Dark Red Single Crystals Research Articles

Synthesis and Crystal Structure of the Europium(II) Hydride Oxide Iodide Eu5H2O2I4 Showing Blue-Green Luminescence.

As the first europium(II) hydride oxide iodide, dark red single crystals of Eu5H2O2I4 could be synthesized from oxygen-contaminated mixtures of EuH2 and EuI2. Its orthorhombic crystal structure (a = 1636.97(9) pm, b = 1369.54(8) pm, c = 604.36(4) pm, Z = 4) was determined via single-crystal X-ray diffraction in the space group Cmcm. Anion-centred tetrahedra [HEu4]7+ and [OEu4]6+ serve as central building blocks interconnected via common edges to infinite ribbons parallel to the c axis. These ribbons consist of four trans-edge connected (Eu2+)4 tetrahedra as repetition unit, two H--centred ones in the inner part, and two O2--centred ones representing the outer sides. They are positively charged, according to ∞1{[Eu5H2O2]4+}, to become interconnected and charge-balanced by iodide anions. Upon excitation with UV light, the compound shows blue-green luminescence with the shortest Eu2+ emission wavelength ever observed for a hydride derivative, peaking at 463 nm. The magnetic susceptibility of Eu5H2O2I4 follows the Curie-Weiss law down to 100 K, and exhibits a ferromagnetic ordering transition at about 10 K.

Li9Yb2[PS4]5 and Li6Yb3[PS4]5: two lithium-containing ytterbium(III) thiophosphates(V) revisited

Abstract The lithium ytterbium ortho-thiophosphates Li9Yb2[PS4]5 and Li6Yb3[PS4]5 were prepared through the reaction of stoichiometric amounts of ytterbium metal, elemental sulfur, red phosphorus and lithium hemisulfide at elevated temperatures in sealed silica tubes. The compounds occur as dark red single crystals which crystallize monoclinically in space group C2/c with the lattice parameters a = 1487.98(9), b = 978.63(6), c = 2046.75(12) pm and β = 96.142(3)° for Li9Yb2[PS4]5 (Z = 4) and a = 2814.83(16), b = 997.34(6), c = 3338.52(19) pm and β = 113.685(3)° for Li6Yb3[PS4]5 (Z = 12). Li9Yb2[PS4]5 can be assigned to the structure type of Li9Nd2[PS4]5, whereas the structure of Li6Yb3[PS4]5 the structure is similar to that of the prototypic Li6Gd3[PS4]5. Both structures feature discrete [PS4]3– tetrahedra (d(P–S) = 202–207 pm) and strands of [YbS8]13− polyhedra (d(Yb–S) = 271–319 pm) propagating along [010]. When attributed to the general formula (Li3[PS4]) x (Yb[PS4]) y , ideas of the dimensionality of both structures can be derived. Whilst the lithium-richer Li9Yb2[PS4]5 (x/y = 1.5) develops planes with the composition ∞ 2 { [ Y b [ P S 4 ] 3 ] 6 − } ${}_{\infty }^{2}\left\{{\left[\mathrm{Y}\mathrm{b}{\left[\mathrm{P}{\mathrm{S}}_{4}\right]}_{3}\right]}^{6-}\right\}$ , Li6Yb3[PS4]5 (x/y = 0.667) exhibits a rather complex three-dimensional network of ytterbium-centered polyhedra connected via [PS4]3– tetrahedra with lithium cations in the framework structure ∞ 3 { [ Y b 3 [ P S 4 ] 5 ] 6 − } ${}_{\infty }^{3}\left\{{\left[\mathrm{Y}{\mathrm{b}}_{\mathrm{3}}{\left[\mathrm{P}{\mathrm{S}}_{4}\right]}_{5}\right]}^{6-}\right\}$ . These Li+ cations are hard to locate in both compounds, but reside in four- to sixfold sulfur coordination (d(Li–S) = 235–304 pm). Some Li+ positions are underoccupied and some Li+ cations share sites with Yb3+ cations in Li6Yb3[PS4]5, and even in Li9Yb2[PS4]5 their high displacement values suggest Li+ cation mobility. According to the empirical formulae, three Li+ cations have to be replaced with one Yb3+ cation to reach the lithium-poorer compound and structure (Li6Yb3[PS4]5) starting from the lithium-richer one (Li9Yb2[PS4]5).

