Synthesis and x-ray crystallographic characterization of (μ3-Bi)2Fe3(CO)9: A reformulation of Hieber's Bi2Fe5(CO)20

When [HFe(CO)₄]^? is treated first with NaBiO₃ and then dilute H₂SO₄, a complex mixture of neutral metal carbonyl clusters results, some of which can be extracted into petroleum ether. Upon prolonged standing the extract yields a precipitate which has been characterized by X-ray crystallography as Bi₂Fe₃(CO)₉.The complex Bi₂Fe₃(CO)₉ crystallizes in the centrosymmetric orthorhombic space group Cmcm (D_2h¹⁷; No. 63) with a 10.616(2) Å, b 13.458(3) Å, c 11.347(3) Å, V 1621.1(7) ų and Z = 4. Single-crystal X-ray diffraction data (Mo-K_α, 2θ = 4.5–55.0°) were collected on a Syntex P2₁ four-circle diffractometer and the structure was refined to R_F 5.4% and R_WF 4.5% for all 1039 independent data (R_F 4.5% and R_WF 4.5% for those 851 reflections with |F₀| > 3.0σ(|F₀|)). The molecule lies on a site of crystallographic C_2v symmetry and is disordered. The individual molecules have a trigonal bipyramidal Bi₂Fe₃ core with the bismuth atoms occupying the apical sites (BiFe 2.617(2)–2.643(2) Å, FeFe 2.735(5)–2.757(5) Å). Each iron atom is linked to three terminal carbonyl ligands and the molecule has approximate C_3h symmetry. The nine peripheral oxygen atoms are ordered and define a tricapped trigonal prism. The equatorial iron atoms are disordered with the two Fe₃ triangles mutually displaced by approximately 30°; the disordered ensemble has approximate D_3h symmetry.     

Phases in the Ba3Fe1+xS5 series: The structure of β-Ba9Fe4S15 and its low-temperature α polymorph

The crystal structure of β-Ba₉Fe₄S₁₅ shows that it is a phase in the infinitely adaptive series of compounds Ba₃Fe_1+xS₅, 0 ? x ? 1. The material is synthesized by reacting a slightly sulfur-rich mixture at 900°C in a sealed quartz ampoule. Lattice constants are a = 25.212(3), Å, b = 9.594(1), Å, c = 12.575(1), Å, Pnma, z = 4. Three thousand thirty-three structure amplitudes were refined to R = 0.049. BaS₆ trigonal prisms share triangular faces to form infinite columns; the columns in turn share edges and create nearly hexagonal enclosures. Within these rings are additional Ba and S and tetrahedral interstices are created which can be occupied by Fe. The variation of the Fe occupancy from ring to ring gives rise to phases in which one dimension is an integral multiple of the 8.5-Å repeat observed in one end member of the series, Ba₃FeS₅. The other end member is Ba₃Fe₂S₅. At temperatures below 900°C a polymorphic phase is formed. Its lattice constants are a = b = 9.634(1), Å, c = 34.311(3)Å, $\text{I4}{}_1\text{a}\text{, z = 4}$. One thousand five hundred eighty-three structure amplitudes were refined to R = 0.0483. Trigonal prisms and bisdisphenoids articulate to form a complex three-dimensional structure. Two of the S atoms in the structure have statistical site occupancies.     

Le système Ba2Fe2O5BaZnO2. I. Mise en évidence de trois nouvelles phases

In order to obtain phases with a high deficiency of oxygen, iron is progressively substituted by zinc in Ba₂Fe₂O₅ at 900–1000°C. For 0.05 < x < 0.40 ($\text{x =}\text{Zn}\text{Fe}\text{+}\text{Zn}$), the long-range order between tetrahedra and octahedra of the brownmillerite is destroyed and the cell is perovskite type with up to 23% oxygen vacancies. For x = 0.5 there is a new superlattice and an orthorhombic compound Ba₄Fe₂Zn₂O₉. For 0.7 < x < 0.9 a new cubic phase is formed which is related to BaZnO₂.     

