Crystal structure and luminescence of europium(III) acrylate

The atomic structure of europium acrylate crystals [Eu₂(Acr)₅OH·3H₂O]·2(0.5H₂O) was studied by X-ray analysis (a = 24.360(3) Å, b = 18.466(2) Å, c = 8.5818(9) Å, β = 96.087(2)°, space group C2/c, Z = 6, ρ_calc = 2.036 g/cm³). The crystal structure involves chains of binuclear [Eu₂(C₃H₃O₂)₅OH·3H₂O] molecules, running infinitely in the [101] direction and having pairs of C₉H₉EuO₇H₂O molecules alternating with C₆H₆EuO₄OH·2H₂O molecules that link the pairs. The infinite chains are linked by hydrogen bonds and van der Waals interactions. The thermal behavior of luminescence of the europium(III) complex is discussed.     

Crystal structure and luminescence of antimony(III) bromide with aniline

The atomic structure of antimony(III) bromide crystals with anilinium was determined by X-ray diffraction analysis of (C₆H₅NH₃)₂SbBr₅ (a = 19.704(3) Å, b = 7.914(1) Å, c = 25.556(4) Å; space group Pbca, Z = 8, ρ_calc = 2.365 g/cm³). The crystal structure consists of infinite chains of [SbBr₅]^2? complex anions formed by sharing six vertices and the anilinium (C₆H₅NH₃)⁺ cations, through which the chains are linked in layers by N-H...Br hydrogen bonds. The geometrical aspects that determine the luminescent spectral properties of the complex are discussed.     

Crystal structure and luminescence of antimony(III) chloride complex with anilinium chloride

Crystal structure of (C₆H₅NH₃)₃[SbCl₅]Cl·H₂O is determined by X-ray analysis (a = 9.4155(13) Å, b = 11.4344(16) Å, c = 13.1584(18) Å, α = 113.483(2)°, β = 90.383(2)°, γ = 97.323(2)°, space group P \(\bar 1\), Z = 2, ρ_calc = 1.642 g/cm³). The crystal structure is based on [SbCl₅]^2? anions, anilinium cations (C₆H₅NH₃)⁺, isolated Cl^? anions, and water molecules. Structural features responsible for spectral and luminescent properties of the complex are discussed.     

The First Aqua Pentafluoro Manganates(III) – Syntheses and Structures

For the first time aqua pentafluoro manganate(III) compounds with different organic N-cations have been prepared and their crystal structures have been determined: N,N′-DMenH₂[MnF₅(H₂O)] · H₂O 1 (N,N′-DMen = N,N′-Dimethylethylenediamine), space group P2₁/c, a = 916.0, b = 1004.8, c = 1247.9 pm, β = 106.03°, R = 0.035; NMpipzH₂ · [MnF₅(H₂O)] · H₂O 2 (NMpipz = N-Methylpiperazine), space group P2₁/n, a = 757.7, b = 1261.9, c = 1197.1 pm, β = 105.09°, R = 0.027; N,N′-DMpipzH₂[MnF₅(H₂O)] · 2 HF 3 (N,N′-DMpipz = N,N′-Dimethylpiperazine), space group P1, a = 677.1, b = 863.9, c = 1187.7 pm, α = 79.18°, β = 81.63° γ = 67.62°, R = 0.026; and N,N-DMenH₂[MnF₅(H₂O)] · 1/2 HF 4 (N,N-DMen = N,N-Dimethylethylenediamine), space group P1, a = 859.3, b = 1086.5, c = 1092.0 pm, α = 86.96°, β = 78.52° γ = 89.01°, R = 0.035. In all compounds the [MnF₅(H₂O)]^2– octahedra are connected via H-bonds forming 3 D and 2 D network arrangements. The anions are strongly elongated by the Jahn-Teller effect. The FTIR spectra are presented.     

