EuPtSn2 – A Stannide with Sn2 Dumbbells in a Three-dimensional [PtSn2]2– Polyanion

EuPtSn₂ was obtained by melting of the elements in a sealed tantalum ampoule followed by an annealing sequence for crystal growth. The EuPtSn₂ sample was studied through its Guinier powder pattern and the structure was refined from single-crystal X-ray diffractometer data: CeRhSn₂ type, Cmcm, a = 472.05(3), b = 1724.19(12), c = 957.36(7) pm, wR₂ = 0.0388, 879 F² values and 30 variables. The platinum and tin atoms build up a three-dimensional [PtSn₂]^2– polyanionic network which consists of distorted PtSn₅ square pyramids (265–278 pm Pt–Sn) and Sn₂ dumbbells with 281 and 299 pm Sn–Sn distances. The structural relationship with DyRhGe₂ and Ce₃Pt₄Ge₆ is discussed. EuPtSn₂ shows Curie–Weiss behavior with an experimental magnetic moment of 7.78(1) μ_B / Eu, indicating stable divalent europium. This is corroborated by ¹⁵¹Eu Mössbauer spectroscopy. Antiferromagnetic ordering is detected below 3.4 K. Specific heat measurements confirm the magnetic ordering and indicate a second phase transition through a clear λ-type signal at 7.3 K which might be associated with a structural distortion.     

Bi3GaS5]2[Ga3Cl10]2[GaCl4]2·S8 containing heterocubane-type [Bi3GaS5]2+, star-shaped [Ga3Cl10]-, monomeric [GaCl4]- and crown-like S8

By reaction of elemental bismuth, sulfur, bismuth(III) chloride and gallium(III) chloride in the ionic liquid (BMIm)Cl (BMIm: 1-butyl-3-methylimidazolium), [Bi(3)GaS(5)](2)[Ga(3)Cl(10)](2)[GaCl(4)](2)·S(8) is obtained as red transparent crystals. According to X-ray structure analysis based on single crystals, the title compound crystallizes with triclinic lattice symmetry and is composed of heterocubane-type [Bi(3)GaS(5)](2+) cations, trimeric star-shaped [Ga(3)Cl(10)](-) anions with three (GaCl(4)) tetrahedra sharing a single central chlorine atom, monomeric [GaCl(4)](-) tetrahedra and neutral, crown-shaped S(8)-rings. Here, the heterocubane [Bi(3)GaS(5)](2+) as well as the star-shaped [Ga(3)Cl(10)](-) are observed as building units for the first time. [Bi(3)GaS(5)](2)[Ga(3)Cl(10)](2)[GaCl(4)](2)·S(8) is further characterized by X-ray powder diffraction as well as by thermogravimetry/differential thermal analysis.     

Bi2(IO3)(IO6): First combination of [IO3]− and [IO6]5− anions in three-dimensional framework

A new bismuth (III) iodate periodate, Bi₂(IO₃)(IO₆) was obtained from hydrothermal reactions using Bi(NO₃)₃·5H₂O, and H₅IO₆ as starting materials. Bi₂(IO₃)(IO₆) crystallizes in the monoclinic space group P2₁/c (No. 14) with lattice parameters ɑ = 8.1119(6), b = 5.4746(4), c = 16.357(1) Å, β = 99.187(2)°, V = 717.07(9) ų, Z = 4. The structure of Bi₂(IO₃)(IO₆) features a three-dimensional framework which is a combination of [Bi(1)O₅] tetragonal pyramids, [Bi(2)O₈] bicapped trigonal prisms and [IO₃]⁻ and [IO₆]⁵⁻ anions. Thermal analysis shows that the compound is thermally stable up to about 350 °C. The solid state UV-vis-NIR diffuse reflectance spectrum indicates that Bi₂(IO₃)(IO₆) is a semiconductor with a band gap of 2.76 eV.     

Mild Template Synthesis in the Ni(II)–Dithiooxamide–Acetone Ternary System in Ni2[Fe(CN)6] Gelatin-Immobilized Matrix Implantates

Complexation processes that occur when nickel(II) hexacyanoferrate(II) immobilized in gelatin is brought into contact with aqueous solutions containing dithiooxamide and acetone at pH > 10 were studied. Under these specific conditions, template synthesis takes place to give a 1 : 1 nickel(II) complex with an N,N,S,S-donor ligand, namely, 4,4",6-trimethyl-2,8-dithio-3,7-diaza-6-nonene-1,9-dithioamide, in which dithiooxamide and acetone function as ligand synthons. A scheme for the processes involved is proposed. When dithiooxamide and acetone are in direct contact in the absence of Ni(II), the N,N,S,S-donor ligand is not formed. The reaction of known Ni(II) dithiooxamide complexes with acetone does not give the Ni(II) complex with this ligand either.     