The crystal structure of “Ba2Fe4S5”: A two-dimensional array of FeS4 tetrahedra

The crystal structure of a compound with a nominal composition Ba₂Fe₄S₅ was determined from 432 observed structure amplitudes. The lattice constants are a = 4.016(2), Å, b = 9.616(4), Å, c = 6.514(4), Å, Pmmn, Z = 1. The structure consists of BaS₆ trigonal prisms that share triangular faces to form infinite columns parallel to a. Zig-zag chains of Fe are formed parallel to b by filling the tetrahedral interstices. The structure can also be viewed as an infinite two-dimensional plane of FeS₄ tetrahedra formed by the sharing of two edges of a face in the ±a directions and connecting by corner sharing in the ±b directions. The Ba are in the trigonal prismatic interstices. The apical sulfur atom shows an anomalously large temperature factor and has a 50% site occupancy. On the basis of full occupancy of that site the composition corresponds to BaFe₂S₃. This structure is closely related to the previously reported BaFe₂S₃ and may be an averaged structure due to twinning of a polymorph of BaFe₂S₃.     

Determination des structures de deux ferrites mixtes nouveaux de formule BaLa2Fe2O7 et SrTb2Fe2O7

The structures of the two new ferrites BaLa₂Fe₂O₇ and SrTb₂Fe₂O₇ with tetragonal symmetry have been resolved by X-ray and neutron diffraction performed on powder samples. In both compounds the arrangement of atoms present a close resemblance with the idealized Sr₃Ti₂O₇ structure. It consists of a packing along the c axis of two different blocks. One is formed by the adjunction of two perovskite cells and the other one by a halved rocksalt Sr(Ba)O cell. The iron cation lattice is built by infinite double layers perpendicular to the c axis with the shortest Fe³⁺Fe³⁺ distances inside the double layers much shorter than between the layers. In BaLa₂Fe₂O₇, Ba²⁺ is located on a regular 12-coordinated site and La³⁺ in a regular 9-coordinated polyhedron. Fe³⁺ is surrounded by five oxygen neighbours at 1.98 Å, building a rather regular tetragonal pyramid, with a sixth oxygen at 2.25 Å. In SrTb₂Fe₂O₇, Sr has only eight close neighbours at ～2.80 Å and four more distant at 3.15 Å. Tb³⁺ has seven close neighbours, six building a distorted octahedron with the largest triangular face capped by the seventh oxygen. Fe³⁺ again has five neighbours, but due to the lowering of the symmetry, the square pyramid has become a distorted trigonal bipyramid.     

Détermination de la structure cristalline du ferrite de baryum Ba2Fe6O11

The crystal structure of dibarium triferrite Ba₂Fe₆O₁₁ has been solved by direct methods, using intensity data collected by means of an automated diffractometer (MoKα radiation) and corrected for absorption. It crystallizes in the orthorhombic space group Pnnm: a = 23.024(10)Å, b = 5.181(3) Å, c = 8.900(4) Å, Z = 4. Program MULTAN was successfully used for locating Ba²⁺ and most of the Fe³⁺ ions. The structure was further refined by conventional Fourier and least-squares methods (full-matrix program) to a final R value of 0.045 for 1448 observed reflections. Fe³⁺ ions occur in both octahedral (FeO mean distance: 2.02 Å) and tetrahedral (FeO mean distance: 1.865 Å) coordination. Two types of Ba²⁺ ions are found, with six and seven neighboring oxygen atoms. The structure consists of sheets of edge-shared FeO₆ octahedra which are connected by means of corner-shared tetrahedra.     

Un nouveau tetraedre azote NaN4: Preparation et structure de NaGe2N3

The NaGe₂N₃ nitride is prepared from the NaGeON oxynitride. It presents a normal tetrahedral structure related to the wurtzite type. The unit cell is orthorhombic with a = 9.8662(15), b = 5.7830(9), and c = 5.1221(5) Å, space group Cmc2₁ (No. 36). The structure refinement has been made using multicomponent profile analysis of time-of-flight neutron diffraction data. The germanium and sodium atoms are ordered among one-half of the tetrahedral sites built up by the slightly distorted hexagonal close-packing of the nitrogen atoms. It is the first example of a stable entirely nitrided environment for the sodium atom.     

