni,Co) substances are made up of infinite chains of alternating "hydrated" and "chelated" octahedra bridged by carboxylate groups: M(H2O)4 - M(EDTA)-M(H2O)4-... . XPS enables to ascertain that the coordination of the EDTA ligand in the amorphous phase is identical to that in the crystalline phase, i.e., hexacoordination toward the M atom and two bridging groups in the Ni -Ni, Co - Co compounds.

Ordered Mesoporous Silicon Oxynitrides

Vanadyl phosphate dihydrate, a solid acid: the role of water in VOPO4�2H2O and its sodium derivatives Na x (VIV x VV 1?x O)PO4�(2?x)H2O

Sodium-containing intercalates having as general formula Na x VOPOP4·(2−x)H2O (0.25≤x<0.50) have been obtained and characterized. Orthorhombic phases, which essentially maintain the structure of the layered oxide hydrate VOPO4·2H2O result. Intercalated sodium ions act as ‘pillars’. The presence of H3O+ ions in the parent VOPO4·2H2O and also in some reduced phases, is detected. The understanding of the structural role of the water molecules is advanced and the topotactic dehydration/rehydration processes are studied. The formation of a new metastable VOPO4·H2O phase is established.

Interface charge density matching as driving force for new mesostructured oxovanadium phosphates with hexagonal structure, [CTA]xVOPO4·zH2O

Hexagonal mesostructured mixed-valence oxovanadium phosphates [CTA]xVOPO4·zH2O, in short ICMUV-2, have been synthesized through a S+I- cooperative mechanism using cationic surfactant (cetyltrimethylammonium, CTAB) rodlike micelles as a template. On the lines of the hypothesis that the driving force leading to the formation of mesostructured solids is the charge density matching at the interface between the supramolecular−organic and supramolecular−inorganic moieties, the self-assembling process between CTA+ micelles and VOPO4q- planar anions can be thought of as consequence of the adequate adjustment of the metal mean oxidation state. X-ray powder diffraction and TEM techniques show that th…

Ordered mesoporous materials: composition and topology control through chemistry

Abstract The atrane route constitutes a very versatile technique to obtain ordered mesoporous materials. A wide diversity of silica and silica-doped materials can be prepared by bringing into play fundamental synthesis parameters (like temperature, concentration and pH) which, in turn, allow modulation of the resulting material topology.

Magnetic properties of a binuclear copper(II) complex [Cu(terpy)Cl] (PF6)

Towards the Loewenstein limit (Si/Al = 1) in thermally stable mesoporous aluminosilicates

The use of complexing agents to generate polynuclear precursor species containing both Al and Si allows the synthesis of thermally stable mesoporous aluminosilicates including solely tetrahedrally coordinated aluminium, in which the Si/Al ratio can be modulated down to a minimum Si/Al value of 1.06(4). Cabrera Medina, Saul, Saul.Cabrera@uv.es ; El Haskouri, Jamal, Jamal.Haskouri@uv.es ; Latorre Saborit, Julio, Julio.Latorre@uv.es ; Beltran Porter, Aurelio, Aurelio.Beltran@uv.es ; Beltran Porter, Daniel, Daniel.Beltran@uv.es ; Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es

Synthesis and characterization of mono- and binuclear copper(II) complexes with 2,2′:6′,2″-terpyridine (terpy) and carboxylates: X-ray crystal structure of [Cu(terpy)(OOCH)(OH2)](ClO4) complex

Abstract Perchlorate and hexafluorophosphate salts of monomeric [Cu(terpy)(OOCH)(OH2)]+ and dimeric [Cu(terpy)(OOCR)]22+ cations (terpy = 2,2′:6′,2″-terpyridine, R = CH3 or C2H5) have been synthesized and characterized by IR, electronic and ESR spectra, and analytical data. Spectroscopic results indicate a five-coordinate, close-to-square pyramidal geometry around the copper(II) ion. The half-field absorption in the ΔMs = 2 region of powdered X-band ESR spectra has been observed for the dimeric species. The crystal structure of [Cu(terpy)(OOCH)(OH2)](ClO4) has been determined by X-ray diffraction methods. The compound crystallizes in the space group P21/c with unit-cell dimensions: a = 7.34…

