Metal-(phenylthio)acetic acid interactions—IV. The crystal structure of tetra-μ-[(2,4-dichloro-5-methylphenylthio)acetato-O,O′]-bis[acetonecopper(II)], a dimeric complex having coordinated acetone molecules

The crystal structure of the acetone adduct of copper(II) (2,4-dichloro-5-methylphenylthio)acetate has been determined by single crystal X-ray diffraction and refined by least squares to 0.051 for 3701 “observed” reflections. Crystals of the compound are triclinic, space group P$\text{1}$ with one dimer in a cell with a = 8.357(1), b = 12.502(2), c = 13.721(2) Å, α = 107.20(1), β = 96.09(1), γ = 104.94(1)°. The complex is a tetracarboxylate bridged dimer of the copper acetate hydrate type, with a CuCu separation of 2.646(1) Å and a mean CuO (equatorial) distance of 1.961(4) Å, while the axial positions of the dimer are occupied by coordinated acetone molecules [CuO, 2.206(3) Å]. X-ray crystal data and the results of chemical analyses are also presented, indicating that a second chemical polymorph has both acetone and water molecules, with a similar dimeric structure but having solvated acetone.     

The crystal and molecular structure of bis-dimethylaminotitanium difluoride tetramer

The crystal structure of [(Me₂N)₂TiF₂₄ has been determined by single-crystal X-ray diffraction. The crystals are tetragonal, I$\text{4}$, a = b = 11.313(5), c = 12.862(4) Å, Z = 2. The titanium atoms display a distorted octahedral coordination and are linked by TiFTi and TiNMe₂Ti bridges to form a tetramer, which possesses a crystallographic inverse tetrad axis at its centre. One fluorine and one dimethylamino group do not participate in the bridging. The principal bond lenghts are TiF(bridging) 2.00(2) and 2.06(2), TiF (terminal) 1.77(2), TiN(bridging) 2.14(3) and 2.19(3), TiN(terminal) 1.99(30) Å. The structure has been refined to R = 0.077 for 231 visually estimated unique reflections.     

The crystal structure of hexathallium(I) hexatellurodigermanate(III), Tl6[Ge2Te6]

The new compound Tl₆[Ge₂Te₆] was prepared by thermal synthesis from the elements. The material is triclinic, space group $\text{P}\text{1}$, with a = 9.471(2), b = 9.714(2), c = 10.389(2) Å, α = 89.39(1), β = 97.27(1), γ = 100.79(1)°, and Z = 2. The crystal structure was determined from single-crystal intensity data measured by means of an automated four-circle diffractometer and refined to an R value of 0.053 for 1831 observed reflections. Tl₆[Ge₂Te₆] is characterized by Ge₂Te₆ units with GeGe bonds which are linked into a three-dimensional structure by Tl atoms coordinated to essentially six Te atoms. The most important mean distances are $\text{d}\text{GeGe}\text{) = 2.456}$ Å, $\text{d}\text{(}\text{GeTe}\text{) = 2.573}$ Å, and $\text{d}\text{(}\text{TlTe}\text{) = 3.515}$Å. The lone 6s electron pairs of the thallium(I) atoms exhibit significant stereochemical activity. Tl₆[Ge₂Te₆] represents a new structure type.     

The phase diagrams of Ag2XAgY (X = S,Se, Te; Y = Cl,Br, I): Mixtures and the structure of Ag5Te2Cl