Li17Sb13S28: A New Lithium Ion Conductor and addition to the Phase Diagram Li2S-Sb2S3.

Li17Sb13S28 was synthesized by solid-state reaction of stoichiometric amounts of anhydrous Li2S and Sb2S3. The crystal structure of Li17Sb13S28 was determined from dark-red single crystals at room temperature. The title compound crystallizes in the monoclinic space group C2/m (no. 12) with a=12.765(2) Å, b=11.6195(8) Å, c=9.2564(9) Å, β=119.665(6)°, V=1193.0(2) Å(3), and Z=4 (data at 20 °C, lattice constants from powder diffraction). The crystal structure contains one cation site with a mixed occupation by Li and Sb, and one with an antimony split position. Antimony and sulfur form slightly distorted tetragonal bipyramidal [SbS5E] units (E=free electron pair). Six of these units are arranged around a vacancy in the anion substructure. The lone electron pairs E of the antimony(III) cations are arranged around these vacancies. Thus, a variant of the rock salt structure type with ordered vacancies in the anionic substructure results. Impedance spectroscopic measurements of Li17Sb13S28 show a specific conductivity of 2.9×10(-9) Ω(-1) cm(-1) at 323 K and of 7.9×10(-6) Ω(-1) cm(-1) at 563 K, the corresponding activation energy is EA=0.4 eV below 403 K and EA=0.6 eV above. Raman spectra are dominated by the Sb-S stretching modes of the [SbS5] units at 315 and 341 cm(-1) at room temperature. Differential thermal analysis (DTA) measurements of Li17Sb13S28 indicate peritectic melting at 854 K.

Crystal Structures of Energetic Compounds. I. Safe Small-Scale Preparation and X-Ray Structure Determination of the High-Energy Cobalt(III) Complex [Co(NH3)5N3](N3)2

Well-formed dark red single-crystals of the potentially explosive cobalt(III) azido complex [Co(NH3)5N3](N3)2 (nitrogen content: 72.59%) have been grown using a safe small-scale preparation from [Co(NH3)5N3]Cl2 and sodium azide. The complex crystallizes in the orthorhombic system, space group Pnma with unit cell parameters a = 12.921(3) A, b = 10.346(2) A, c = 8.0315(16) A, V = 1,073.7(4) A3 and Z = 4. Five NH3 ligands and the azide anion surround the Co3+ ion in a nearly perfect octahedral geometry. Two azide anions are non-coordinating, and no water of crystallization is present in the crystal structure. Well-formed dark red single-crystals of the potentially explosive cobalt(III) azido complex [Co(NH3)5N3](N3)2 (nitrogen content: 72.59%) have been grown using a safe small-scale preparation from [Co(NH3)5N3]Cl2 and sodium azide. Five NH3 ligands and the azide anion surround the Co3+ ion in a nearly perfect octahedral geometry. Two azide anions are non-coordinating, and no water of crystallization is present in the crystal structure.

Ba3YRu0.73(2)Al1.27(2)O8 and Ba5Y2Ru1.52(2)Al1.47(2)O13.5: New Perovskite Ruthenates with Partial Octahedra Replacement