Potentiometric and spectral studies of complex formation of La(III), Pr(III) and Lu(III) with aspartic acid and asparagine

The composition and stability of La³⁺, Pr³⁺ and Lu³⁺ complexes with aspartic acid and asparagine were analysed. The formation of complexes of the typeML andMHL was determined for La³⁺ and Pr³⁺ with aspartic acid, and of the typeMHL for Lu³⁺ with aspartic acid. For La³⁺, Pr³⁺ and Lu³⁺ with asparagine the formation ofML(OH) complexes was observed. By means of¹H NMR and¹³C NMR studies the participation in the coordination of both -COOH groups was determined for aspartic acid, whereas for asparagine the participation of the -COOH group was determined in complexes with La³⁺, Pr³⁺, and of the -COOH and the -NH₂ groups in the complex with Lu³⁺.

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Potentiometrische und spektroskopische Untersuchungen an La(III), Pr(III) und Lu(III)-Komplexen von Asparaginsäure und Asparagin

Zusammenfassung Die Zusammensetzung und die Stabilität von La³⁺, Pr³⁺ und Lu³⁺-Komplexen mit Asparaginsäure und Asparagin wurden untersucht. Es wurde die Bildung von La³⁺ und Pr³⁺-Komplexen des TypsML undMHL, und ein Lu³⁺-Komplex des TypsMHL mit Asparaginsäure festgestellt. Für diese drei Lanthaniden wurde auch die Bildung von Komplexen des TypsML(OH) mit Asparagin beobachtet. Mit Hilfe von¹H-NMR und¹³C-NMR-Untersuchungen wurde für Asparaginsäure die Teilnahme der beiden -COOH-Gruppen, für Asparagin die Teilnahme der -COOH-Gruppe in den Komplexen mit La³⁺, Pr³⁺ und der-COOH und -NH₂-Gruppen in dem Komplex mit Lu³⁺ an der Koordinierung festgestellt.

     

121,123Sb NQR investigation of chlorofluoroantimonates(III) M2SbCl3F2 (M = Rb. Cs,and NH4)

Antimony(m) chlorofluoride complexes M₂SbCl₃F₂ (M = Rb, Cs, or NH₄) were studied by the^121,123Sb NQR method. A temperature range (77–285 K) with anomalous change in the NQR parameters and a second-order phase transition at 250–280 K for (NH₄)₂SbCl₃F₂ were found.Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 382–385, February, 1996     

Thermal analysis and spectroscopic characteristics of tetrabutylammonium tetrachloroferrate(III)

The IR, far-IR, Raman and Mössbauer spectra have been utilized to identify a new compound consisting of a tetrachloroferrate(III) anion and a tetrabutylammonium cation [(C₄H₉)₄N][FeCl₄]. Its degradation has been studied by thermal analysis using TG, TG-MS, DTG and DTA, as well as DSC techniques. The measurements were run in static air and in argon atmosphere. Solid residues were identified by elemental analysis, far-IR and Mössbauer spectroscopy. The discussion was focused on processes proceeding during the first step of the thermal decomposition.     

Synthese und Kristallstrukturen der Thiochloroantimonate(III) PPh4[Sb2SCl5] und (PPh4)2[Sb2SCl6] · CH3CN

Syntheses and Crystal Structures of the Thiochloroantimonates(III) PPh₄[Sb₂SCl₅] and (PPh₄)₂[Sb₂SCl₆]. CH₃CN (PPh₄)₂Sb₃Cl₁₁, obtained from Sb₂S₃, PPh₄Cl and HCl, reacts with Na₂S₄ in acetonitrile forming PPh₄[Sb₂SCl₅]. From this and Na₂S₄ or from (PPh₄)₂[Sb₂Cl₈] and Na₂S₄ or K₂S₅ in acetonitrile (PPh₄)₂[Sb₂SCl₆] · CH₃CN is obtained. Data obtained from the X-ray crystal structure determinations are: PPh₄[Sb₂SCl₅], monoclinic, space group P2₁/c, a = 1002.9(3), b = 1705.6(5), c = 1653.7(5) pm, β = 99.12(2)°, Z = 4, R = 0.068 for 1283 reflextions; (PPh₄)₂[Sb₂SCl₆] · CH₃CN, triclinic, space group P1 , a = 1287.8(7), b = 1343.6(9), c = 1696.5(9) pm, α = 69.82(5), β = 85.08(4), γ = 71.54(6)°, Z = 2, R = 0.059 for 6409 reflexions. In every anion two Sb atoms are linked via one sulfur and one ore two chloro atoms, respectively. Paris of [SbSCl₅]^? ions are associated via Sb …? S and Sb …? Cl contacts forming dimer units. In both compounds every Sb atom has a distorted octahedral coordination when the lone electron pair is included in the counting.     