Synthesis,Crystal Structure,Vibrational Spectroscopy and Thermal Behavior of the First Alkali Metal Hydrated Hexaborate： K2[B6O9（OH）2]

New hydrated potassium hexaborate K2[B6O9（OH）2] has been synthesized under mild solvothermal conditions. The structure was determined by single-crystal X-ray diffraction and further characterized by FT-IR, Rarnan spectra and DTA-TG. It crystallizes in the monoclinic system with space group P21/n, a=0.9036（2） nm, b=0.66052（18） nm, c=1.5997（4） nm, β=91.862（4）°, V=0.9543（4） nm^3 and Z=4. Its crystal structure consists of K-O polyhedra and 1-D stepped polyborate chains constructed by new [B6O9（OH）2]2- fundamental building blocks. 1-D polyborate chains contain 3,8-membered boron rings. Adjacent chains are further linked via H-bonding interactions into 2-D layers. The K^＋ cations reside not only between the layers but also in the 8-membered boron rings of the chains, compensating the negative charges of the borate chains and holding the layers together into the 3-D structure through bonding with oxygen atoms of the chains.     

Binary group 15 polyazides. structural characterization of [Bi(N3)4]-, [Bi(N3)5]2-, [bipy·Bi(N3)5]2-, [Bi(N3)6]3-, bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2 and on the lone pair activation of valence electrons

The binary group 15 polyazides As(N(3))(3), Sb(N(3))(3), and Bi(N(3))(3) were stabilized by either anion or donor-acceptor adduct formation. Crystal structures are reported for [Bi(N(3))(4)](-), [Bi(N(3))(5)](2-), [bipy·Bi(N(3))(5)](2-), [Bi(N(3))(6)](3-), bipy·As(N(3))(3), bipy·Sb(N(3))(3), and [(bipy)(2)·Bi(N(3))(3)](2). The lone valence electron pair on the central atom of these pnictogen(+III) compounds can be either sterically active or inactive. The [Bi(N(3))(5)](2-) anion possesses a sterically active lone pair and a monomeric pseudo-octahedral structure with a coordination number of 6, whereas its 2,2'-bipyridine adduct exhibits a pseudo-monocapped trigonal prismatic structure with CN 7 and a sterically inactive lone pair. Because of the high oxidizing power of Bi(+V), reactions aimed at Bi(N(3))(5) and [Bi(N(3))(6)](-) resulted in the reduction to bismuth(+III) compounds by [N(3)](-). The powder X-ray diffraction pattern of Bi(N(3))(3) was recorded at 298 K and is distinct from that calculated for Sb(N(3))(3) from its single-crystal data at 223 K. The [(bipy)(2)·Bi(N(3))(3)](2) adduct is dimeric and derived from two BiN(8) square antiprisms sharing an edge consisting of two μ(1,1)-bridging N(3) ligands and with bismuth having CN 8 and a sterically inactive lone pair. The novel bipy·As(N(3))(3) and bipy·Sb(N(3))(3) adducts are monomeric and isostructural and contain a sterically active lone pair on their central atom and a CN of 6. A systematic quantum chemical analysis of the structures of these polyazides suggests that the M06-2X density functional is well suited for the prediction of the steric activity of lone pairs in main-group chemistry. Furthermore, it was found that the solid-state structures can strongly differ from those of the free gas-phase species or those in solutions and that lone pairs that are sterically inactive in a chemical surrounding can become activated in the free isolated species.     

K5[InSe4] and K12[InS4]2(S): New Alkali Chalcogenido Indates with [InQ4]5– ortho Anions