Synthesis and crystal chemistry of BaNd2Ti3O10, BaNd2Ti5O14, and Nd4Ti9O24

Two new ternary compounds BaNd₂Ti₃O₁₀ (1:1:3) and BaNd₂Ti₅O₁₄ (1:1:5) have been identified in the BaONd₂O₃TiO₂ system. Single crystals of the compounds were grown and unit cell dimensions and space group symmetry were determined. BaNd₂Ti₃O₁₀ is orthorhombic with a = 3.8655 ± 0.0003, b = 28.156 ± 0.003 and c = 7.6221 ± 0.0007 Å and possible space groups are Cmcm or Cmc2. The compound melts congruently at 1640 ± 20°C. BaNd₂Ti₅O₁₄ is also orthorhombic with a = 22.346 ± 0.002, b = 12.201 ± 0.001 and c = 3.8404 ± 0.0003 Å and possible space groups are Pbam and Pba2. This compound melts congruently at 1540 ± 20°C. Single crystals of the binary compound Nd₄Ti₉O₂₄ were also grown and found to be orthorhombic with a = 35.289 ± 0.003, b = 13.991 ± 0.001, c = 14.479 ± 0.001 Å, space group Fddd.     

Etude cristallographique et par effet Mössbauer du fluorure ferrimagnétique Na5Fe3F14γ

The structure of ferrimagnetic γ-Na₅Fe₃F₁₄ has been determined by single-crystal X-ray diffraction. The cell is tetragonal with space group P4₂2₁2 and parameters a = 7.345 ± 0.007 Å and c = 10.400 ± 0.007 Å. The iron atoms occupy a twofold and a fourfold position in the lattice and are octahedrally surrounded by fluorines. These octahedra share corners and form two-dimensional layers of formula (Fe₃F₁₄)^5n?_n. The Mössbauer spectra were measured from 4.2 to 293°K and the results are discussed in terms of the position and environment of iron atoms in the lattice.     

Structural behavior of the ferromagnetic spinels AlxMo2S4 and GaxMo2S4, containing tetrahedral clusters of molybdenum atoms

The structure of the ferromagnetic spinels Al_xMo₂S₄ and Ga_xMo₂S₄ (x ～ 0.5) was determined from powder diffraction data. The Al and Ga atoms order on the tetrahedral sites. The space group is $\text{F}\text{4}\text{3m; a = 9.726}$ Å for Al_xMo₂S₄ and 9.739 Å for Ga_xMo₂S₄. The Mo atoms were found to shift towards the tetrahedral site vacancies, created by the lower Al and Ga concentrations. This results in tetrahedral clusters of Mo around the vacancies. Their semiconducting and magnetic behavior was explained on the basis of the structural behavior of the molybdenum lattice in these spinel compounds.     

Crystal structures of V3S4 and V5S8

Crystal structures of the ordered phases of V₃S₄ and V₅S₈ were refined with single crystal data. Both are monoclinic. Chemical compositions, space groups and lattice constants are as follows: VS_1.47, $\text{I2}\text{m}$ (No. 12), a = 5.831(1), b = 3.267(1), c = 11.317(2)Å, β = 91.78(1)° and VS_1.64, $\text{F}\text{2}\text{m}$ (No. 12), a = 11.396(11), b = 6.645(7), c = 11.293(4), Å, β = 91.45(6)°. In both structures, short metal-metal bonds were found between the layers as well as within them. In comparison with the structure of Fe₇S₈, the stability of NiAs-type structure was discussed based on the detailed metal-sulfur distances.     

La3Os2O10, a new compound containing isolated clusters Os2O10 with metal-metal bonds

The formula of a new compound isolated in the LaOsO system has been established by means of crystal structure determination. There are two La₃Os₂O₁₀ units in a face-centered monoclinic unit cell (S.G. $\text{C2}\text{m}$); a = 7.911(2) Å, b = 7.963(2) Å, c = 6.966(2)Å, β = 115.76(2)°;. For 1082 intensities, collected on an automated single-crystal diffractometer, the final R value was 0.025 after absorption corrections. The structure consists of isolated Os₂O₁₀ clusters composed of two edge-shared OsO₆ octahedra. These dimeric units are connected together by two types of La³⁺ ions in eightfold coordination. In view of the OsOs distance inside the pair (2.462 Å), La₃Os₂O₁₀ provides an example of metal-metal bonding involving a transition metal in a half-integral formal oxidation state of 5.5.     