The phase diagrams of Ag₂SAgI, Ag₂SeAgI, Ag₂TeAgI, Ag₂TeAgBr, and Ag₂TeAgCl were investigated. The system Ag₂S-AgI shows two broad regions of solid solution which are based on the structure of the high-temperature phases of the constituent compounds. The high-temperature modification of Ag₃SI is part of one of these regions. The system Ag₂SeAgI resembles the system Ag₂TeAgI; both contain limited regions of terminal solid solutions. The AgI-based solid solutions decompose peritectically. In the system Ag₂TeAgBr a compound Ag₃TeBr was found. Ag₃TeBr undergoes a phase transition at 590 ± 20 K. The low-temperature form has hexagonal symmetry with the lattice parameters a = 748.8(1) pm and c = 4357.6(6) pm. The compound Ag₅Te₂Cl was found in the Ag₂TeAgCl system. In both systems a restricted terminal solid solution, based on the high-temperature form of Ag₂Te, was observed. Ag₅Te₂Cl has a reversible phase transformation at 329 ± 3 K with ΔH_tr = 9.82 ± 0.4 kJ mole^?1. β-Ag₅TeCl, the low-temperature form probably has the space group $\text{P2}{}_{\mathrm{<mtext>1</mtext><mtext>n</mtext>}}\text{, a = 1365.5(1), b = 1386.1(1), c = 764.23(2)}$, β = 90.201(1)°, and Z = 4, α-Ag₅Te₂Cl has the space group $\text{I4}{}_{\mathrm{mcm}}$ with a = 975.5(3), c = 783.0(1) pm, and Z = 4. The anion sublattice is built of octahedra, which share all their vertices with neighboring octahedra. The Ag⁺ ions are distributed over octahedral holes of this network. The phase is similar in behavior to Ag₈GeTe₆ and may be a silver-ion conductor.     

Phase relationships in the uranium-palladium-sulfur system: I. Characterization and crystal structure of UPd2S4

The new compound UPd₂S₄ was prepared by reacting stoichiometric amounts of US₂, Pd, and S in evacuated quartz ampoules. UPd₂S₄ crystallizes in the tetragonal system, a = b = 6.734(1), c = 11.841(4)Å, space group $\text{I4}{}_1\text{a}\text{, Z = 4}$. The crystal structure was determined from single-crystal X-ray diffraction data and refined to a conventional R factor of 0.054. Palladium has a square planar sulfur coordination with PdS distances = 2.33 Å. Uranium is coordinated with eight sulfur atoms, with a mean US distance of 2.83 Å characteristic of uranium in the tetravalent state.     

Metal—metal bonding in dinuclear complexes of platinum(I). The crystal and molecular structure of carbonyl(chloro)-bis-μ-[bis(diphenylphosphino)methane]diplatinum hexafluorophosphate

The structure of [Pt₂Cl(CO) (μ-Ph₂PCH₂PPh₂)₂] [PF₆] was determined by $\text{X}$-ray methods and refined to $\text{R}$ = 0.082, using diffractometric intensities of 5646 independent reflections. The crystals are monoclinic, space group $\text{P}$2₁/$\text{n}$, $\text{a}$ = 12.919(3), $\text{b}$ = 15.576(6), $\text{c}$ = 25.151(5)Å, β = 94.82(3)°, $\text{Z}$ = 4. They are built of octahedral hexafluorophosphate anions and dinuclear platinum(I) cations. The latter contain PtCl and PtCO fragments linked to one another by a PtPt σ-bond and by two bridging bis(diphenylphosphino)methane ligands. The platinum atoms are in square planar environments and the dihedral angle between the two coordination planes is 40.1°. Selected bond lengths are: PtPt 2.620(1), PtCl 2.384(5), PtC 1.89(3) and PtP 2.291(5) – 2.308(5)Å.     

Structure of sodium tetradeuteroborate,NaBD4

The structure of NaBD₄ was determined from powder neutron data and refined using Rietveld's method. The compound has a sodium chloride-type structure, in space group $\text{F}\text{4}\text{3m, a = 6.137(7)}$, Å, BD, 1.160(7); angle DBD, 109.5(2)° at 295 K, with D atoms tetrahedrally oriented about B (at $\text{1}\text{2}\text{,0,0}$, etc.), and along all cube diagonals. This gives a random distribution of BD^?₄ tetrahedra in two different configurations.     