Dark red single crystals of the new phases Ba3YRu0.73(2)Al1.27(2)O8 and Ba5Y2Ru1.52(2)Al1.47(2)O13.5 have been grown from powder mixtures of BaCO3, Y2O3, Al2O3, and RuO2 . The compositions given in the formulas result from the refinements of the crystal structures based on single crystal X-ray diffraction data (hexagonal P63/mmc (No. 194), Z = 2, Ba3 YRu0.73(2)Al1.27(2)O8: a = 5.871(1), c = 14.633(3) Å , R1 = 0.035, wR2 = 0.069 and Ba5Y2Ru1.52(2)Al1.47(2)O13.5: a = 5.907(1), c = 24.556(5) Å, R1 = 0.057, wR2 = 0.114). Ba3YRu0.73(2)Al1.27(2)O8 crystallizes in a 6H perovskite structure, Ba5Y2Ru1.52(2)Al1.47(2)O13.5 has been characterized as a 10H Perovskite. Due to similar spatial extensions of (Ru2O9) facesharing pairs of octahedra and (Al2O7) vertex-sharing pairs of tetrahedra, both structures show partial mutual substitution of these units. Consequently, the title compounds may be written as Ba3Y(Ru2O9)1−x(Al2O7)x, x = 0.64(1) and Ba5Y2RuO6(Ru2O9)1−x(Al2O7)x, x = 0.74(1). This interpretation is supported by the results of electron probe microanalysis using wavelength-dispersive X-ray spectroscopy. An oxidation state of Ru close to +5 for the (Ru2O9) units, as can be derived from the distances d(Ru-Ru), additionally leads to similar charges of both the (Ru2O9) and the (Al2O7) units.

Syntheses, structure, magnetism, and optical properties of the partially ordered quaternary interlanthanide sulfides Pr LnYb 2S 6 ( Ln=Tb, Dy)

Dark red single crystals of Pr LnYb 2S 6 ( Ln=Pr/Yb, Tb, Dy) have been synthesized through the reactions of elemental rare earth metals and S using a Sb 2S 3 flux at 1000 °C. These isotypic compounds adopt the F- Ln 2S 3 three-dimensional open-channel structure type. Eight-coordinate Pr 3+ ions sit in the channels that are constructed from three different edge-shared double chains running down the b-axis that contain Yb(1)S 6 octahedra, Yb(2)S 6 octahedra, and LnS 7 monocapped trigonal prisms. Each double chain connects to four other neighbors by sharing vertices and edges. Considerable disordering in Ln positions was observed in single X-ray diffraction experiments only in the case of Pr/Yb. Least-squares refinements gave rise to the formulas of Pr 1.34Yb 2.66S 6, of PrTbYb 2S 6, and PrDyYb 2S 6, which are confirmed by the elemental analysis and magnetic susceptibility measurements. Pr 1.34Yb 2.66S 6, PrTbYb 2S 6, and PrDyYb 2S 6 are paramagnetic down to 2 K, without any indications of long-range magnetic ordering. The optical transitions for Pr 1.34Yb 2.66S 6, PrTbYb 2S 6, and PrDyYb 2S 6 are at approximately 1.6 eV. Crystallographic data are listed as an example for PrTbYb 2S 6: monoclinic, space group P2 1 /m, a=10.9496(10) Å, b=3.9429(4) Å, c=11.2206(10) Å, β=108.525(2)°, V=459.33(7) Å 3, Z=2.

Crystal Structure and Characterisation of Mercury(II) Dichromate(VI)

Dark-red single crystals of HgCr2O7 were grown by reacting HgO and CrO3 in excess at 200°C for four days. The crystal structure (space group P32, Z = 3, a = 7.2389(10), c = 9.461(2) A, 1363 structure factors, 57 parameters, R[F2>2σ(F2)] = 0.0369, wR(F2 all) = 0.0693) was determined from a crystal twinned by merohedry according to (110). It consists of nearly linear HgO2 units (\({\bar {d}}\)(Hg–O) = 2.02 A) and dichromate units that are linked into infinite chains ‘O3Cr–O–CrO3–Hg–O3Cr–O–CrO3’ running parallel to the c-axis. Six additional Hg–O contacts between 2.73 and 2.96 A stabilise the structural arrangement. The dichromate anion exhibits a staggered conformation with a bent Cr–O–Cr bridging angle of 140.7(6)°. Upon heating above 300°C, HgCr2O7 decomposes in a two-step mechanism to Cr2O3. The title compound was additionally characterised by vibrational spectroscopy.