Structure of ten-layer orthorhombic Ba5Fe5O14 (BaFeO2.8) determined from single crystal X-ray diffraction

The structure of the mixed-valent Ba₅Fe₅O₁₄ (BaFeO_2.8), prepared using a molten KOH-Ba(OH)₂ flux, has been determined using single crystal X-ray diffraction. Ba₅Fe₅O₁₄ forms twinned crystals with the orthorhombic space group Cmcm, a=5.7615(8), b=9.9792(14) and c=24.347(3) Å, Z=4. The structure, which is closely related to the 10H BaFeO_2.65 perovskite, is composed of two oxygen-deficient BaO₂ layers and eight BaO₃ layers with a (hchhc)₂ stacking sequence, where h and c denote hexagonal or cubic layers. A displacement of barium and oxygen atoms in the BaO₂ layers from hexagonal special positions lowers the symmetry from hexagonal to orthorhombic. This combination of stacking and vacancies creates trimers of face-sharing FeO₆ octahedra pillared by dimers of corner-sharing FeO₄ tetrahedra. The Fe⁴⁺ atoms are located in the center of the trimer and in the tetrahedral sites. The magnetism of Ba₅Fe₅O₁₄, investigated using SQUID magnetometry, is characteristic of a strongly coupled antiferromagnet.     

The crystal and molecular structures of the compounds [(η5-C5H5)Fe(CO)2]2(CH2)n, where 0 n = 3 and 4

The crystal stuctures of [(η⁵-C₅H₅)Fe(CO)₂]₂(CH₂)_n, n = 3 and 4, have been determined.[(η⁵-C₅H₅)Fe(CO)₂]₂(CH₂)₃: a = 21.20, b = 10.39, c = 7.88Å, β = 101.6°, U = 1699ų, C2/c, Z = 4, R = 0.059, 1036 observed data.[(η⁵-C₅H₅)Fe(CO)₂]₂(CH₂)₄: a = 7.63, b = 10.54, c = 21.87Å, β = 96.4°, U= 1748ų, P2₁/c, Z = 4, R = 0.051, 1418 observed data.In each compound the iron atoms are joined by simple chains of sigma bonded CH₂ groups. Bond lengths are similar in both: mean Fe-CO 1.75, C-O 1.15, FeC(cp) 2.11, FeCH₂ 2.08, (cp)CC(cp) 1.41, CH₂CH₂ 1.55Å. The (CH₂)₃ compound retains a 2-fold axis of symmetry in the crystal. The (CH₂)₄ compound has no imposed symmetry, but closely approximates centrosymmetry. The effects of molecular symmetry on the IR spectrum between 2100 and 1900 cm^-1 are discussed. The¹³C and₁H (270 MHz) NMR spectra in solution are shown to be consistent with the structures found crystallographically.     

Synthese,structure cristalline et analyse vibrationnelle de l'hexathiohypodiphosphate de lithium Li4P2S6

The crystalline compound Li₄P₂S₆ is obtained either by devitrification of Li₄P₂S₇ glass at 450°C with sulfur formation or by crystallisation at 450°C of a Li₂S, P and S melt. The structure determination has been solved by X-ray diffraction on a monocrystal. The unit cell is hexagonal $\text{P6}{}_3\text{mcm}$ with a = 6.070(4), c = 6.577(4) Å, V = 209 ų, Z = 1. Intensities were collected at 293°K with Kα (λ = 0.71069 Å) Mo radiation on an automatic Nonius CAD-4 diffractometer. The structure was solved under the assumption of random disorder of P atoms over two sites (occupancy factor of 0.5). Anisotropic least-squares refinement with W = 1 gave R = 0.047 for 90 independent reflections and 9 variables. The structure is built according to an ABAB sequence sulfur packing. Per unit cell, four out of six octahedral sites are occupied by Li ions, and the other two are statistically filled (0.5) by PP pairs. The PP central bond (2.256(13) Å) links two staggered PS₃ groups (PS = 2.032(5) Å) to form the D_3d symmetry P₂S^4?₆ anion. Infrared and Raman spectra show features very similar to those of Na₄P₂S₆, 6H₂O and M^IIPS₃ compounds. A new assignment in terms of symmetry species is proposed for the P₂S₆ internal modes, which is confirmed by a normal coordinate calculation using a valence force field; the stretching force constants f_PP and f_PS are equal to 1.6 and 2.7 mdyne Å^?1, respectively.     

