Synthesis of a New Modification of Aluminum Oxide, Gahnite, and Zincite in Detonation

Results of studying the products of explosion of aluminum and octogen charges enclosed by a brass shell under conditions of complete burning out in air are described. Gahnite ZnAl₂O₄, a new (metastable) modification of aluminum oxide, and small quantities of zinc oxide were identified in the condensed explosion products. The x-ray pattern of the aluminum oxide was indexed in a face-centered cubic lattice with the parameters a = 7.854(1) Å, V = 484.4(2) ų. The possible Fedorov groups are Fm3m, F432, and F43m.     

Synthesis of nonstoichiometric aluminomagnesium spinel with a tetragonal lattice (review)

The results of x-ray diffraction and IR-spectroscopic studies of samples of nonstoichiometric aluminomagnesium spinel Mg_1?x Al_2?y O_4?z (OH)_z formed after treating aluminomagnesium spinel synthesized by the sol-gel method at temperatures of 800 and 1100°C with concentrated acids, are reported. It was found that three phases of nonstoichiometric aluminomagnesium spinel Mg_1?x Al_2?y O_4?z (OH)_z with tetragonal lattices and a different type of superstructure are formed. The x-ray patterns of the two phases correspond to body-centered lattices with parameters a = 5.712(3) Å, c = 8.092(3) Å, and a = 5.714(3) Å. The x-ray pattern of the third phase was indexed in a primitive tetragonal lattice: a = 5.718(3) Å, c = 24.261(27) Å.     

Model bulk Mo–V–Te–O catalysts for selective oxidation of propane to acrylic acid

The crystal structures and chemical compositions of the M1 and M2 phases proposed as active and selective in propane oxidation to acrylic acid over the bulk mixed Mo–V–Te–O catalysts were investigated by the transmission electron microscopy, coupled with energy dispersive analysis of X-rays. The results revealed that the crystal structure of the M1 phase is orthorhombic with space group Pbca, lattice parameters a=21.25 Å, b=27.14 Å, c=4.03 Å and composition Mo_0.64V_0.32Te_0.1O_3.05 (Mo/V ∼2), whereas M2 is hexagonal with space group P6mm, lattice parameters a=7.10 Å, c=4.05 Å and composition Mo_1.79V_1.85Te_0.1O_11.36 (Mo/V ∼1). The M1 phase was dominant in the Mo–V–Te–O catalyst. The results obtained indicated that the bulk Mo–V–Te oxides represent a well-defined model catalytic system for the studies of the surface molecular structure-activity/selectivity relationships in propane oxidation to acrylic acid.     

SHS of single crystals in the B-C-Mg system: Crystal structure of new modification of B25C4Mg1.42 = [B12]2[CBC][C2]Mg1.42

A new modification of B₂₅C₄Mg_1.42, [B₁₂]₂[CBC][C₂]Mg_1.42, was prepared by magnesiothermic SHS and characterized by XRD. This compound was found to have the following crystallographic parameters: a = 9.626(1), b = 11.329(1), c = 8.966(1) Å, β = 105.80(3)°, V = 940.8(2) ų, space group P2₁/b, Z = 4, R = 0.032. SHS-produced crystals exhibited high acid resistance and hardness and can be recommended as a starting compound for synthesis of other modifications of carboboride.     

Synthesis and crystal structure of a new oxohalide CdPb<Subscript>2</Subscript>O<Subscript>2</Subscript>Cl<Subscript>2</Subscript>

A new compound, CdPb₂O₂Cl₂, is synthesized by the method of solid-phase reactions. The compound has monoclinic symmetry, space group C2/m, a = 12.392(8) Å, b = 3.8040(14) Å, c = 7.658(5) Å, β = 122.64(5)°, and V = 304.0(3) ų. The structure contains one symmetrically independent position of the Pb²⁺ cation coordinated by three O^2? anions (Pb²⁺-O^2? = 2.29–2.34 Å) and five Cl^? anions (Pb²⁺-Cl^? = 3.35–3.57 Å). The Cd²⁺ cation has a symmetric coordination with the formation of two bonds Cd-O = 2.15 Å and four bonds Cd-Cl = 2.73 Å. The oxygen atom is tetrahedrally coordinated by three Pb²⁺ cations and one Cd²⁺ cation, which leads to the formation of oxo-centered heterometallic OPb₃Cd tetrahedra. The tetrahedra are linked together into chains through common Pb atoms and into layered complexes due to sharing of the equatorial Cd atoms. The chlorine atoms are located above the cavities of the oxo-centered layer.     