Crystal structure and spectroscopic study of [Cu(BPCA)(OH2)(O2CCH3)·H2O complex; BPC = N-2-pyridinylcarbonyl-2-pyridinecarboximidate anion

Abstract The crystal and molecular structure of the [Cu(BPCA)(OH2)(O 2CCH3]·H2O complex (BPCA = N-2-pyridinylcarbonyl-2-pyridinecarboximidate anion) has been determined by X-ray diffraction methods. It crystallizes in the triclinic space group P l with two formula units in a cell of dimensions: a = 7.416(2), b = 8.632(4), c = 13.034(3) A, α = 74.55(3), β = 84.84(3), γ = 81.04(5)°. Least-squares refinement of 2534 reflections with I > 2.5σ(I) and 218 parameters gave a final R = 0.047 and Rw = 0.049. The structure consists of discrete [Cu(BPCA)(OH2)(O2CCH3)] neutral units linked through hydrogen bonding. The coordination geometry around copper ions can be described as tetragonal square pyrami…

Scale-up low-cost synthesis of bimodal mesoporous silicas

Porous pure and doped silicas with pore sizes at two length scales (meso/macroporous) have been prepared through a large scale one-pot surfactant assisted reproducible procedure by using a simple template agent and starting from non-expensive sodium silicate as silicon source. Together with the relative low-cost of the reagents we have used, the simplicity of this method, which moreover is scalable and provides high yields, could be a strong argument for considering its suitability for the production of bimodal porous silicas. Additionally, we present a simple chemical scheme that allows directing the synthesis towards different related materials including both bimodal nanoparticulated meso…

Design of ordered bimetallic complexes, Part 2:Trans-1,2-cyclohexanediaminetetraacetate bimetallates

Knowledge of the kinetic and thermodynamic behaviour of aqueous solutions containing two divalent cations andtrans-1,2-cyclohexanediaminetetraacetate has been used to design synthetic pathways to ordered bimetallic complexes

Spectroscopic studies and crystal structure of bis(N-2-pyridinylcarbonyl-2-pyridinecarboximidato) manganese(II) monohydrate: Zero-field splitting param

Abstract The X-ray crystal structure of bis(N-2-pyridinylcarbonyl-2-pyridinecarboximidato)manganese(II) monohydrate, Mn(BPCA)2·H2O, has been determine

Selective oxidative activation of isobutane on a novel vanadium-substituted bimodal mesoporous oxide V-UVM-7

Abstract New vanado-silicates with a bimodal mesoporous system (V-UVM-7) and high vanadium contents (Si/V ≥ 7) have been prepared by a modification of the so-called atrane method. Its morphology consists of aggregation of nano-particles with V-MCM-41 structure, creating a second broader porous system in their interparticle space. Its structure allows to incorporate a high V contents into tetrahedral sites of the framework while keeping vanadium dispersion. V-UVM-7 catalysts are very active and selective for the direct transformation of isobutane to isobutene and methacrolein. Total conversion and methacrolein-to-isobutene ratio in the products increased with increasing vanadium contents. Th…

Crystal structure and magnetism of Co(HPO3)⋅H2O : A novel layered compound of Co(II)

Under the terms of the Creative Commons Attribution (CC BY) license to their work.-- et al.

