Die Kristallstruktur des 1 : 1-Adduktes zwischen Antimontrichlorid und Diphenylammoniumchlorid,SbCl3 · (C6H5)2NH2+Cl−

The Crystal Structure of the 1:1 Addition Compound between Antimony Trichloride and Diphenylammonium Chloride, SbCl₃ · (C₆H₅)₂NH₂⁺Cl^? The 1:1 addition compound between antimony trichloride and diphenylammoniumchloride SbCl₃ · (C₆H₅)₂NH₂⁺Cl^? crystallizes in the monoclinic space group P2₁/n with a = 5.668(8), b = 20.480(12), c = 14.448(17) Å, β = 110.4(1)° and Z = 4 formula units. Chains of SbCl₃ molecules and anion cation chains are bridged by Cl ions and form square tubes. The coordination of the Sb atoms by Cl atoms by Cl atoms and Cl ions is distorted octahedral. Mean distances are Sb? Cl = 2.37 Å for Sb? Cl (3×), 3.09 Å for Sb…Cl^? (2×) and 3.42 Å for Sb…Cl (1×). The Sb…Cl^? contacts and hydrogen bonds NH…Cl^? at 3.15 Å generate tetrahedral coordination of the Cl ions.     

Nd2(SeO3)2(SeO4) · 2H2O – a Mixed‐Valence Compound containing Selenium in the Oxidation States +IV and +VI

Pale pink crystals of Nd₂(SeO₃)₂(SeO₄) · 2H₂O were synthesized under hydrothermal conditions from H₂SeO₃ and Nd₂O₃ at about 200 °C. X‐ray diffraction on powder and single‐crystals revealed that the compound crystallizes with the monoclinic space group C 2/c (a = 12.276(1) Å, b = 7.0783(5) Å, c = 13.329(1) Å, β = 104.276(7)°). The crystal structure of Nd₂(SeO₃)₂(SeO₄) · 2H₂O is an ordered variant of the corresponding erbium compound. Eight oxygen atoms coordinate the Nd^III atom in the shape of a bi‐capped trigonal prism. The oxygen atoms are part of pyramidal (Se^IVO₃)^2? groups, (Se^VIO₄)^2? tetrahedra and water molecules. The [NdO₈] polyhedra share edges to form chains oriented along [010]. The selenate ions link these chains into layers parallel to (001). The layers are interconnected by the selenite ions into a three‐dimensional framework. The dehydration of Nd₂(SeO₃)₂(SeO₄) · 2H₂O starts at 260 °C. The thermal decomposition into Nd₂SeO₅, SeO₂ and O₂ at 680 °C is followed by further loss of SeO₂ leaving cubic Nd₂O₃.     

Low‐Dimensional Structural Units in Amine‐Templated Uranyl Oxoselenates(VI): Synthesis and Crystal Structures of [C3H12N2][(UO2)(SeO4)2(H2O)2](H2O), [C5H16N2]2[(UO2)(SeO4)2(H2O)](NO3)2, [C4H12N][(UO2)(SeO4)(NO3)], and [C4H14N2][(UO2)(SeO4)2(H2O)]

The crystals of four amine‐templated uranyl oxoselenates(VI), [C₃H₁₂N₂][(UO₂)(SeO₄)₂(H₂O)₂](H₂O) ( 1 ), [C₅H₁₆N₂]₂[(UO₂)(SeO₄)₂(H₂O)](NO₃)₂ ( 2 ), [C₄H₁₂N][(UO₂)(SeO₄)(NO₃)] ( 3 ), and [C₄H₁₄N₂][(UO₂)(SeO₄)₂(H₂O)] ( 4 ) were prepared by evaporation from aqueous solution of uranyl nitrate, selenic acid and the respective amine. The crystal structures of all four compounds have been solved by direct methods from X‐ray diffraction data. The structure of 1 (triclinic, , a = 7.5611(16), b = 7.7650(17), c = 12.925(3) Å, α = 94.605(18), β = 94.405(17), γ = 96.470(17)°, V = 748.8(3) ų, R₁ = 0.029 for 2769 unique observed reflections) is based upon 0D‐units of the composition [(UO₂)₂(SeO₄)₄(H₂O)₄]^4?. These discrete units are composed from two pentagonal [UO₇]^8? bipyramids linked via [SeO₄]^2? tetrahedra and are unknown in structural chemistry of uranium so far. The structure of 2 (monoclinic, C2/c, a = 28.916(5), b = 8.0836(10), c = 11.9856(16) Å, β = 110.909(11)°, V = 2617.1(6) ų, R₁ = 0.035 for 2578 unique observed reflections) contains [(UO₂)(SeO₄)₂(H₂O)]^2? chains of corner‐sharing pentagonal [UO₇]^8? bipyramids and [SeO₄]^2? tetrahedra. The chains run parallel to the c axis and are arranged into layers parallel to (100). In the structure of 3 (monoclinic, C2/m, a = 21.244(5), b = 7.1092(11), c = 8.6581(18) Å, β = 97.693(17)°, V = 1295.8(4) ų, R₁ = 0.027 for 1386 unique observed reflections), pentagonal [UO₇]^8? bipyramids share corners with three [SeO₄]^2? tetrahedra each and an edge with a [NO₃]^? anion to form [(UO₂)(SeO₄)(NO₃)]^? chains parallel to the b axis. In the structure of 4 (triclinic, , a = 6.853(2), b = 10.537(3), c = 10.574(3) Å, α = 99.62(3), β = 94.45(3), γ = 100.52(3)°, V = 735.6(4) ų, R₁ = 0.045 for 2713 unique observed reflections), one symmetrically independent pentagonal [UO₇]^8? bipyramid shares corners with four [SeO₄]^2? tetrahedra to form the [(UO₂)(SeO₄)₂(H₂O)]^2? chains parallel to the a axis. A comparison to related uranyl compounds is given.     