The reactions of 2-[(dimethylamino)methyl]phenylcopper and -lithium tetramer with cuprous and cupric halides

2-[(Dimethylamino)methyl]phenylcopper tetramer (R₄Cu₄) forms a red $\text{1}\text{1}$ complex (RCu - CuBr)_n with cuprous bromide. The $\text{1}\text{1}$ interaction of 2-[(dimethylamino)methyl]phenylcopper with cupric halides results in the formation of the dimer RR, the 2-halo-substituted benzylamine R—Halide and minor amounts of N,N-dimethylbenzylamine RH. The formation of these products can be explained on the basis of an intramolecular electron-transfer redox reaction taking place in innersphere activated complexes of the type R₄Cu₃Cu - - - X - - - Cu^IIX(Cu^IIX₂)_n-1. The course of the metathesis reaction of 2-[(dimethylamino)methyl]phenyllithium with cuprous bromide depends on the order of addition of the reactants. Reversed addition (RLi to CuBr) results in the formation of an inseparable mixture of complexes of the type (RCu)_x- (CuBr)_y. Upon addition of CuBr to RLi the uncomplexed organocopper compound R₄Cu₄ is formed.     

Die molekül- und kristallstruktur von thallium-tris(bistrimethylsilylamin), Tl[N(SiMe3)2]3

The molecular and crystal structure of tris(bistrimethylsilylamin)thallium was determined by means of single-crystal X-ray spectroscopy: in the space group P$\text{3}$1c with a = 16.447(7), c = 8.456(7) Å; and D_c = 1.149 g cm^?3 two molecules are located in the unit cell. The compound is isomorphous to the analogues Fe[N(SiMe₃)₂]₃ or Al[N(SiMe₃)₂]₃, respectively, which show a propellar-twist of the Si₂N-groups versus the plane of the metal atom and the three nitrogen-atoms: Tl(N)₃/Si₂N 49.1°; SiNSi 122.6°; NSiC 111.8°; CSiC 107.1°; TlN 2.089 Å;; SiN 1.738 Å;; $\text{SiC}$ 1.889 Å;.     

Phase equilibria and thermodynamics of coexisting phases in rare-earth element-iron-oxygen systems. II. The praseodymium-iron-oxygen system

The phase equilibria and the thermodynamics of coexisting phases in the PrFeO system have been studied using static and dynamic methods for attaining equilibrium with subsequent annealing and identification of the condensed phases by X-ray analysis. Equilibrium phase diagrams have been constructed to define the changes that take place in the PrFeO system on variation of the partial oxygen pressure, the temperature, and the composition of the initial mixture of oxides. An isothermal cross section at 1300°K and equilibrium diagrams of the type P_O2 = f(composition) with with one composition parameter fixed and T = f(composition) with P_O2 = constant have been constructed. It has been shown in the PrFeO system that only one ternary compound with perovskite structure, PrFeO₃, is formed, and furthermore, it is stable no matter how high the partial oxygen pressure.     

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.     

The crystal structure of tris(triphenylphosphine)gold(I)-[dodecahydrido-6-thia-nido-decaborate(1—)]

The crystal structure of tris(triphenylphosphine)gold(I)[dodecahydrido-6-thia-nido-decaborate(1—)], [(C₆H₅)₃P]₃AuB₉H₁₂S, has been determined using X-ray techniques and counter data. The compound is a salt consisting of [(C₆H₅)₃P]₃Au⁺ cations and B₉H₁₂S^? anions. The cation is trigonal and nearly planar with AuP distances of 2.382(5) Å and PAuP anglés of 119.3(36)°. The B₉H₁₂S^? thiaborane anion is an open icosahedral fragment with the S atom in the 6 position, on the periphery of the decaborane polyhedron. The structure is the same as that found in solution for the isoelectronic B₁₀H₁₄^2? anion. Crystals are triclinic, space group P$\text{1}$, with a = 13.086(12), b = 19.635(32), c = 11.180(8) Å, α = 103.60(16), β = 72.10(9), and γ = 94.76(15)°. The structure was refined by least squares to a conventional R of 0.077.     