Crystal structure of β-CaNi5D0.77 by rietveld analysis of neutron powder-diffraction data

β-CaNi₅D_0.77 is orthorhombic (a = 8.6033(13) b = 5.0810(9) c = 7.8557(15)Å, Pmcm, Z = 4, D_x = 6.48 g cm^?3, V = 343.4ų, FW = 1339.8 amu. Rietveld analysis of a neutron powder-diffraction pattern shows that D atoms occupy the centers of [Ni₄Ca₂] square dipyramids (“octahedra”) linked through the Ca atoms at opposite apices and forming chains. About 80% of the deuterium atoms occupy fairly regular sites (DNi = 1.53, 1.80, 1.86, 1.86 Å; DCa = 2.42, 2.45 Å). The remaining 20% occupy very distorted sites (DNi = 1.21, 1.38, 2.07, 2.07 Å; DCa = 2.54, 2.60 Å). The average DD distance in a chain is 4.3 Å.     

New SbS2 strings in the BaSb2S4 structure

The new compound BaSb₂S₄ crystallizes in the monoclinic system (space group: $\text{P2}{}_1\text{c}$, No. 14) with a = 8.985(2) Å, b = 8.203(3) Å, c = 20.602(5) Å, β = 101.36(3)°. SbS₃ ψ tetrahedra and ψ-trigonal SbS₄ bipyramids are connected by common corners and edgers to infinite strings. These are arraged cross-wise in sheets perpendicular to the c axis.     

The crystal structure of niobium trisulfide,NbS3

The crystal structure of NbS₃ was determined from single-crystal diffractometer data obtained with MoKα radiation. The compound is triclinic, space group $\text{P}\text{1}$, with: a 4.963(2) Å; b = 6.730(2) Å; c = 9.144(4)Å; α = 90°; β = 97.17(1)°; γ = 90°. The structure is closely related to the ZrSe₃ structure type; it shows that the compound can be formulated as Nb⁴⁺(S₂)^2?S^2?, in agreement with XPS spectra. The main difference with ZrSe₃ is that the Nb atoms are shifted from the mirror planes of the surrounding bicapped trigonal prisms of sulfur atoms to form NbNb pairs (NbNb = 3.04 Å); this causes a doubling of the b axis relative to ZrSe₃ and a decrease of the symmetry to triclinic.     

L'oxyde double Fe2WO6. I. Structure cristalline et filiation structurale

The authors have found a new structural type, related to α-PbO₂, called tri-α-PbO₂. The oxide Fe₂WO₆ is the prototype. It crystallizes in the orthorhombic system with the following cell parameters: a = 4.576 Å, b = 16.766 Å, and c = 4.967Å. The space group is Pbcn. The structure has been determined by X-ray single-crystal methods and refined by least-squares procedures (R = 0.065).The structure consists of zig-zag chains parallel to the c-axis. Each such chain is built up by MO₆ (M = Fe or W) octahedra-sharing edges. The chains are linked together by corner sharing. There are two types of chains: one containing only iron atoms, the other being an ordered 1-1 arrangement of iron and tungsten atoms.     

Fe3PO7, Un cas de coordinence 5 du fer trivalent,etude structurale et magnetique

The structure of Fe₃PO₇ is established from a single crystal. The cell is trigonal R3m, with, in hexagonal reference a = 8,006(5), c = 6,863(5)Å, Z = 3. The structure is determined with the direct method and refined to R = 0,027. The PO₄ tetraedra are isolated; the iron atoms are in a five coordinated site constituted of trigonal bipyramids sharing 2 edges and forming groups of 3 hexaedra; through these shared edges the iron atoms are at 3.13 Å a distance rather short which brings a repulsion causing the off centering of the cation along the pseudo axis of the bipyramid. The magnetic measurements and the Mössbauer spectroscopy show antiferromagnetism behaviour and, in the paramagnetic state, outstanding parameters (μ = 6.45 μ_B, θ_p = ?1707 K) recalling however Ca₂Fe₂O₅ or LaFeO₃. The Mössbauer spectroscopy gives, at room temperature, parameters classical for trivalent iron; through cooling, it points to a magnetic transition temperature of 160 ± 3 K below which the spectrum displays at least 2 hyperfine patterns. The magnetic interactions are discussed.