Two tris(oxalato)ferrate(III) hybrid salts with pyridinium derivative isomers as counter cations: synthesis,crystal structures,thermal analyses,and magnetic properties

Two organic–inorganic hybrid salts, tris(2-amino-4,6-dimethylpyridinium) tris(oxalato)ferrate(III), (C₇H₁₁N₂)₃[Fe(C₂O₄)₃] (1), and tris(4-dimethylaminopyridinium) tris(oxalato)ferrate(III) tetrahydrate, (C₇H₁₁N₂)₃[Fe(C₂O₄)₃]·4H₂O (2), have been synthesized and characterized by elemental and thermal analyses, IR spectroscopy, single-crystal X-ray diffraction, and SQUID magnetometry. Compounds 1 and 2 crystallize in triclinic P-1 and monoclinic C2/c space groups, respectively. Each compound contains the anionic complex [Fe(C₂O₄)₃]^3- in which the central metal is six-coordinate in a slightly distorted octahedron defined by three chelating oxalate(2-) ligands. The two substituted pyridinium cations are isomers. However, due to the great steric hindrance provided by the bulky cation, 2-amino-4,6-dimethylpyridinium, only the 4-dimethylaminopyridinium cation, the smallest of this series, led to formation of 2 with enough vacant spaces to be occupied by four solvent water molecules. In the crystals, cations and anions are connected via hydrogen-bonds of the types N–H?O in 1 and N–H?O and O–H?O in 2, with π–π stacking interactions between the pyridine rings stabilizing the 3-D framework. The thermal studies confirmed the anhydrous character of salt 1 and the presence of water molecules in salt 2. The magnetic susceptibility measurements in the 2–300 K temperature range revealed weak antiferromagnetic coupling in the two salts.     

Crystal structure of dimethylgold(III) 8-hydroxyquinolinate and 8-mercaptoquinolinate

A crystal-chemical study of dimethylgold(III) complexes with 8-hydroxyquinoline (CH₃)₂Au(OR) and 8-mercaptoquinoline (CH₃)₂Au(SR) (R = C₉H₆N) was performed. Crystal data for (CH₃)₂Au(OR): a = 8.7133(17) Å, b = 27.875(6) Å, c = 8.6688(17) Å, β = 102.76(3)°, Z = 8, ρ(calc) = 2.401 g/cm³, space group P2₁/c, R = 0.0909; for (CH₃)₂Au(SR): a = 3.5401(7) Å, b = 15.689(3) Å, c = 19.910(4) Å, β = 99.81(3)°, Z = 4, ρ(calc) = 2.361 g/cm³, space group P2₁/c, R = 0.0712. Both structures are molecular and involve neutral (CH₃)₂Au(L) molecules, L = C₉H₆NO or C₉H₆NS. In the structures, the molecules are arranged in stacks joined by van der Waals interactions. The average Au…Au intrastack distances are 3.57 Å and 4.34 Å for (CH₃)₂Au(OR) and 3.5 Å for (CH₃)₂Au(SR).     