The structure of a carbon monoxide adduct of cobalt-exchanged zeolite A (Co5.25Na1.5A · 1.5CO) by neutron profile refinement

The structure of a carbon monoxide adduct of cobalt-exchanged zeolite A, CO_5.25Na_1.5A · 1.5CO, has been determined by Rietveld neutron profile refinement. The space group used was $\text{Fm}\text{3}\text{c}$ with a = 24.1557(14) Å; the final R_pw was 13.8%. All exchangeable cations are located in sites adjacent to the 6-rings; 3.75 of the cobalt cations sit 0.4 Å inside the β-cage (Co(2)) and are arranged tetrahedrally about the eight 6-ring sites in the β-cage. The sodium cations (Na(1)) reside just inside the α-cage in sites similar to those found previously for zeolites 3A, 4A, and 5A. The remaining 1.5 cobalt cations (Co(1)) are located in sites similar to those for sodium, but they are also coordinated to the carbon monoxide molecules, which lie on, or close-to, the threefold axis which passes through the 6-ring. Inside the β-cage there is a tetrahedral aluminum complex of AlO₄ type, the oxygen atoms (O1) of which point toward six rings not occupied by cobalt cations, Co(2). Each of the oxygen atoms of this complex is involved in a hydrogen bond (2.83 Å) to the 6-ring oxygen O(3). Approximately $\text{2}\text{3}$ of these bonds are of type O1H···O(3) and $\text{1}\text{3}$ of type O1···HO(3).     

Structural studies in the Li2MoO4MoO3 system: Part 1 the low temperature form of lithium tetramolybdate,LLi2Mo4O13

LLi₂Mo₄o₁₃ crystallizes in the triclinic system with unit-cell dimensions a = 8.578 Å, b = 11.450 Å, c = 8.225 Å, α = 109.24°, β = 96.04°, γ = 95.95° and space group $\text{P}\text{1}\text{, Z = 3}$. The calculated and measured densities are 4.02 g/cm³ and 4.1 g/cm³ respectively. The structure was solved using three-dimensional Patterson and Fourier techniques. Of the 2468 unique reflections collected by counter methods, 1813 with I ? 3σ(I) were used in the least-squares refinement of the model to a conventional R of 0.031 (ωR = 0.038). LLi₂Mo₄O₁₃ is a derivative of the V₆O₁₃ structure with oxygen ions arranged in a face-centred cubic type array with octahedrally coordinated molybdenum and lithium ions ordered into layers.     

The chemistry and the stereochemistry of poly(n-alkyliminoalanes) : III. The crystal and molecular structure of the adduct (HalN-i-Pr)6AlH3

The crystal and molecular structure of the adduct (HAlN-i-Pr)₆AlH₃ has been determined from single-crystal and three dimensional X-ray diffraction data collected by counter methods. The cage-type molecular structure consists of two six-membered rings, (AlN)₃, joined together by four adjacent transverse AlN bonds; the loss of two of these bonds allows the complexation of one alane molecule, with five-coordination of the aluminum (trigonal bipyramidal geometry), through two AlN bonds and two AlHAl bridge bonds. The AlN bond lengths range from 1.873 to 1.959 Å; the average AlH bond length is 1.50(1) Å for the four-coordinated aluminum atoms; the average distance of the two apical hydrogens from the five-coordinated aluminum atom is 1.92(5) Å. Colourless prismatic crystals of the compound have the following crystal data: triclinic space group P$\text{1}$; a = 17.13(2); b = 10.78(2); c = 10.20(2) Å; α = 124.3(4), β = 92.0(4), γ = 92.1(5); Z = 2; calculated density 1.157 g/cm³. The structure has been refined by block-matrix, least-squares methods using 4358 independent reflections to a standard unweighted R factor of 4.9%.     

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.     