The new chalcogenido ortho indates(III) K₅[InSe₄] and K₁₂[InS₄]₂(S) were synthesized from melts of the elements (Se) [or with S/In₂S₃ as chalcogen source] at maximum temperatures of 700/800 °C. The two potassium salts, which were characterized by means of X-ray single crystal structure analysis, contain isolated tetrahedral ortho anions [InQ₄]^5–. K₅[InSe₄] crystallizes in a new structure type [monoclinic, space group C2/c, a = 2014.2(2), b = 1553.1(2), c = 1661.1(2) pm, β = 94.716(2)°, Z = 16, R₁ = 0.0317]. The complex structure contains two crystallographically different [InSe₄]^5– tetrahedra [d(In ··· Se) = 254.3–263.6 pm], which are arranged into 4⁴ [In(1), A ] and 3².4.3.4 [In(2), B ] nets. These nets are |: ABA ' B ':| stacked along the a axis. The 11 crystallographically independent K⁺ ions are coordinated by four (1×), five (3×) and six (7×) selenido anions [d(K–Se) = 309–415 pm]. The crystal structure and the calculated electronic structure of the pure ortho indate K₅[InSe₄] are compared with the known “double salts” K₉[InSe₄]₂(Se) and K₉[InSe₄](Se₂)(Se), which exhibit selenide (and diselenide) anions in addition to the ortho metallate. Similarly, the new sulfido indate K₁₁[InS₄]₂(S) contains sulfide anions besides the indate tetrahedra. In the chiral structure (K₆[InTe₄](Cl)-type, hexagonal, space group P6₃mc, a = 1026.22(10), c = 752.34(7) pm, Z = 2, R1 = 0.0332) layers of similarly oriented [InS₄] tetrahedra [d(In ··· Se) = 246.6/248.1 pm] are hexagonally |: AB :| stacked along one threefold axis. The additional sulfide anions are centered in K⁺ octahedra. In contrast to the isotypic chloride, only every second polyhedron within the columns of face-sharing K₆ octahedra is statistically occupied by a sulfide ion. Both of the two different K positions exhibit a sixfold coordination by sulfide anions, with K–S distances between 307.1 and 382.1 pm. In the two title compounds, each of the [InQ₄] tetrahedra is overall enclosed by 18 potassium cations. The crystal chemistry of the new indates is discussed and compared with that of the (yet comparatively low number) of alkali chalcogenido metallates(III) of Fe, Al and Ga containing isolated metallate tetrahedra.     

Synthesis and Structure of 6'-Diethylamino-2'-phenacylami nospiro-[isobenzofuran- 1 (3H), 9'- [9H]xanthen]-3-one

1mTRODUCTIONWehavereportedsomenuorancomPoundswithdifferentsubstitutedgroups"~'>.Thispaperdescribesacontinuationofourinvestigationonthenuoranderivatives.ThecrystalstructureofthecomPOundC,zHzsNzo'(I)(whereRl-NEt2,R2=H,R3=NHCHzCoCeHs,R`=H)wasdeterminedbyX-raydiffractionmethod.Inaddition,wealsocomparethetitlecomPOundwithotherfluorancomPounds.2EXPERIMENTAL2.1SynthesisAmixtureof2'-carboxy-4-diethylamino-2-hydrzophenoneandP-hydroxy-acetanilide(molarratio1:l)insulfuricacidwasheated…     

Retracted: The Effect of Air on the Oxidation Decomposition of Cationic Exchange Resins in a Ternary Li2CO3−Na2CO3−K2CO3 Molten-Salt System

The molten-salt oxidation method (MSO) can be applied for disposal of spent cationic exchange resins (CERs) after the treatment of nuclear industry wastewater. In this work, the oxidation decomposition of resins in carbonate molten salt in N₂ and air atmospheres was investigated. The SEM morphology and FTIR spectrograms indicated that the addition of air obviously prompted the oxidation decomposition of the benzene ring, S−O bond and S−C bond in residues and the decomposition efficiency of resins reached 98.69 % at 800 °C. The XPS analysis showed the conversion of sulfur species in residues. The peroxide and superoxide ions in carbonate molten salt prompted the decomposition of thiophene sulfur and resulted in the formation of sulfate. The retention rate of sulfur in spent salt was 84.36 % at 800 °C. This work provided more theoretical guidance for the treatment of resins and technical support for the sustainable development of nuclear industry.     

Synthesis and structure of antimony iodide complexes: [Ph3MeP] + 2 [SbI5]2−, [Ph3MeP] + 3 [Sb3I12]3−·Me2C=O, [Ph3MeP] + 3 [Sb3I12]3−, and [Ph3MeP] + 3 [Sb2I9]3−

Complexes with antimony-containing anions, [Ph₃MeP] ₊ ² [SbI₅]^2? (I), [Ph₃MeP] ₊ ² [Sb₃I₁₂]^3? (II), [Ph₃MeP] ₊ ³ [Sb₃I₁₂]^3? · Me₂C=O (III), and [Ph₃MeP] ₊ ³ [Sb₂I₉]^3? (IV), were synthesized by reacting triphenylmethylphosphonium iodide with antimony iodide. The central atom in the cations of the complexes has a distorted tetrahedral coordination. In the trinuclear anions of complexes II and III, each of the terminal SbI₃ groups is bound to the central Sb atom through two μ₂- and one μ₃ iodine bridges (SbSbSb angles are 103.0° and 102.2°, respectively). In the binuclear anion of complex IV, antimony atoms are linked with each other via three bridging iodine atoms.     

