Kristallstruktur von (NMe4)2[Re3Br11(H2O)] [Re3Br9(H2O)3](H2O)2

Crystal Structure of (NMe₄)₂[Re₃Br₁₁(H₂O)] [Re₃Br₉(H₂O)₃](H₂O)₂ . (NMe₄)₂[Re₃Br₁₁(H₂O)] [Re₃Br₉(H₂O)₃](H₂O)₂ crystallizes from hydrobromic acid solution of Re₃Br₉ · 2 H₂O and NMe₄Br at 0 – 5°C. The crystal structure (monoclinic; P2₁/m (Nr. 11); a = 967.9(3); b = 1 529.7(4); c = 1 710.9(4) pm; β = 91.66(2)°; Z = 2; R = 0.113; R_w = 0.068) has been determined from four-circle diffractometer data. The structure contains two different cluster units of trivalent rhenium, isolated anionic [Re₃Br₁₁(H₂O)]^2? units and neutral cluster units that are connected through crystal water molecules to chains{[Re₃Br₉(H₂O)₃](H₂O)₂}.     

Kristallstrukturen von Säurehydraten und Oxoniumsalzen. 36 [1]. Selensäure-Tetrahydrat. Ionisch gemäß (H5O2)2SeO4 in einer orthorhombischen sowie einer tetragonalen Form

Crystal Structures of Acid Hydrates and Oxonium Salts. 36 [1]. Selenic Acid Tetrahydrate. Ionic as (H₅O₂)₂SeO₄ in an Orthorhombic as well as a Tetragonal Form Low-melting selenic acid tetrahydrate has been studied for the first time by crystal structure analysis. Two forms have been observed, an orthorhombic one with space group Pnma and Z = 4 and a tetragonal one with space group P4 2₁c and Z = 2. The lattice parameters at ?150°C are a = 6.130(3), b = 12.776(6) and c = 9.299(5) Å for the orthorhombic and a = 7.676(4) and c = 6.378(3) Å for the tetragonal form. Both forms are oxonium salts, corresponding to (H₅O₂)₂SeO₄. The ions are hydrogen-bonded into a three-dimensional array. The bonds within the diaquahydrogen cations have O ?O distances of 2.422(5) and 2.425(4) Å. The tetragonal form is isotypic to the tetrahydrate of sulfuric acid.     

Synthesis,Crystal Structure and Properties of Novel Composite Complex: [La(Nmp)4(H2o)4][HsiMo12O40]·2nmp·H2o

A new composite complex of [La(NMP)₄(H₂O)₄][HSiMo₁₂O₄₀]·2NMP·H₂O (NMP = N-methyl-2- pyrrolidone) was synthesized and characterized by IR, UV, ESR, TG-DTA and single crystal structural analysis. The water and organic ligands (NMP) coordinate directly with La(III) to form a dodecahedral complex and the SiMo₁₂O^4? ₄₀ anion is the counter ion. IR and X-ray analysis show that there is strong interaction between the polyoxometalate and organic donors. The complex is strongly photosensitive under irradiation with sunlight, resulting in a charge-transfer complex by oxidation of the N-methyl-2-pyrrolidone and reduction of the polyoxometalate. Low temperature ESR spectra indicate thermal electron delocalization among the Mo atoms in the title compound.     

Neue ternäre KäfigVerbindungen in den Systemen Barium–2B(3B)-Element-Germanium

New Ternary Clathrate Compounds in the Systems Barium–2B(3B)-Elements–Germanium In the ternary systems Barium–2B(3B) elements–germanium new ternary variants of the K₈Ge₄₆ clathrate structure and hints to clathrates of another composition have been found. Results of structure determination of Ba₈Cd₈Ge₃₈ (cubic, a = 1096.2 pm; space group Pm3n) show a prevailing ordered distribution of Cd and Ge in the sites of the structure building atoms. According to electron balance Ba₈Cd₈Ge₃₈ can be assumed to be a ternary Zintl compound.     

CRYSTAL STRUCTURE AND POWDER DIFFRACTION OF Na5Y（WO4）4

<正> Title compound Na5Y (WO4)4 (Mr = 1195. 24) crystallizes in the space group I41/a with the cell parameters a= 11. 447(7), c= 11. 336(1) A , Z = 4, V = 1485(2) A3, A = 5. 34 g/cm3. A(MoKα) = 0. 71069 A. F(000) = 2702, final R = 0. 045,Rw = 0. 054 for 936 observed reflections with I≥3σ(I). The title compound has a scheelite structure.In this paper, we also give the X-ray powder diffraction data of Na5Y(WO4)4 obtained by using a D/max-ra type diffractometer.     