Tuning the pore size from micro- to meso-porous in thermally stable aluminophosphates

Thermally stable porous aluminophosphates (ICMUV-3) with P/Al molar ratios in the range 0.15 <= P/Al <= 0.75 and showing continuously adjustable pore sizes from 13 to 37 Å have been prepared through a surfactant-assisted procedure without changing the surfactant length and/or addition of organic expansors. Cabrera Medina, Saul, Saul.Cabrera@uv.es ; El Haskouri, Jamal, Jamal.Haskouri@uv.es ; Beltran Porter, Aurelio, Aurelio.Beltran@uv.es ; Beltran Porter, Daniel, Daniel.Beltran@uv.es ; Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es

Oxidative dehydrogenation of isobutane over Co-MCM-41 catalysts

Abstract Cobalt-containing mesoporous silicates with MCM-41-like structure, with Si/Co≥49, are active and selective catalysts for the oxidative dehydrogenation (ODH) of isobutane. The formation of dehydrogenation products is analysed in terms of the nature of the cobalt species, tetrahedral Co(II), and heterogeneously initiated gas-phase reactions inside the mesopores.

Prediction of Magnetic Properties in Oxovanadium(IV) Phosphates: The Role of the Bridging PO4 Anions

Oxovanadium phosphates constitute a crystallochemically very rich family that, in turn, results in a seemingly intricate magnetochemistry including from isolated dimers to 3-D systems. This magnetic diversity is due, in part, to the possible participation of phosphate groups in the spin transfer between VIV centers. This way, 31P solid-state NMR becomes a key tool in determining the exchange paths involving phosphorus orbitals. The magnetic behavior of several layered oxovanadium phosphates M(VOPO4)2·4H2O (M = Na+, Ca2+, Ba2+, and Pb2+) has been investigated. Like it occurs in the case of other previously studied lamellar derivatives, the best fit of the temperature-dependent magnetic susce…

Generalised syntheses of ordered mesoporous oxides: the atrane route

Abstract A new simple and versatile technique to obtain mesoporous oxides is presented. While implying surfactant-assisted formation of mesostructured intermediates, the original chemical contribution of this approach lies in the use of atrane complexes as precursors. Without prejudice to their inherent unstability in aqueous solution, the atranes show a marked inertness towards hydrolysis. Bringing kinetic factors into play, it becomes possible to control the processes involved in the formation of the surfactant–inorganic phase composite micelles, which constitute the elemental building blocks of the mesostructures. Independent of the starting compositional complexity, both the mesostructu…

Synthesis of a new mesostructured lamellar oxovanadium phosphate assembled through an S+X-I0 Mechanism

A new lamellar mesostructured oxovanadium(V) phosphate, (DDAH)0.9(Cl)0.9VOPO4·1.5H2O (DDA = dodecylamine), has been synthesized through a S+X-I0 cooperative mechanism using protonated dodecylamine ...

Crystal structure of a new polytype in the V–P–O system: is ω-VOPO4 a dynamically stabilised metastable network?

Abstract ω-VOPO 4 has been prepared by thermal decomposition of different oxovanadium hydrogen phosphates, namely VO(HPO 4 ) n H 2 O ( n =2( α ), 2(β) and 4) and β-NH 4 (VO 2 )(HPO 4 ). The ω-VOPO 4 phase only remains well crystallised at relatively high temperatures. Its crystal structure has been determined ab initio from X-ray powder diffraction data collected at 475°C. The cell is tetragonal (space group P4 2 /mmc) with a =4.8552(3) A and c =8.4301(6) A. Starting positional parameters were obtained by direct methods, and the structure was refined using Rietveld profile refinement principles. Disorder of two oxygen sublattices is observed. To rationalise some features of the crystal stru…

Direct oxidation of isobutane to methacrolein over V-MCM-41 catalysts

High vanadium content mesoporous vanado-silicates with MCM-41-like structure, obtained by the atrane route, catalyse the direct oxidation of isobutane to methacrolein with 30% selectivity, and a total dehydrogenation (olefin plus methacrolein) selectivity up to 74%.

Lattice dynamics of superconducting zirconium and hafnium nitride halides

We have performed a study of the Raman active modes of β-HfNCl, β-ZrNCl, and β-ZrNBr and Na-doped β-HfNCl in various scattering configurations. The experimental values are compared with a lattice dynamical calculation andassigned to definite atomic motions. The variation of the atomic force constants are analyzed as a function of the bond length, relating their relative strength with the atomic characteristics of the compound.