Extreme differences in oxidation states: synthesis and structural analysis of the germanide oxometallates A10[Ge9]2[WO4] as well as A(10+x)[Ge9]2[W(1–x)Nb(x)O4] with A = K and Rb containing [Ge9]4- polyanions

Semitransparent dark-red or ruby-red moisture- and air-sensitive single crystals of A(10+x)[Ge(9)](2)[W(1-x)Nb(x)O(4)] (A = K, Rb; x = 0, 0.35) were obtained by high-temperature solid-state reactions. The crystal structure of the compounds was determined by single-crystal X-ray diffraction experiments. They crystallize in a new structure type (P2(1)/c, Z = 4) with a = 13.908(1) ?, b = 15.909(1) ?, c = 17.383(1) ?, and β = 90.050(6)° for K(10.35(1))[Ge(9)](2)[W(0.65(1))Nb(0.35(1))O(4)]; a = 14.361(3) ?, b = 16.356(3) ?, c = 17.839(4) ?, and β = 90.01(3)° for Rb(10.35(1))[Ge(9)](2)[W(0.65(1))Nb(0.35(1))O(4)]; a = 13.8979(2) ?, b = 15.5390(3) ?, c = 17.4007(3) ?, and β = 90.188(1)° for K(10)[Ge(9)](2)WO(4); and a = 14.3230(7) ?, b = 15.9060(9) ?, c = 17.8634(9) ?, and β = 90.078(4)° for Rb(10)[Ge(9)](2)WO(4). The compounds contain discrete Ge(9)(4-) Wade's nido clusters and WO(4)(2-) (or NbO(4)(3-)) anions, which are packed according to a hierarchical atom-to-cluster replacement of the Al(2)Cu prototype and are separated by K and Rb cations, respectively. The alkali metal atoms occupy the corresponding tetrahedral sites of the Al(2)Cu prototype. The amount of the alkali metal atoms on these diamagnetic compounds corresponds directly to the amount of W substituted by Nb. Thus, the transition metals W and Nb appear with oxidation numbers +6 and +5, respectively, in the vicinity of a [Ge(9)](4-) polyanion. The crystals of the mixed salts were further characterized by Raman spectroscopy. The Raman data are in good agreement with the results from the X-ray structural analyses.     

K4H2[PMo9V3O40]·10H2O的合成及其晶体结构

采用低温技术,用 X 射线单晶衍射法测定了标题化合物的结构.晶体属 P4/mnc 空间群,a=12.515(3),c=17.636(7),Z=2.用788个独立可观测反射精修所有结构参数得 R=0.061.钼钒磷杂多酸阴离子中,PO_4四面体是无序的,P—O 键长1.54.M(Mo,V)是6配位,M—O 键长1.62—2.48.K 是7配位,K—O 键长2.84—3.10.     

The Crystal and Electronic Structure of A Reticular Type Mo-Fe-S Cluster Compound [Et_4N]_4[Mo2Fe_4S_9(SCH_2CH_2S)_2]

The single crystal of [Et4N]4 [MO2Fe4S9(SCH2CH2S)2] was obtainedby reaction of (NH4)2HoS4, FeCl3 , HSCH2CH2SH and Et4 NBr in CH3CN and MeOH-MeONa. Cluster compound [Et4N]4 [Mo2Fe4S9(SCH2CH2S)2] crystal -Lized in the monoclinic space group C2/c with unit cell parameters:a = 17. 672(2)A, b = 33. 851(4)A, c = l3. 900(3)A, β=135.11(4)°, V=5868.8 (3.9)A3 and Z = 4. On the basis of 3514 unique data (I>2σ(I)) the structure was refined to R = 0.0575. The anion [Mo2Fe4S9(SCH2CH2S)2]4-of the cluster compound includes doubly bridging (μ2-S), triply bridging (μ3-S) and quadruply bridging (μ4 -S) . The structrue analysis gives a rule with bond lengths decreasing in the order of Fe-(μ4-S)> Fe-(μ3-s)> Fe-(μ2 -s) and EHMO calculation gives the other rule with bond order increasing in the order of Fe-(μ4-S)< Fe-(μ3-S)相似文献   

The first decaruthenium hydrido cluster: synthesis and crystal structure of [N(PPh3)2]2[Ru10C(CO)24]·C6H14 and [N(PPh3)2][HRu10C(CO)24]

X-ray structural studies of new thermolysis products from the reaction of Ru₃(CO)₁₂ in heptane in the presence of 1,3,5-trimethylbenzene (mesitylene) confirm that they are the decaruthenium carbido-cluster dianion [Ru₁₀C(CO)₂₄]²⁻ (I) and the hydrido decaruthenium carbido-cluster monoanion [HRu₁₀C(CO)₂₄]⁻ (II). Both anions have the giant tetrahedron Ru₁₀ metal framework, and the monohydride provides the first example of a hydrido ligand in a tetrahedral Ru₄ cavity.     