A novel two-dimensional chiral coordination polymer: bis(S-(-)-lactate)zinc(II)

The synthesis and X-ray characterization of a novel chiral two-dimensional condensed metal–organic coordination polymer, bis(S-(-)-lactate)zinc(II) (1), are reported. Its crystal structure determination shows that a chiral cavity with approximate dimensions of 5.4×5.4 Ų is present. Crystallographic data for 1, C₆H₁₀O₆Zn, monoclinic P2₁, a=7.4440(15), b=7.4550(15), c=7.4550(15) Å, β=95.73(3)°, V=429.48(15) ų, R₁=0.0272, wR₂=0.0751.     

One-pot template synthesis and crystal structure of two new polyaza copper(II) complexes

A new 14-membered hexazamacrocyclic copper(II) complex [Cu(H₂L¹)](ClO₄)₄(L¹=1,8-bis(2-aminoethyl)-1,3,6,8,10,13-hexaazacyclotetradecane) has been prepared by the one-pot reaction of ethylenediamine and formaldehyde in the presence of the Cu(II) ion. The crystal structure of [Cu(H₂L¹)](ClO₄)₄ was determined by X-ray diffraction. It crystallizes in the triclinic space group P−1 with a=12.118(2) Å, b=12.438(2) Å, c=12.466(2) Å, α=102.26(1)°, β=112.82(1)°, γ=111.51(1)°, and Z=2. The coordination geometry around the copper(II) ions is axially elongated octahedral with four nitrogen atoms of the macrocycle [Cu–N 2.012(7) Å for Cu(1) and 2.013(6) Å for Cu(2), average value] and two oxygen atoms of two ClO₄⁻ anions [Cu–O=2.550 Å for Cu(1) and 2.601(6) Å for Cu(2)]. [CuL²](ClO₄)₂(L²=3,7-bis(2-aminoethyl)-1,3,5,7-tetraazabicyclo[3,3,2]decane) with a novel tetraazabicyclic ligand was obtained from the same reaction system as an additional product. Crystal structure of [CuL²](ClO₄)₂: monoclinic space group Cc, a=16.393(3) Å, b=8.8640(18) Å, c= 13.085(3) Å, β=105.01(3)°, and Z=4.     

Solid-phase synthesis and characterization of rare-earth chromates

Simple chromates(V) MCrO₄ (M = Sc, Y, Gd, Er, or Yb) and chromate(V) vanadates Gd(CrO₄) _x (VO₄)_{1 ? x} have been synthesized by a solid-phase method. All compounds crystallize in the xenotime-type structure, space group I4₁/amd, Z = 4. The unit cell parameters have been calculated as follows: for GdCrO₄, a = 7.209(5) Å, c = 6.318(4) Å; for ErCrO₄, a = 7.088(2) Å, c = 6.231(1) Å; for YbCrO₄, a = 7.034(1) Å, c = 6.205(2) Å; for YCrO₄, a = 7.108(3) Å, c = 6.254(3) Å; and for ScCrO₄, a = 7.012(2) Å, c = 6.188(2) Å. Symmetry D _2d , established for the CrO₄ tetrahedron during the Rietveld structure refinement, is verified by IR spectroscopy. The MCrO₄ simple chromates are paramagnets; their magnetic moments range from 1.7 to 8.1 μ _B .     

A novel double-helical-chain coordination polymer constructed from 2,2′-biphenyldicarboxylate-linked binuclear-copper motif

The first 1-D double-helical-chain coordination polymer, [(H₂O)Cu(BPDC)] (2,2^′-biphenyldicarboxylate), based upon the binuclear square pyramidal copper(II)-pair motifs has been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction technique. [(H₂O)Cu(BPDC)] crystallized in orthorhombic crystal system, space group Cmca with unit cell dimensions a=21.073(6) Å, b=7.118(2) Å and c=17.670(5) Å, Z=8.     