The Ternary Stannides MgRuSn4 and MgxRh3Sn7—x (x = 0.98—1.55)

The magnesium transition metal stannides MgRuSn₄ and Mg_xRh₃Sn_7—x (x = 0.98—1.55) were synthesized from the elements in glassy carbon crucibles in a water‐cooled sample chamber of a high‐frequency furnace. They were characterized by X‐ray diffraction on powders and single crystals. MgRuSn₄ adopts an ordered PdGa₅ type structure: I4/mcm, a = 674.7(1), c = 1118.1(2) pm, wR2 = 0.0506, 515 F² values and 12 variable parameters. The ruthenium atoms have a square‐antiprismatic tin coordination with Ru—Sn distances of 284 pm. These [RuSn_8/2] antiprisms are condensed via common faces forming two‐dimensional networks. The magnesium atoms fill square‐prismatic cavities between adjacent [RuSn₄] layers with Mg—Sn distances of 299 pm. The rhodium based stannides Mg_xRh₃Sn_7—x crystallize with the cubic Ir₃Ge₇ type structure, space groupe Im3m. The structures of four single crystals with x = 0.98, 1.17, 1.36, and 1.55 have been refined from X‐ray diffractometer data. With increasing tin substitution the a lattice parameter decreases from 932.3(1) pm for x = 0.98 to 929.49(6) pm for x = 1.55. The rhodium atoms have a square antiprismatic tin/magnesium coordination. Mixed Sn/Mg occupancies have been observed for both tin sites but to a larger extend for the 12d Sn2 site. Chemical bonding in MgRuSn₄ and Mg_xRh₃Sn_7—x is briefly discussed.     

SrPtIn,Sr2Pt3In4, and Ca2Au3In4 – Alkaline Earth Compounds with Complex Three-Dimensional [PtIn], [Pt3In4], and [Au3In4] Polyanions

Single phase SrPtIn, Sr₂Pt₃In₄ and Ca₂Au₃In₄ were prepared by high-frequency melting of the elements in water-cooled glassy carbon crucibles. X-ray diffraction of powders and single crystals yielded Pnma, oP12, a = 758.57(9) pm, b = 451.52(6) pm, c = 846.0(2) pm, wR2 = 0.0937, 467 F² values, 20 variables for SrPtIn, P62m, hP36, a = 1465.9(2) pm, c = 448.24(6) pm, wR2 = 0.0722, 1059 F² values, 44 variables for Sr₂Pt₃In₄ and Pnma, oP36, a = 1463.6(4) pm, b = 443.23(9) pm, c = 1272.3(2) pm, wR2 = 0.0694, 1344 F² values, 56 variables for Ca₂Au₃In₄. SrPtIn adopts the TiNiSi type structure. The indium atoms have a distorted tetrahedral platinum coordination. These InPt_4/4 tetrahedra are edge- and corner-shared, forming a three-dimensional [PtIn] polyanion in which the strontium atoms are embedded. Sr₂Pt₃In₄ crystallizes with the Hf₂Co₄P₃ type structure with the more electronegative platinum atoms occupying the phosphorus sites while the indium atoms are located on the cobalt positions. Ca₂Au₃In₄ is a new site occupancy variant of the YCo₅P₃ type. Gold atoms occupy the phosphorus sites and indium the cobalt sites, but one cobalt site is occupied by calcium atoms leading to the composition Ca₂Au₃In₄. Common geometrical motifs of both structures are condensed, platinum(gold)-centered trigonal prisms formed by the alkaline earth and indium atoms. The platinum (gold) and indium atoms form complex three-dimensional [Pt₃In₄] and [Au₃In₄] polyanions, respectively. The alkaline earth cations are located in distorted hexagonal tubes.     

Y[PS4]: An Unusual ABX4 Compound with a PtS-Related Crystal Structure

Pale yellow single crystals of Y[PS₄] (tetragonal, I4₁/acd; a = 1065.72(5), c = 1899.23(9) pm, Z = 16) can easily be obtained by the reaction of the elements without using a flux to avoid the entrapment of alkali metals. The structure consists of isolated [PS₄]^3- tetrahedra (d(P-S) = 203 pm, 4×) each surrounded by four Y³⁺ cations resulting in a S₄N₄-analogous arrangement of the metal cations and sulfur atoms about the phosphorus in the center of this polyhedron. Both crystallographically different Y³⁺ cations are eightfold coordinated by sulfur in the shape of trigonal dodecahedra (d(Y-S) = 280 - 300 pm, CN = 8) which in turn belong to four exclusively edge-attached [PS₄]^3- tetrahedra. These build up a distorted cubic closest packing where the Y³⁺ cations are situated in one half of the tetrahedral holes the same way as S^2- in the Pt²⁺ arrangement of the PtS-type structure.     

