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, …

Order and disorder in mixed metal linear chains: The homo and heterobimetallic EDTA (M(H2O)4OIOII)[M?(EDTA)] � 6H2O complexes (M = Mg, Mn, Co, Zn and Ni; M? = Co, Ni, Cu and Zn)

Polymetallic solid solutions of the ethylenediaminetetracetic acid (EDTA) and six divalent metal ions exist in the range: MgαMnβCoγZnδNieCuτ(EDTA) · 6H2O where α + β + γ + δ + e + τ=2, 0⩽τ⩽1, 0⩽γ,e,δ⩽2, 0⩽α, β⩽1. This type of structure is characterized by the presence of two different octahedral carboxylate-bridged coordination sites forming infinite zig-zag chains. Visible and i.r. spectra and t.g.a. analysis show that there is occupational preference for the two coordination sites in the crystalline structure. Due to this preference, and also to the structural features, the heterobimetallic MM′(EDTA) · 6H2O compounds constitute a structurally new class of materials which can be described …

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 …

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…

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…

Crystal structure and spectroscopic studies of bis(N-2-pyridinylcarbonyl-2-pyridinecarboximidato)copper(II) monohydrate. Local bonding effects

Abstract The crystal and molecular structure of bis(N-2- pyridinylcarbonyl-2-pyridinecarboximidato)copper(II) monohydrate, Cu(BPCA)2·H2O, has been determined from single crystal X-ray data. It crystallizes in the monoclinic space group P21/c with four formula units in a cell of dimensions: a = 8.917(1), b = 8.932(1), c = 28.794(17) A, β= 95.49(2)°.Least- squares refinement of 2754 reflections with I > 2.5σ(I) and 379 parameters gave a final R = 0.037 (Rw = 0.036). The structure consists of discrete neutral Cu(BPCA)2 entities linked two by two through water molecules hydrogen bonded to ligand carbonyl groups. The coordination geometry around copper ions can approximately be described as orth…

New Family of Ruddlesden−Popper Strontium Niobium Oxynitrides:  (SrO)(SrNbO2-xN)n (n = 1, 2)

The new family (SrO)(SrNbO2-xN)n (n = 1, n = 2) constitutes the first example of strontium niobium Ruddlesden−Popper oxynitrides and provides layered structures to obtain mixed valence niobium comp...

Kineticversus thermodynamic synthesis pathways of solid bimetallic coordination compounds ? Synthesis and crystal structure of some bimetallic compounds of glycineN,N?-1,2-cyclohexanedylbis[N-(carboxymethyl)]

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…

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

A new intermediate intercalate in superconducting sodium-doped hafnium nitride chloride

Anew phase has been observed during the sodiumintercalation of hafnium nitride chloride as intermediate between the host β-HfNCl and the already reported Na 0.29 HfNCl with Tc of 24 K; the new intermediate shows interlayer spacings ranging from 9.48 to 9.67 A°, corresponds to a second stage intercalate of HfNCl and is superconducting with a critical temperature of 20 K. Beltran Porter, Daniel, Daniel.Beltran@uv.es

Synthesis and crystal structure of the α polytype of HfNBr

Abstract α-HfNBr has been prepared at 760 °C in a sealed evacuated fused silica tube by reaction between NH4Br and Hf followed by purification through chemical vapour transport under a temperature gradient. The crystal structure of this compound at room temperature has been determined for the first time by Rietveld refinement of X-ray powder diffraction data, electron diffraction and high resolution electron microscopy. It crystallises in the orthorhombic space group Pmmn with the unit cell parameters a=4.1165(2), b=3.5609(2), c=8.6440(3) A. α-HfNBr is isotypic to FeOCl and is built from layers of composition BrHfNNHfBr stacked along c that are separated by a Van der Waals gap. The haf…

Anion ordering and defect structure in Ruddlesden-Popper strontium niobium oxynitrides

The crystal structure of the n = 1 member of the Ruddlesden-Popper family (SrO)(SrNbO(2)N)(n) was refined by the Rietveld method using neutron powder diffraction data. This complex crystallizes in the I4/mmm space group with cell parameters a = 4.0506(2) and c = 12.5936(9) angstroms. The refined composition was Sr(2)NbO(3.28)N(0.72), which corresponds to a formal oxidation state for Nb of +4.72, meaning 72% Nb(V) and 28% Nb(IV). The nitrogen atoms order in the equatorial sites of the niobium octahedra according to Pauling's second crystal rule as the more charged anion occupies the site showing the larger bond strength sums. Pauling's second crystal rule is shown to be able to predict the d…

Crystal structure of Bi_{6}Sr_{8-x}Ca_{3+x}O_{22}(-0.5\leq x\leq1.7)$: a mixed valence bismuth oxide related to perovskite

Abstract: The crystal structure of BiSr8-xCa3+xO22 has been determined by single-crystal X-ray diffraction. This phase is the same as Bi9Sr11Ca5Oy that was previously studied by several authors as a secondary phase in the Bi-Sr-Ca-Cu-O system and coexists in thermodynamic equilibrium with the superconductors Bi2Sr2CuO6 and Bi2Sr2CaCu2O8 It crystallizes in the monoclinic space group P2(1)/c, with cell parameters a 11.037(3) Angstrom, b = 5.971(2) Angstrom, c = 19.703(7) Angstrom, beta = 101.46(3)degrees Z = 2. The structure was solved by direct methods and full-matrix least-squares refinement. It is built up by perovskite-related blocks of composition [Sr8-xBi2Ca3+xO16] that intergrow with d…

ChemInform Abstract: Crystal Structure and Spectroscopic Studies of Bis(N-2-pyridinylcarbonyl-2-pyridinecarboximidato)copper(II) Monohydrate. Local Bonding Effects

Abstract The crystal and molecular structure of bis(N-2- pyridinylcarbonyl-2-pyridinecarboximidato)copper(II) monohydrate, Cu(BPCA)2·H2O, has been determined from single crystal X-ray data. It crystallizes in the monoclinic space group P21/c with four formula units in a cell of dimensions: a = 8.917(1), b = 8.932(1), c = 28.794(17) A, β= 95.49(2)°.Least- squares refinement of 2754 reflections with I > 2.5σ(I) and 379 parameters gave a final R = 0.037 (Rw = 0.036). The structure consists of discrete neutral Cu(BPCA)2 entities linked two by two through water molecules hydrogen bonded to ligand carbonyl groups. The coordination geometry around copper ions can approximately be described as orth…

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.