两个双核铁（Ⅲ）和三足配体的配合物的合成和晶体结构

运用三足四齿配体三（2－甲基吡啶）胺（TPA）或三（2－甲基苯丙咪唑）胺（TBA）,得到两个双核铁(III)配合物，[Fe₂L₂(μ₂-O)(μ₂-p-NH₂-C₆H₄COO)]³⁺ (L = TPA, 1 和 L = TBA, 2)。两个配合物均为单斜晶系，空间群为P2(1)/c.晶胞参数 1: a = 1.4529(4), b = 1.6622(5), c = 2.0625(6) nm, β= 100.327(5)º, V = 4.900(3) nm³, z = 4, F(000) = 2344, 分子量M_r = 1142.91, Dc = 1.549 g/cm³, R₁ = 0.0544, R₂ = 0.0962. 2: a = 1.3378(4), b = 2.1174(7), c = 2.4351(7) nm, β= 97.315(6)º, V = 6.842(4) nm³, z = 4, F (000) = 3116, 分子量M_r = 1505.08, Dc = 1.444 g/cm³, R₁ = 0.0793, R₂ = 0.1623. 在两个双核铁(III)配合物中，中心的三价铁和配体TPA或TBA上的四个氮原子和两个氧原子通过不同的桥形成一个畸变的八面体构型。     

The structure and vibrational spectra of some ferroelectric and ferroelastic alkylammonium halogenoantimonates(III) and bismuthates(III)

Crystals from the rich family of alkylammonium halogenoantimonates(III) and bismuthates(III) containing small bioctahedra as well as infinite two- or one-dimensional polyoctahedral units attract particular attention from the point of view of possible applications. Such crystals exhibit a wealth of phase transitions including those to ferroelectric and ferroelastic phases. The analysis of vibrational spectra performed in this paper with respect to modes assigned to alkylammonium group shows that their interactions with polyanionic sublattice is of medium strength. The absorption pattern and particularly the splitting of bands on cooling very well correlates with other anomalies of physical properties and particularly with the behaviour of second moment of PMR lines and T₁ and T_1ρ relaxation times as functions of temperature. The temperature behaviour of modes is well described in terms of pseudospin–phonon coupling model that we presented for different modes in various crystals. The role of anionic dynamics is not sufficiently recognised but in one case, namely for the low temperature transition in (MA)₃Bi₂Br₉ crystal this role is predominant, according to vibrational and NQR spectra of methylammonium and isostructural caesium salt.     

Co(III) complexes of the type [(L)Co(O2CO)] (L = tripodal tetraamine ligand): Synthesis,structure, DFT calculations and Co NMR

The syntheses and characterisation of the Co(III) complexes [(L)Co(O₂CO)]ClO₄ (L = a tripodal tetraamine ligand = baep, abap, uns-penp, dppa, trpn) are reported. Geometric isomers are possible for all but the trpn complex, owing to the non-equivalence of the three arms on the tripodal ligand, and both NMR and X-ray crystallography are used to identify the single isomer formed. X-ray crystal structures of the complexes [(L)Co(O₂CO)]ClO₄ · xH₂O (L = baep, x = 0.5; L = abap, x = 0; L = uns-penp, x = 1; L = dppa, x = 0; L = trpn, x = 1) are reported; little variation is observed in the geometry of the carbonate chelate ring while significant lengthening of bonds and expansion of angles involving the cobalt ion occurs as the number of six-membered chelate rings in the complex cations increases. ⁵⁹Co NMR chemical shift data for the complexes show the expected linear relationship between λ_max, the wavelength of the lowest energy d–d transition, and γ, the magnetogyric ratio of the ⁵⁹Co nucleus. An excellent correlation between Δ, the d orbital splitting parameter, and δ(⁵⁹Co) also exists for these complexes. Rate data for the acid hydrolysis of [(L)Co(O₂CO)]⁺ (L = uns-penp, dppa) in 1.0 M HClO₄ differ by two orders of magnitude, and this is attributed to the differing steric accessibility of the endo O atoms in each complex. DFT calculations on the complexes reproduce the isomeric preferences, UV–Vis and ⁵⁹Co NMR spectroscopic data well, provided that solvent effects are included.     