Caesium Heptaiodo‐Dititanate(III), CsTi2I7.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Caesium Heptaiodo‐Dititanate(III), CsTi2I7

AbstractCaesium heptaiodo‐dititanate(III), CsTi2I7, is obtained from CsI, Ti and TiI4 at 250 °C in a sealed tantalum ampoule as dark red single crystals. The crystal structure (trigonal, R‐3, a = 1706.6(3), c = 2088.3(5) pm, Z = 12, R1 = 0.0619) contains [TiI4] tetrahedra sharing common vertices (with Ti—I—Ti angles of 180°) to isolated ditetrahedra [Ti2I7]—. It may also be described as a cubic closest packing of alternating CsI3 and I4 layers between which neighbouring tetrahedra are occupied in a way that [Ti2I7]— ditetrahedra are achieved.http://www.gerdmeyer.de

Synthesis, Structural and Spectroscopic Characterization of the α,ω-Diammonioalkane Hexabromorhodates( III) [H3N(CH2)xNH3]2[H5O2][RhBr6]Br2 (x = 3, 4) – IR Spectra of [H5O2]+ Ions with Weak Solid State Interactions

The reaction of rhodium(III) chloride trihydrate with 1,3-diaminopropane and 1,4-diaminobutane in concentrated hydrobromic acid results in the formation of the bis(α,ω-diammonioalkane) diaquahydrogen(1+) hexabromorhodate(III) dibromides [H3N(CH2)xNH3]2[H5O2][RhBr6]Br2 (x = 3, 4). Dark red single crystals were obtained by diffusion-controlled crystallization at room temperature. Both compounds crystallize in space group type P1̄ and their structures are closely related. In view of crystal engineering they are inorganic-organic hybrid materials built up from octahedral [RhBr6]3−, simple Br− and flexible chain-like [H3N(CH2)xNH3]2+ ions with the [H5O2]+ and further Br− ions incorporated and thus might be considered as addition compounds [H3N(CH2)xNH3]2[RhBr6]Br ∙ [H5O2]Br. Cationic and anionic moieties in the crystal are held together by a complex system of N-H∙∙∙Br and O-H∙∙∙Br hydrogen bonds. Geometric features of O-H∙∙∙Br hydrogen bonding as well as the pronounced disorder of the [H5O2]+ ions in the diammoniopropane salt indicate the weak association of these species in the solids. Weak association of the ions is also documented by difference ATR-FT-IR spectra of the compounds and related diammonioalkane dibromides that show the stretching modes of the terminal O-H bonds above 3300 cm−1. Further characteristic bands are recognized at ca. 1635 (s), 985 (vs), and 670 (m) cm−1.

Zinc- and Tin-Mediated C−C Coupling Reactions of Metalated (2-Pyridylmethyl)(trialkylsilyl)amines − Mechanistic, NMR Spectroscopic, and Structural Studies