Multinuclear Metal Carbonyl Alkoxide and Aryloxide Derivatives as Models for Metal Carbonyls Adsorbed on Metal Oxide Supports

The synthesis and characterization of two tungsten carbonyl dimers containing bridging alkoxide or aryloxide ligands are described. The crystal and molecular structures of [PPN]₂[W₂(CO)₈(OCH₂CF₃)₂], 1, and [Et₄N]₃[W₂(CO)₆-(OPh)₃]-CH₃CN, 2 , are reported and compared with the structures of tetranuclear tungsten derivatives previously described. The dimer 1 crystalizes in the triclinic space group P 1 with unit cell parameters a = 13.460(11) Å, b = 12.318(5) Å, c = 13.842(10) Å, α = 82.73(5)°, β = 59.11(5)°, γ= 80.09(5)°, V = 1938(2) ų, and Z = 1. The complex 2 crystalizes in the monoclinic space group P2₁/n with unit cell parameters a = 11.954(2) Å, b = 19.359(4) Å, c = 26.462(5) Å, β = 102.50(16)°, V = 5979(2) ų, Z = 4. Molecular modeling software was utilized to construct a tetranuclear derivative from 1 similar to the structurally characterized [W(CO)₃OH]₄₋⁴ tetramer. The two tetramers were found to possess similar molecular parameters. This supports the contention that dimers of type 1 are the precursors of the tetramers. Comparisons of the tungsten alkoxides and aryloxides with the behavior of W(CO)₆ on γ-alumina are provided.     

The synthesis and crystal structure of [M{H2B(tz*)2}2(H2O)] (M=Cu,Zn and tz*=3,5-dimethyl-1,2,4-triazole)

New ligand [KH₂B(tz^*)₂] (tz*=3,5-dimethyl-1,2,4-triazolyl) has been synthesized and the reactions of two different metal salts (copper and zinc) with the new ligand in agar gave two similar crystalline polymorphic forms: [Cu{H₂B(tz^*)₂}₂(H₂O)] (1) and [Zn{H₂B(tz^*)₂}₂(H₂O)] (2). A single crystal X-ray study revealed that the compound 1 was the monoclinic system with space group C2/c and a=8.462(3) Å, b=14.039(6) Å, c=19.991(8) Å, β=94.622(7)°, Z=4, R₁=0.0451, wR₂=0.1110. And the compound 2 was the monoclinic system with space group C2/c and a=8.4214(4) Å, b=13.8765(7) Å, c=20.2969(6) Å, β=95.615(2)°, Z=4, R₁=0.0667, wR₂=0.1375. The metal(II) ion in the complex is five-coordinated with four nitrogen atoms which come from triazolyl and one oxygen atom which come from water molecular. In both compounds, the hydrogen atoms of water molecule are connected by hydrogen bonding with N atoms of two adjacent complex molecules to form 2-D planes. The spectroscopic results are consistent with the crystallographic study.     

Synthesis and characterization of yttrium iron garnet nanoparticles doped with cobalt

In this work, we have synthesized and characterized yttrium iron garnet nanoparticles doped with cobalt. The X-ray diffraction data showed a single phase, belonging to the cubic structure of Y₃Fe₅O₁₂. Rietveld refinement revealed variation of the angles and interionic distances (Fe³⁺(a)-O^2-Y³⁺(c) and Fe³⁺(d)-O^2--Y³⁺(c) when Fe³⁺ ions are replaced by Co³⁺ ions in the tetrahedral (d) and octahedral (a) sites of YIG. In addition, the lattice parameter a, decreases from 12.3846?Å to 12.3830?Å with the increasing of cobalt concentration. The analysis by Infrared and Raman spectroscopies has shown a slight stretching at lower wave numbers as the dopant concentration increased. The magnetic measurements confirm the substitution of Fe³⁺ by Co³⁺ in the a-sites and d-sites with the reduction of the saturation magnetization from 26.63?emu/g to 24.92?emu/g, for 0.000?≤?y?≤?0.030. Changes in the coercive field varying the dopant concentration were related to the particle size and pinning centers existence.     

Synthesis and crystal structure of the disordered modification of Tl6Si2O7

A new compound ??-Tl₆Si₂O₇ has been investigated using the methods of IR spectroscopy and microprobe and X-ray diffraction analysis. The elementary unit parameters were as follows: P6₃/m, a = 9.673(2) Å, c = 3.9169(9) Å, and V = 317.4(1) ų. The structure was resolved by direct methods and corrected until R ₁ = 0.029 (wR ₂ = 0.047) for 240 reflections [F _o] ?? 4?? _F . The crystal structure of ??-Tl₆Si₂O₇ contains one symmetrically independent position of the Tl⁺ cation that forms three short (??Tl-O?? = 2.54 Å) bonds and one weak bond (2.93 Å) with the oxygen atom. One can observe a strong disordering of silicon atoms (Si-Si = 0.64 Å). The distorted tetragonal pyramids TlO₄ are linked through silicate tetrahedra into a three-dimensional framework. The interesting feature of the crystal structure of ??-Tl₆Si₂O₇ is in the presence of wide channels occupied by lone electron pairs on Tl⁺ cations. One can also mention that in most of the structures of Tl⁺ oxygen-containing salts the lone pairs are associated into separate parts in the form of micelles in channels of frameworks or other structural cavities.     