A neutron powder diffraction study of the κ phase in the FeWC system

The crystal structure of the κ-carbide in the FeWC system has been refined from neutron powder diffraction data using the Rietveld profile analysis method. κ-(FeWC) is isostructural with κ-(CoWC); space group $\text{P6}{}_3\text{mmc}$; unit cell dimensions a = 7.7982(2)Å, c = 7.8298(4) Å. The structure refinement indicates $\text{Fe}\text{W}$ substitution at two of the tungsten sites, and 46% vacancies at one of the carbon sites. The composition corresponds to the formula Fe_3+xW_10?xC_4?y, with x = 0.57(3) and y = 0.46(1).     

The chemical behaviour of the azido group bonded to copper(I): Synthesis and reactivity of thiothiatriazolato and alkynyl complexes

The copper(I) azido-derivatives, (PPh₃)(phen)CuN₃ (Ia) and (PPh₃)(TMP)CuN₃ (Ib) (phen = 1,10-phenanthroline; TMP = 3,4,7,8-tetramethyl-1,10-phenanthroline), obtained from [(PPh₃)₂CuN₃]₂ and the bidentate ligand (biL), react with CS₂ to give the thiothiatriazolato-copper(I) complexes, (PPh₃)(phen)Cu$\text{NC(S)SNN}$ (IIa) and (PPh₃)(TMP)Cu$\text{NC(S)SNN}$ (IIb). The preparation of IIa and IIb occurs only when free triphenylphosphine is present in the reaction medium. The isothiocyanate complexes, (PPh₃)(biL)Cu(NCS) (biL = phen, IIIa; biL = TMP, IIIb) are formed, instead of IIa and IIb, when free PPh₃ is not added to the reaction medium. The complexes IIIa and IIIb are also obtained when CH₂Cl₂ solutions of IIa and IIb are stirred for 15 h in the absence of light; if longer reaction times are used, the dimeric isothiocyanato complexes [(biL)Cu(NCS)]₂ are formed. Compounds IIa and IIb react with PhCOCl to give (PPh₃)(biL)CuCl and 4-benzoyl-1,2,3,4-thiatriazole-5-thione, PhCO$\text{NC(S)SNN}$.Treatment of Ia and Ib, or [(PPh₃)₂CuN₃]₂, with COS did not lead to isolation of characterizable products. An unsaturated molecule such as ethyl propriolate, EtO₂CCCH, does not behave as a 1,3-dipolarophile in its reactions with Ia and Ib, the alkynyl derivatives [(biL)Cu₂(CCCO₂Et)₂]_n (_n is probably 2; biL = phen, IVa; biL = TMP, IVb), being obtained. Similarly the azido-complex [(PPh₃)₂CuN₃]₂ reacts with ethyl propiolate to give the asymmetric binuclear alkynyl derivative, (PPh₃)₃Cu₂(CCCO₂Et)₂ (V). The reaction of V with hydrogen chloride gives EtO₂CCCH and the known complex (PPh₃)₃Cu₂Cl₂, confirming the above formulation. The reactions of V with neutral ligands such as TMP, phen and CyNC have also been studied, leading to the isolation of new copper(I) alkynyl-derivatives.     

The crystal and molecular structure of μ-μ-dichlorobis(hexafluorobut-2-enyl)-bis(cycloocta-1,5-dienyl)diiridium(III).

The title compound is isolated from reaction of hexafluorobut-2-yne with μ-μ-Dichlorobis(cycloocta-1,5-diene)diiridium(I) at 90°C. Crystals of the complex, solvated with deuterobenzene, are monoclinic, space group $\text{P}$2₁/$\text{n}$ with $\text{a}$ = 10.97 $\text{+}$ 0.02, $\text{b}$ = 17.96 $\text{+}$ 0.03, $\text{c}$ = 11.63 $\text{+}$ 0.02 », β = 127.4 $\text{+}$ 0.60°. The acetylene has abstracted a hydrogen atom forming a σ-bonded $\text{cis}$-vinylic group and the original cyclooctadiene, having lost a proton, is coordinated as the cycloocta-1,5-dienyl ligand. Mean bond lengths are IrCl 2.467, IrC (allylic) 2.17, IC (olefinic) 2.36 and IrC (vinylic) 2.09 ».