X-ray structural study of the first bicluster π-arene complex [η6-PhCo4(CO)9]2CH2 and binuclear complex [η6-PhCr(CO)3]2CH2

It has been established by X-ray structural study that the bicluster cobalt -arene complex of diphenylmethane [⁶-PhCo₄CO₉]₂CH₂ and binuclear complex [⁶-PhCr(CO)₃]₂CH₂ have ans-trans-s-trans conformation in their crystals.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1111–1117, June, 1995.This work was supported by the Russian Foundation for Basic Research (Projects No. 93-03-4028 and 94-03-08338).     

Synthesis and physicochemical study of diazabicycloundecene hexamolybdochromate [C9H16N2]H3[CrMo6O18(OH)6] · 2H2O

Quinazoline hexamolybdochromate [C₉H₁₆N₂]H₃[CrMo₆O₁₈(OH)₆] · 2H₂O has been synthesized and studied by mass spectroscopy, X-ray powder diffraction, thermogravimetry, and IR and NMR spectroscopy. The compound crystallizes in triclinic system with the unit cell parameters a = 15.06 Å, b = 13.08 Å, c = 8.17 Å, α = 59.85°, β = 123.15°, γ = 107.01°, V = 1165.62 ų, ρ_pycn = 3.58 g/cm³, and Z = 2.     

Synthesis and Crystal Structure of the Mixed-quadriligand Bismuth Complex [Bi(S2CNEt2)2(NO3)]·[1,10-Phen]

The mixed-quadriligand bismuth complex [Bi(S2CNEt2)2(NO3)]([1,10-Phen] has been synthesized, and its crystal structure was determined by X-ray single-crystal diffraction. The crystal belongs to monoclinic, space group P21/n with a = 10.074(17), b = 15.05(2), c = 18.99(3)(°A), β = 98.85(3)o, V = 2845(8)(°A)3, Z = 4, F(000) = 1464, Dc = 1.746 g/cm3, μ = 6.523 mm-1, R = 0.0333 and wR = 0.0703. In this complex, the bismuth atom is eight-coordinated in a capped distorted pentagonal bipyramidal geometry.     

Crystal and molecular structure of the [Nd2(H2O)8(C6F5COO)6]·2H2O Compound

A compound with the composition Nd(C₆F₅COO)₃· H₂O (I) is prepared. Single crystals are grown, and their single crystal XRD analysis of the Nd₂(H₂O)₈(C₆F₅COO)₆]·2H₂O (II) compound is performed. The crystals are triclinic: a = 7.693(2) Å, b = 9.394(2) Å, c = 18.203(4) Å, α = 81.91(3)°, β = 84.41(3)°, γ = 88.97(3)°, Z = 1, d _x = 2.223 g/cm³. The structure is composed of symmetrical molecules of the binuclear [Nd₂(H₂O)₈(C₆F₅COO)₆] complex and crystallization water molecules. The C₆F₅COO^- ligands are monodentate and tridentate bridging- chelating, which results in a closure of two four-membered chelate cycles NdO₂C and a four-membered metal cycle Nd₂O₂. The NdO₉ polyhedron is a distorted one-capped tetragonal antiprism.     

First example of the cluster ammine complex [Re6Se7Br(NH3)6]3+: synthesis and structure of the [Re6Se7Br(NH3)6][Re6Se7BrBr6]·12H2O salt

The reaction of Cs₃[Re₆Se₇BrBr₆] with aqueous ammonia afforded the octahedral rhenium ammine cluster complex cation [Re₆Se₇Br(NH₃)₆]³⁺. This cation crystallized as the [Re₆Se₇Br(NH₃)₆][Re₆Se₇BrBr₆]·12H₂O compound. The crystal structure of this compound was established. The presence of the NH₃ ligands in the coordination environment about the Re atom was confirmed by thermogravimetry, vibrational spectroscopy, and high-resolution mass spectrometry. The resulting compound is the first example of salts composed of the cluster cation and cluster anion possessing the same {Re₆Se₇Br} cluster core.