Structure of the dye 2,6-dichloro-4′-N,N-diethylaminoazobenzene

The structure of 2,6-dichloro-4′-N,N-diethylaminoazobenzene has been determined from X-ray diffractometer data: C₁₆H₁₇Cl₂N₃, MW = 322·2, monoclinic, P2₁/n, a = 11·160 (2), b = 12·066 (2), c = 13·633 (3) Å, β = 116·46 (2)°, V = 1643·5 ų, Z = 4, D_c = 1·30 g cm^?3, F(000) = 672, λ(MoKα) = 0·71069 Å, μ(MoKα) = 3·94 cm^?1. The structure was solved by direct methods and refined to R = 0·073 for 1495 independent reflexions. The molecule is non-planar with a dihedral angle of 87·8° between the phenyl rings. The effects of substituents on the aromatic ring geometry are discussed. Significant molecular parameters are: NN, 1·164 (9) Å; mean ClC, 1·741 (6) Å; mean CN(azo), 1·487 (9) Å; NNC, 112·4 (2)° and 109·1 (2)°; NCC (cis relative to NN), 125·5 (3)° and 122·4 (2)°; NCC (trans relative to NN) 114·0 (3)° and 119·5 (3)°; mean CC(Cl)C, 122·3 (3)°.     

Structure of a biologically active binuclear palladium complex,bis(bis[(μ<Subscript>2</Subscript>-cysteine)(2,2′-dipyridyl)-palladium(II)]) · hexanitrates · novemhydrates

The structure of a biologically active binuclear palladium complex, namely, [(dipy)Pd(μ-cysH) (μ-cys)Pd(dipy)]³⁺ · 3NO ₃ ^? · 4.5H₂O (dipy = 2,2′-dipyridyl, C₁₀H₈N₂; cys = cysteine, C₃H₇NO₂S), has been determined from X-ray diffractometry data. The compound crystallizes in the triclinic system, symmetry space group P1, with the unit cell parameters a = 13.863(1) Å, b = 13.819(1) Å, c = 12.170(1) Å, α = 122.13(1)°, β = 103.61(1)°, γ = 91.40(1)°, V = 1887.02 ų, Z = 2, and ρ = 1.82 g/cm³. The final discrepancy factor is R1 = 0.0495 for 12884 symmetrically nonequivalent reflections with F ₀ ≥ 4σ(F ₀), wR2 = 0.1071, and GooF = 0.978. The unit cell contains two chemically equivalent but crystallographically independent positively charged binuclear palladium complexes, six NO ₃ ^? anions, and nine water molecules. The π-π stacking interaction between the nearest pyridyl rings of the neighboring layers takes place. Moreover, the interlayer and intralayer interactions occur through van der Waals interactions and a complex three-dimensional system of hydrogen bonds, which are formed by water molecules, NH ₃ ⁺ groups, and carboxyl groups.     

Crystal structure and thermodynamic parameters of Nylon-1010

WAXD, SAXS, FTIR, DSC and density techniques have been used to investigate the crystal structure, crystal density ρ_c, amorphous density p_a equilibrium heat of fusion δH°_m and equilibrium melting temperature T°_m. By extrapolating the straight lines in the FTIR absorbance against density plot to zero intensity. ρ_c and ρ_a were estimated to be 1.098 and 1.003 g/cm³ respectively. The ρ_c obtained was too low in value. From X-ray diffraction patterns of uniaxially oriented fibres, the crystal structure of Nylon-1010 was determined. The Nylon-1010 crystallized in the triclinic system, with lattice dimensions: a = 4.9 Å, b = 5.4 Å, c = 27.8 Å, α = 49°, β = 77°, γ = 63.5°. The unit cell contained one monomeric unit, the space group was P1 , and the correct value of ρ_c was 1.135 g/cm³. The degree of crystallinity of the polymer was determined as about 60% (at RT) using Ruland's method. SAXS has been used to investigate the crystalline lamellar thickness, long period, transition zone, the specific inner surface and the electron density difference between the crystalline and amorphous regions for Nylon-1010. The analysis of data was based upon a one-dimensional electron-density correlation function. δ H°_m was estimated to be 244.0 J/g by extrapolation of δH°_m in the plot of heat of fusion against specific volume of semicrystalline specimens to the completely crystalline condition (V = 1/ρ_c). Owing to the ease of recrystallization of melt-crystallized Nylon-1010 specimens, the well-known Hoffman's T_m-T_c method failed in determining T°_m and a Kamide double extrapolation method was adopted. The T°_m value so obtained was 487 K.     