Hydrolysis of antimony(III) fluoride complexes

Vibrational and ¹⁷O NMR spectroscopy in combination with quantum chemical calculations are used to investigate the hydrolysis of antimony(III) fluoride complexes. A hydrolytic decomposition of SbF₃ and [SbF₄]^? is accompanied by oligomerization with the formation of edge-and corner-connected dimers ([Sb₂O₂F₄]^2?, [Sb₂OF₈]^4?) and trimers ([Sb₃O₃F₆]^3?, [Sb₃OF₉]^2?) with bridging oxygen atoms. The hydrolysis of [SbF₄]^? is also characterized by the presence in the solution of a discrete cation of [SbF₅]^2? which is least hydrolized. Only a partial isomorphic substitution of fluoride ion by hydroxide one is possible, which is reflected in the composition of K₂Sb(OH)_xF_5?x (x = 0.3) crystals isolated from the fluoride aqueous solution.     

Synthesis, characterization and crystal structure of a 6,8,15,17-tetramethyldibenzo [b,i] (1,4,8,11)tetraaza (14)-annulene yttrium (III) complex

In this study, the sandwich complex of tmtaa, Y(tmtaa) (Htmtaa)·2THF (H₂tmtaa=6,8,15,17-tetramethyldibenzo [b,i] , respectively. The distances of the yttrium to the planes of the 4 nitrogen atoms for tmtaa and Htmtaa are 1.44 (2) and 1.51 (2) Å, respectively.     

Die Chlorooxoarsenate(III) (PPh4)2[As4O2Cl10] · 2 CH3CN und (PPh4)2[As2OCl6] · 3 CH3CN

The Chlorooxoarsenates(III) (PPh₄)₂[As₄O₂Cl₁₀] · 2 CH₃CN and (PPh₄)₂[As₂OCl₆] · 3 CH₃CN (PPh₄)₂[As₂Cl₈] can be prepared from As₂O₃, SOCl₂ and PPh₄Cl in acetonitrile. Its oxidation with chlorine yields PPh₄[AsCl₆]. This was also obtained directly from arsenic, chlorine and PPh₄Cl, (PPh₄)₂[As₄O₂Cl₁₀] · 2 CH₃CN being a side product; the latter was obtained with high yield from AsCl₃, As₂O₃ and PPh₄Cl in acetonitrile. By addition of PPh₄Cl it was converted to (PPh₄)₂[As₂OCl₆] · 3 CH₃CN. According to their X-ray crystal structure analyses, both crystallize in the triclinic space group P 1. The [As₄O₂Cl₁₀]^2– ion can be regarded as a centrosymmetric association product of two Cl₂AsOAsCl₂ molecules and two Cl^– ions, each Cl^– ion being coordinated with all four As atoms. In the [As₂OCl₆]^2– ion the As atoms are linked via the O atom and two Cl atoms.     

Synthesis,Characterization and Crystal Structure of an Unsymmetric Samarium(III) Cryptate

Abstract

The complex [Sm(H₃L)(NO₃)(H₂O)](NO₃)₂ · H₂O was synthesized by the (2+3) condensation of tris(2-aminoethyl)amine with 2,6-diformyl-4-chlorophenol in the presence of Sm³⁺. Its crystal structure has been determined. In the complex the coordination number of Sm³⁺ is nine. A water molecule is encapsulated in the cryptate as a guest, confirmed by electrospray mass spectrometry, thermal analysis and the X-ray crystal structure.     