The zincation of (2-pyridylmethyl)(triisopropylsilyl)amine (1) gives dimeric methylzinc (2-pyridylmethyl)(triisopropylsilyl)amide (2). Further addition of dimethylzinc to a toluene solution of 2 at raised temperatures yields the C−C coupling product [1,2-dipyridyl-1,2-bis(triisopropylsilylamido)ethane]bis(methylzinc) (3). Heating of molten 2, or UV irradiation of 2, results in the formation of 3 and zinc bis[(2-pyridylmethyl)(triisopropylsilyl)amide] (4). The reaction between the zinc dihalide complexes of 1 [5a (X = Cl) and 5b (X = Br)] and methyllithium yields the C−C coupling product 3 and the heteroleptic complex 2, observed by NMR spectroscopy. During this reaction, zinc metal precipitates. The magnesiation of 1 with dibutylmagnesium gives magnesium bis[(2-pyridylmethyl)(triisopropylsilyl)amide] (6) in a quantitative yield. Subsequent addition of dimethylmagnesium results in a dismutation reaction and the formation of heteroleptic methylmagnesium (2-pyridylmethyl)(triisopropylsilyl)amide (7). Treatment of 1 with dimethylmagnesium also gives 7. This complex slowly undergoes an intramolecular metalation during which dark red single crystals of (tetrahydrofuran)magnesium 2-(triisopropylsilylamidomethylidene)-1-azacyclohexa-3,5-dien-1-ide (8) precipitate. In this compound the aromaticity of the pyridyl fragment is abolished. The magnesiation of (tert-butyldimethylsilyl)(2-pyridylmethyl)amine (I) proceeds quantitatively to give methylmagnesium (tert-butyldimethylsilyl)(2-pyridylmethyl)amide (9). This compound also undergoes an intramolecular metalation reaction, which results in the loss of the aromaticity of the pyridyl substituent and the formation of (tetrahydrofuran)magnesium 2-(tertbutyldimethylsilylamidomethylidene)-1-azacyclohexa-3,5dien-1-ide (10). The metalation of 1 with tin(II) bis[bis(trimethylsilyl)amide] yields [bis(trimethylsilyl)amido]tin(II) (2-pyridylmethyl)(triisopropylsilyl)amide (11). The elimination of tin metal occurs even at room temperature, and the C−C coupling product [1,2-dipyridyl-1,2-bis(triisopropylsilylamido)ethane]tin(II) (12) is formed. The metalation of (tert-butyldimethylsilyl)(2-pyridylmethyl)amine with Sn[N(SiMe3)2]2 gives [bis(trimethylsilyl)amido]tin(II) (tert-butyldimethylsilyl)(2-pyridylmethyl)amide (13). Within a few minutes, precipitation of tin metal takes place and the C−C coupled product [1,2-bis(tert-butyldimethylsilylamido)-1,2-dipyridylethane]tin(II) (14) is produced. In order to examine the importance of the pyridyl ligand for the C−C coupling reactions, zinc bis[N-(tert-butyldimethylsilyl)benzylamide] (15) was prepared by means of the metathesis reaction between lithium N-(tert-butyldimethylsilyl)benzylamide and zinc(II) halide. Treatment of 15 with dimethylzinc yields heteroleptic methylzinc N-(tert-butyldimethylsilyl)benzylamide (16). Refluxing of 16 with an excess of dimethylzinc in toluene does not give any C−C coupling reactions.

Synthesis and crystal structure of Cu 4TiS 4: a novel chalcogenide with tetrahedrally coordinated titanium

Dark red single crystals of Cu 4TiS 4 were prepared by reacting an intimate mixture of Cu 2S, Ti and S at 500°C. Cu 4TiS 4 is tetragonal, space group I 42m with a = 5.448(1) A ̊ , c = 10.565(2) A ̊ , Z = 2 . The crystal structure is of a new type. It was determined from diffractometer data and refined to a conventional R of 0.024 for 132 F 0s and 17 variables. The crystal structure is based on a cubic close packing of chalcogen with Cu and Ti in tetrahedral interslices. This results in a three-dimensional framework of vertex sharing CuS 4 tetrahedra which are connected with the almost regular TiS 4 tetrahedra through common edges. The bond lengths are d( TiS) = 2.278 A ̊ and d( CuS) = 2.333 to 2.351 A ̊ .