Hydrogendiazid Synthese und Kristallstruktur von PPh4[N3HN3]

Hydrogen Diazide – Synthesis and Crystal Structure of PPh₄[N₃HN₃] PPh₄[N₃HN₃] has been prepared from PPh₄N₃ and Me₃SiN₃ by the reaction with water or ethanol forming colourless nonexplosive crystal needles, which were characterized by IR spectroscopy and by a crystal structure determination. Space group C2/c, Z = 12, lattice dimensions at –70 °C: a = 3782.4(3), b = 727.8(2), c = 2512.4(2) pm, β = 110.13(1)°, R = 0.0841. The [N₃HN₃]^– ion is characterized by an asymmetric N–H…N hydrogen bridge with a NN distance of 272(1) pm.     

Kristallstruktur und Bindungsverhältnisse von [W(O-t-Bu)4(THF)]

Crystal Structure and Bonding of [W(O- t -Bu)₄(THF)] [W(O-t-Bu)₄(THF)] is formed from [WCl₄(SEt₂)₂] and LiO-t-Bu in boiling tetrahydrofuran and characterized by a crystal structure analysis. The compound crystallizes in the tetragonal space group I4 with Z = 2 and the lattice dimensions a = b = 1158.8(2) and c = 940.7(2) pm at 80 °C. [W(O-t-Bu)₄(THF)] shows the molecular structure of a tetragonal pyramid with the oxygen atom of the THF molecule in the apical position. Surprisingly, the tungsten atom is deflected by 34 pm from the plane of the four oxygen atoms of the O-t-butyl groups against the direction of the W–O(THF) bond. The bonding modes are discussed on the basis of MO considerations.     

Synthesis,Crystal Structures and Magnetic Properties of Ion-Pair Complexes with Hydrogen Bonding Network: Ln(DMA)n(H2O)m Cr(CN)6· xH2O(Ln = Sm,Gd: n = 4, m = 3, x = 2; Ln = Er: N = 3, m = 4, x = 0)

Three ion-pair Ln-Cr complexes [Sm(DMA)₄(H₂O)₃][Cr(CN)₆] · 2H₂O, [Gd(DMA)₃(H₂O)₄][Cr(CN)₆] · 2H₂O and [Er(DMA)₃(H₂O)₄][Cr(CN)₆] (DMA = dimethylacetamide) have been synthesized. X-ray structure analyses of the title complexes revealed that there is a hydrogen-bonding network through CN groups and H₂O molecules. Variable temperature magnetic susceptibilities indicate weak antiferromagnetic interactions between cation and anion pairs moderated through the hydrogen bonding network.     

CRYSTAL AND MOLECULAR STRUCTURE OF 4-CHLORO-5- ETHYL-5-METHYL-3-PHENYL-1, 3, 4-DIAZAPHOSPHOLIDIN-2-THIONE-4-SULFIDE

<正> Crystal of the title compound Mr=304. 80 belongs to the triclinic, space group P1, with a = 7. 282)2), b=9. 064(2), c=11. 737(5) A , α=75. 79 (3), β=78. 70(3), γ=88. 49(2)°, V-736. 21 A3, Z=2, Dx = l. 375 g/cm3. The final refinement is converged with R=0. 062 and Rw= 0. 069.The five-membered heterocycle is in envelope conformation. The P - N bond length (1. 68(1)) indicates that the dπ-Pπ bond between P and N of the title compound is stronger than that of the corresponding 4-phenyl compound.     