Crystal structure and thermal expansion of ammonium pentaborate NH<Subscript>4</Subscript>B<Subscript>5</Subscript>O<Subscript>8</Subscript>

Anhydrous ammonium pentaborate NH₄B₅O₈ has been synthesized by thermal dehydration of larderellite NH₄[B₅O₇(OH)₂] · H₂O at a temperature of 290°C for 7 h. The crystal structure has been determined from the X-ray powder diffraction data: a = 7.58667(5) Å, b = 12.00354(8) Å, c = 14.71199(8) Å, R _p = 6.23, R _wp = 7.98, R _B = 12.7, R _F = 8.95, and β-KB₅O₈ structure type. The double interpenetrating framework is formed by pentaborate groups, each consisting of a boron-oxygen tetrahedron and four triangles, in which all oxygen atoms are bridging. The thermal behavior of the NH₄B₅O₈ compound has been investigated using thermal X-ray diffraction. As for other pentaborates of this type, the thermal expansion of the NH₄B₅O₈ compound is anisotropic and reaches a maximum along the a axis. The thermal expansion coefficients are as follows: α _a = 39 × 10^?6, α _b = 6 × 10^?6, α _c = 20 × 10^?6, and α _V = 65 × 10^?6 °C^?1.     

Structure of a biologically active binuclear palladium complex in the compound bis(bis[(μ<Subscript>2</Subscript>-2-chloroethylammonium) (1,10-phenanthroline)-palladium(I)]) · octanitrates · dihydrates

The structure of a biologically active binuclear palladium complex, namely, [(1,10-phenanthroline) Pd(μ₂-2-chloroethylammonium) ₂ ⁴⁺ · 4NO ₃ ^? · H₂O, has been determined using X-ray diffraction analysis. The compound crystallizes in the monoclinic system, space group of symmetry Cc, with the unit cell parameters a = 24.527(3) Å, b = 13.097(1) Å, c = 22.651(3) Å, β = 104.23(1)°, V = 7052(2) ų, Z = 8, and ρ = 1.88 g/cm³. The final discrepancy factor is R1 = 0.0316 for 15581 symmetrically nonequivalent reflections with I ≥ 2σ(I), wR2 = 0.0513, and GooF = 1.047. The palladium atoms reside in the oxidation state of 1+, which is rarely encountered in organometallic compounds. The asymmetric part of the unit cell contains two chemically equivalent but crystallographically independent positively charged binuclear palladium complexes, eight NO ₃ ^? anions, and two water molecules. The π-π stacking interaction between the nearest 1,10-phenanthroline rings of the neighboring layers takes place. Moreover, the interlayer and intralayer interactions occur through electrostatic interaction forces and a complex three-dimensional system of hydrogen bonds, which are formed by water molecules and N ₃ ⁺ groups.     

Structure of a biologically active binuclear palladium complex in the compound (bis[(μ<Subscript>2</Subscript>-2-chloroethylammonium)(1,10-phenanthroline)-palladium(I)]) · tetranitrates · hydrate

The structure of a biologically active palladium complex [(1,10-phenanthroline)Pd(μ₂-2-chloroethylammoniu)] ₂ ⁴⁺ · 4NO ₃ ^? · H₂O has been determined from the diffractometric data. The compound crystallizes in the triclinic crystal system, space group of symmetry P \(\bar 1\), with the unit cell parameters a = 12.8352(8) Å, b = 14.4040(8) Å, c = 12.1668(9) Å, α = 116.16(1)°, β = 115.72(1)°, γ = 91.09(1)°, V = 1756.3 ų, Z = 2, and ρ = 1.892 g/cm³. The final reliability factor is R ₁ = 0.0351 for 7357 nonequivalent reflections with I ≥ 2σ(I), wR ₂ = 0.0970, and S = 1.044. The asymmetric part of the unit cell contains one positively charged binuclear palladium complex, four NO ₃ ^?1 anions, and one water molecule. The nanocomplexes are involved in the stacking π-π interaction by pairs: each complex forms a stacking with only one adjacent complex. The interaction between layers and inside each layer occurs through the van der Waals interactions and a three-dimensional system of hydrogen bonds, which are formed by the N ₃ ⁺ groups and water molecules.