Synthesis, Crystal and Magnetic Structures of the Sodium Ferrate (IV) Na4FeO4 Studied by Neutron Diffraction and Mössbauer Techniques

The alkali sodium ferrate (IV) Na₄FeO₄ has been prepared by solid-state reaction of sodium peroxide Na₂O₂ and wustite Fe_1−xO, in a molar ratio Na/Fe=4, at 400°C under vacuum. Powder X-ray and neutron diffraction studies indicate that Na₄FeO₄ crystallizes in the triclinic system P−1 with the cell parameters= a=8.4810(2) Å, b=5.7688(1) Å, c=6.5622(1) Å, α=124.662(2)°, β=98.848(2)°, γ=101.761(2)° and Z=2. Na₄FeO₄ is isotypic with the other known phases Na₄MO₄ (M=Ti, Cr, Mn, Co and Ge, Sn, Pb). The solid solution Na₄Fe_xCo_1−xO₄ exists for x=0-1 and we have followed the evolution of the cell parameters with x to determine the lattice parameters of the triclinic cell of Na₄FeO₄. A three-dimensional network of isolated FeO₄ tetrahedra connected by Na atoms characterizes the structure. This compound is antiferromagnetic below T_N=16 K. At 2 K the magnetic cell is twice the nuclear cell and the magnetic structure is collinear (μ_Fe=3.36(12) μ_B at 2 K). This black compound is highly hygroscopic. In water or on contact with the atmospheric moisture it is disproportionated in Fe³⁺ and Fe⁶⁺. The Mössbauer spectra of Na₄FeO₄ are fitted with one doublet (δ=− 0.22 mm/s, Δ=0.41 mm/s at 295 K) in the paramagnetic state and with a sextet at 8K. These parameters characterize Fe⁴⁺ high-spin in tetrahedral FeO₄ coordination.     

Crystal Structure and Magnetic Properties of a New Iron(III) Silicophosphate Fe3P5SiO19 Studied by Neutron Diffraction and Mössbauer Techniques

Fe₃P₅SiO₁₉ has been prepared by solid state reaction of Fe(PO₃)₃, FePO₄, and SiO₂ at 1000°C. The structure has been determined from a single crystal through direct methods and difference Fourier synthesis and refined to R=0.052. The unit cell is hexagonal, space group P6₃, with a=14.4804(8) Å, c=7.4256(2) Å, and Z=4. The three-dimensional framework is built up from [Fe₂O₉] units of two faces sharing octahedra and Si₂O₇ disilicates linked by PO₄ tetrahedra. Fe₃P₅SiO₁₉ is isotypic with V₃P₅SiO₁₉. Fe₃P₅SiO₁₉ is antiferromagnetic below T_N=35 K. The magnetic structure has been determined by means of powder neutron diffraction methods: the magnetic moments are antiferromagnetically coupled inside the [Fe₂O₉] units, in agreement with the Goodenough rules. These units are linked to each other through several Fe-O-P-O-Fe super-superexchange pathways and form antiferromagnetic [001] rows. The moment direction lies in the (001) plane (μ_Fe=4.56(5) μ_B at 2 K). There is a competition between the intra- and interunits interactions which all are antiferromagnetic and cannot be simultaneously satisfied without frustration. Mössbauer spectra are fitted with two doublets and two sextuplets in the paramagnetic and antiferromagnetic states, respectively. Their rather high isomer shifts are explained by the inductive effect. The magnetic interactions are discussed.     

209Bi NQR study of bismuth(III) complexes

Potassium pentafluorobismuthate(III), nitrate-chloride Bi^III complexes MBiCl₃NO₃ (M=K, (NH₂)₂CNH₂), sulfate-chloride Bi^III complexes MBiCl₂SO₄ (M=K, Rb, NH₄, (NH₂(₂CNH₂), and Bi^III complexonates with the anions of ethylenediaminetetraacetic acid M[Bi(edta)]₂·nH₂O (M=Mg, Ca, Ni, Cd) and nitrilotriacetic acid Bi(nta)·2H₂O, and Bi(nta)·3thio·H₂O (thio is thiourea) were studied by²⁰⁹Bi NQR spectroscopy. A second-order phase transition was observed in K₂BiF₅ at 100 K. The compounds Bi(nta)·2H₂O, (NH₂)₂CNH₂BiCl₃NO₃, and MBiCl₂SO₄ (M=K, NH₄) are piezoelectrics. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2237–2240, November, 1998.