Self-Assemblies of Extended Hydrogen-Bonded Arrays Using 1,4-Butanebisphosphonic Acid as a Versatile Building Block

Two organic salts of 1,4-butanebisphosphonic acid, bis(ethylenediammonium) butanebisphosphonate hydrate ( 1 ) and bis(hexamethylenediammonium) butanebisphosphonate hydrate ( 2 ), have been structurally characterized using single-crystal x-ray diffraction analyses. Compound 1 exhibits a H-bonded pillared bilayered structure, in which etheylenediammonium cation acts as a spacer between the anions resulting in the formation of two types of cavities. The larger cavity is filled by four water molecules though having hydrophobic character. Thus, the material behaves as a nanoporous organic solid. Compound 2 shows a multidimensional hydrogen bonding networks: one-dimensional arrays parallel to the b axis and two-dimensional sheets parallel to the ab plane. The N--H·;·;·;O--P hydrogen bonds, forming H-bonded supramolecular networks, are regarded to be strong and directional hydrogen bonds.     

First Characterization of an Extended Ammonium‐Ammonia Complex [{NH4(NH3)4}+(μ‐NH3)2] in the Crystal Structure of [NH4(NH3)4][Co(C2B9H11)2] · 2 NH3

The compound [NH₄(NH₃)₄][Co(C₂B₉H₁₁)₂] · 2 NH₃ ( 1 ) was prepared by the reaction of Na[Co(C₂B₉H₁₁)₂] with a proton‐charged ion‐exchange resin in liquid ammonia. The ammoniate 1 was characterized by low temperature single‐crystal X‐ray structure analysis. The anionic part of the structure consists of [Co(C₂B₉H₁₁)₂]^‐ complexes, which are connected via C‐H···H‐B dihydrogen bonds. Furthermore, 1 contains an infinite equation/tex2gif-stack-2.gif[{NH₄(NH₃)₄}⁺(μ‐NH₃)₂] cationic chain, which is formed by [NH₄(NH₃)₄]⁺ ions linked by two ammonia molecules. The N‐H···N hydrogen bonds range from 1.92 to 2.71Å (DHA = Donor···Acceptor angles: 136‐176°). Additional N‐H···H‐B dihydrogen bonds are observed (H···H: 2.3‐2.4Å).     

Urea-Functionalized Fe4L6 Cages for Supramolecular Gold Catalyst Encapsulation to Control Substrate Activation Modes

The excellent catalytic performances of enzymes in terms of activity and selectivity are an inspiration for synthetic chemists and this has resulted in the development of synthetic containers for supramolecular catalysis. In such containers the local environment and pre-organization of catalysts and substrates leads to control of the activity and selectivity of the catalyst. Herein we report a supramolecular strategy to encapsulate single catalysts in a urea-functionalized Fe₄L₆ cage, which can co-encapsulate a functionalized urea substrate through hydrogen bonding. Distinguished selectivity is obtained, imposed by the cage as site isolation only allows catalysis through π activation of the substrate and as a result the selectivity is independent of catalyst concentration. The encapsulated catalyst is more active than the free analogue, an effect that can be ascribed to transitionstate stabilization rather than substrate pre-organization, as revealed by the MM kinetic data. The simple strategy reported here is expected to be of general use in many reactions, for which the catalyst can be functionalized with a sulfonate group required for encapsulation.     

Synthesis and Structure of BaPtIn3 and BaTl0.63In3.33. Two Contrasting Examples of Preferential Site Occupation in BaAl4‐Type Structures

The title compounds have been synthesised by high temperature means and characterized by single crystal X‐ray diffraction analysis. The compounds crystallize in the tetragonal structure type of BaAl₄, I4/mmm, Z = 2 (a = 4.8130(7), 5.0196(8) Å; c = 11.669(2), 11.900(3) Å for BaPtIn₃ and BaTl_0.63In_3.37, respectively).Platinum and thallium randomly substitute for 50 % of the In in the apical 4e and for 30 % in the basal 4d positions in the two networks, respectively. Consistent with both size and relative electronegativity factors, the basal positions in BaAl₄‐type structure are appropriate for substitution by dimensionally and chemically similar atoms (Tl), which is different from the apical sites in which electronegativities or bond strengths are more important (Pt).     

Synthesis and Crystal Structure of Ammonium Cyanimide NH4HCN2

The compound NH₄HCN₂ ( 1 ) was prepared by the reaction of H₂CN₂ with liquid ammonia. The ammonium salt 1 was characterized by a low temperature single‐crystal X‐ray structure analysis. The anionic part of the structure consists of HCN₂^? anions, which are connected via N–H···N bonds (H···N distance: 2.47Å, DHA: 165°). The N–H···N hydrogen bonds of the ammonium ion to the anions range from 2.00 to 2.14Å (DHA = Donor···Acceptor angles: 165–176°), all N–H···N interactions together give rise to a three‐dimensional network. 1 decomposes quantitatively to dicyandiamide at room temperature.     