Synthesis, crystal structure and electrochemistry of bis( N,N-dimethylammonium) tris(1,2-benzenedithiolato)titanate(IV)

Synthesis, electrochemical and structural data for [NH 2(CH 3) 2] 2[Ti(S 2C 6H 4) 3] ( 1 are described. Treating Ti{N(CH 3) 2} 4 with 1,2-(HS) 2C 6H 4 in a 1 : 3 ratio affords 1 in 94% isolated yield. Dark red single crystals of 1, suitable for X-ray crystallography, were obtained from CH 3CNEt 2O mixtures. The molecular structure of the anion of 1, [Ti(S 2C 6H 4) 3] 2−, provides a rare example of a homoleptic thiolate complex of titanium, but more importantly, the titanium centre contains the unusual TiS 6 coordination of a skew-trapezoidal bipyramid (S-TzBP) with angular coordinates φ A = 60°, φ B = 140 E = 75°. The S 6 polyhedron in 1 can be alternatively described as a pentagonal bipyramid with an equatorial vertex missing. A spectropotentiostatic experiment for 1 verified that a reversible one-electron reduction occurs at −1.51 V ( vs Ag/AgCl, DMF). The electrochemical product was characterized by UV-vis (347, 414 and 434 nm) and ESR (77 K, rhombic: g 1 = 2.18 g 2 = 2.04 and g 3 = 2.00) spectroscopies.

Acetylenkomplexe von Rhenium(+ VI). Die Kristallstrukturen von [ReCl4(n-C3H7 – C= C – n-C3H7)(POCl3)] und ReCl4(THF)2 / Alkyne Complexes of Rhenium(+VI). The Crystal Structures of [ReCl4(n-C3H7 – C= C – n-C3H7)(POCl3)] and ReCl4(THF)2

The results of the magnetic susceptibility measurements of the previously reported rhenium alkyne complexes [ReCl4(PhC≡CPh)]2.2 CH2Cl2 and [ReCl4(PhC=CPh)(CH3CN)] in the temperature range of 4.2-293 K suggest d1-configurations, corresponding with oxidation state +VI for the rhenium atoms. The new alkyne complex [ReCl4(n-C3H7–C=C–n-C3H7)(POCl3)] has been prepared by the reaction of ReCl5·OPCl3 with n-C3H7-C≡C–n-C3H7 in CCl4 solution, forming dark red single crystals, which were characterized by IR spectroscopy as well as by a crystal structure determination with X-ray methods (space group P2,/c, Z = 4, 3235 observed unique reflexions, R = 0.026; lattice dimensions at –70 °C: a = 805.6(2), b = 1000.6(4), c = 2188.8(6) pm, β = 79.59(2)°). [ReCl4(n-C3H7-C=C–n-C3H7)(POCl3)] has a molecular structure with the alkyne ligand bonded side-on (bond lengths Re-C 198.4 and 198.2(5) pm). The oxygen atom of the solvating POCl3 molecule is coordinated in trans position to the ReC2 unit of the alkyne ligand (bond length Re—O = 223.7(3) pm). In THF solutions the alkyne complexes of this type undergo a slow reaction forming ReCl4(THF)2, which was also characterized by IR spectroscopy and a crystal structure determination (space group P212121, Z = 4, 2243 observed unique reflexions, R = 0.053; lattice dimensions at –70 °C: a = 773.0(14), b = 1267.1(6), c = 1398.6(7) pm). In ReCl4(THF)2 the THF molecules coordinate in cis-position (bond lengths Re–O 208 and 212(1) pm).

Notizen: Molekülstruktur von Re3Cl6(Acac)3 im Feststoff / Molecular Structure of Re3Cl6(Acac)3 in the Solid State

Dark red single crystals of Re3Cl6(Acac)3 are obtained from a solution of “ReCl3·2H2O” in acetylacetone by slow evaporation. The unit cell (monoclinic, P21/c, a = 1687.3(9), b = 963.4(5), c = 1664.3(9) pm, β = 108.97(4)°) contains four molecules of Re3Cl6(Acac)3. Each of the bidentate Acac(—) ligands substitutes one of the in-plane terminal and one of the out-of-plane terminal ligands with respect to the Re3 triangle.

Perylene–Hexacyanobutadiene (HCBD) Complex

Abstract Hexacyanobutadiene (HCBD) gives dark red single crystals with equimolar perylene. The crystal structure analysis shows that the complex has mixed regular stacks. The physical properties of the single crystals indicate that the complex is an insulator with neutral ground state and close to neutral-ionic boundary.