Organophosphorverbindungen mit tertiären Alkylsubstituenten. V. Synthese und Reaktionen triphenylmethyl-substituierter Dihalogenphosphine TrtPX2 (Trt = Triphenylmethyl-, X = F,Cl, Br); Kristallstrukturen von Triphenylmethyldichlorphosphin TrtPCl2 und Triphenylmethylthiophosphonsäuredifluorid TrtP(:S)F2

Organophosphorus Compounds with Tertiary Alkyl Substituents. V Synthesis and Reactions of triphenylmethyl-substituted Dihalophosphines TrtPX₂ (Trt = Triphenylmethyl-, X = F, Cl, Br); X-Ray-Crystal Structures of Triphenylmethyl dichlorophosphine TrtPCl₂ and Triphenylmethylthiophosphonic Difluoride TrtP(:S)F₂ The dihalophosphines TrtPX₂ (X = Cl: 2 , Br: 3 ) were obtained in the reaction of TrtP(:O)(H)OH 1 with PCl₃ and PBr₃, respectively. 2 could also be synthesized from TrtMgCl and PCl₃, 3 from 2 /Me₃SiBr. TrtPF₂ 4 was prepared by the fluorination of 2 with NaF or from TrtLi/PF₂Cl. The reduction of 2 with LiAlH₄ or HSiCl₃/NaOH_(aq) yielded TrtPH₂ 6 , the reaction with NaF/H₂O led to TrtP(:O)(H)F 9 . (TrtPCl₂)₂Mo(CO)₄ 10 was observed in the system 2 /(NOR)Mo(CO)₄ by ³¹P-NMR-spektroscopy. 4 was oxidized with TrtN₃ or sulfur to give the λ⁴P(V)-compounds TrtP(:NTrt)F₂ 11 and TrtP(:S)F₂ 12 respectively. Whereas the oxidation of 4 and ^tBuPF₂ with tetrachloro-o-benzoquinone (TOB) led to the corresponding difluorophosphoranes 13 and 14 , no reaction could be observed when 4 was treated with hexafluoroacetone (HFA) at elevated temperatures. In a fashion typical of difluorophosphines, 4 reacted with (COD)MCl₂ (M = Pd, Pt) or (NOR)Mo(CO)₄ to give the co-ordination compounds 15, 16 and 18 a . Upon heating cis-(TrtPF₂)₂Mo(CO)₄ 18 a isomerized to give the thermodynamically favoured trans-complex 18 b . The reaction of 4 with Fe₃(CO)₁₂ led to (TrtPF₂)Fe(CO)₄ 17 as the only phosphorus-containing product, instead of the phosphinidene complex TrtP(μ-F)₂Fe₃(CO)₉. X-ray structure analyses of compounds 2 and 12 were carried out. The P? C bond in 2 is unusually long (193.3 pm). The F? P? F angle in 12 is narrow (98.14°).     

Neue mehrkernige Organozinn(IV)–Stickstoff‐Verbindungen. Synthese und Kristallstrukturen von [(PhSn)4(NPh)5Cl2] und [(MeSn)4(NHPh)4(NPh)4]

New Polynuclear Organotin(IV)–Nitrogen Compounds. Synthesis and Crystal Structures of [(PhSn)₄(NPh)₅Cl₂] and [(MeSn)₄(NHPh)₄(NPh)₄] The reaction of the organotin halides PhSnCl₃ and MeSnCl₃ with LiNHPh leads to the formation of two new nitrogen bridged organotin compounds, [(PhSn)₄(NPh)₅Cl₂] ( 1 ) and [(MeSn)₄(NHPh)₄(NPh)₄] ( 2 ). The crystal structures of 1 and 2 have been determined by low temperature X‐ray diffraction. 1 contains a bicyclic Sn₄N₅ framework, which consists of two six‐membered Sn₃N₃‐rings. All tin atoms are coordinated nearly tetrahedrally. Two tin atoms are bonded to a phenyl group and three nitrogen atoms, the other two tin atoms are coordinated by a phenyl group, two nitrogen atoms and a terminal chlorine atom. In 2 the tin atoms define the corners of a distorted square. Each edge of the square is bridged by a μ²‐NHPh and a μ²‐NPh group. The bridging NHPh and NPh groups are arranged at opposite sides of the Sn₄ plane. The tin atoms are coordinated square pyramidally by 4 nitrogen atoms and a methyl group.