Die Kristallstruktur des 2:1-Adduktes zwischen Antimontrichlorid und Diphenylamin, 2SbCl3 · (C6H5)2NH

The Crystal Structure of the 2:1 Addition Compound between Antimony Trichloride and Diphenylamine, 2SbCl₃ · (C₆H₅)₂NH The 2:1 molecular compound between antimony trichloride and diphenylamine, 2SbCl₃ · (C₆H₅)₂NH, crystallizes in the monoclinic space group P2₁/c with a = 7.802(2) Å, b = 9.415(3) Å, c = 26.037(8) Å, β = 91.08(2)⁰ and Z = 4. The two independent SbCl₃ molecules point with the Sb atom to a phenyl ring each of the diphenylamine molecule. Inspite of slightly different orientations the distances to the ring planes are about equal (3.08 and 3.09 Å). The conformation of the diphenylamine molecule is an intermediate between the planar and the twist form. The mean bond distance Sb? Cl is 2.37 Å. Longer Sb…Cl contacts of 3.35 to 3.50 Å and π-donor-acceptor interactions complete the distorted octahedral coordination respectively, of the and ψ-octahedral coordination, respectively, of the Sb-atoms.     

Die kristallstruktur des 2;1-Adduktes zwischen Antimontrichlorid und Diphenyl, 2SbCl3 · (C6H5)2

The Crystal Structure of the 2:1 Addition Compound between Antimony Trichloride and Diphenyl, 2SbCl₃ · (C₆H₅)₂ The 2:1 adduct of antimony trichloride with diphenyl, 2SbCl₃ · (C₆H₅)₂, crystallizes in the triclinic space group P1 with a = 13.498(5) Å, b = 7.884(2) Å, c = 9.341(3) Å, α = 86.40(2)°, β = 110.05(3)⁰, γ = 91.41(2)° and Z = 2. Each SbCl₃ molecule points to a phenyl ring of the diphenyl molecule. The distances from the two independent Sb atoms to the phenyl ring planes differ (3.26 and 3.08 Å). The torsion angle between the phenyl ring planes within the diphenyl molecule is 40.5°. The mean Sb? Cl bond distance is 2.39 Å. Longer Sb…Cl contacts of 3.44 to 3.46 Å and the π-donor-acceptor interactions complete the distorted octahedral coordination, and ψ-octahedral coordination respectively, of the Sb atoms.     

Hydrothermal Synthesis and Crystal Structures of Na2Be3(SeO3)4·H2O and Cs2[Mg(H2O)6]3(SeO3)4

The selenites, Na₂Be₃(SeO₃)₄ · H₂O and Cs₂[Mg(H₂O)₆]₃(SeO₃)₄, were synthesized under hydrothermal conditions. The crystal structures of Na₂Be₃(SeO₃)₄ · H₂O and Cs₂[Mg(H₂O)₆]₃(SeO₃)₄ were determined by single‐crystal X‐ray diffractions. Na₂Be₃(SeO₃)₄ · H₂O crystallizes in the triclinic space group P1 (no. 2) with unit cell parameters a = 4.8493(9), b = 12.013(2), c = 12.077(2) Å, and Z = 2, whereas Cs₂[Mg(H₂O)₆]₃(SeO₃)₄ crystallizes in the monoclinic space group C2/m (no. 12) with lattice cell parameters a = 12.596(6), b = 7.297(4), c = 16.914(8) Å, and Z = 2. Na₂Be₃(SeO₃)₄ · H₂O features a three‐dimensional open framework structure formed by BeO₄ tetrahedra and SeO₃ trigonal pyramids. Na cations and H₂O molecules are located in different tunnels. Cs₂[Mg(H₂O)₆]₃(SeO₃)₄ has a structure composed of isolated [Mg(H₂O)₆] octahedra and SeO₃ trigonal pyramids interacted by hydrogen bonds, and Cs cations are resided in‐between. Both compounds were characterized by thermogravimetric analysis and FT‐IR spectroscopy.     

Die Kristallstrukturen von [Cu2Cl2(AA · H+)2](NO3)2 und [AA · H+]Pikr− (AA · H+ = Allylammonium; Pikr− = Pikrat)

The Crystal Structures of [Cu₂Cl₂(AA · H⁺)₂](NO₃)₂ and [AA · H⁺]Picr^? (AA · H⁺ = Allylammonium; Picr^? = Picrat) By an alternating current electro synthesis the crystal-line π-complex [Cu₂Cl₂(AA · H⁺)₂](NO₃)₂ has been obtained from CuCl₂ · 2H₂O, allylamine (AA), and HNO₃ in ethanolic solution. X-ray structure analysis revealed that the compound crystallized in the monoclinic system, space group P2₁/a, a = 7.229(3), b = 7.824(3), c = 26.098(6) Å, γ = 94.46(5)°, Z = 4, R = 0.025 for 2 023 reflections. The crystal structure is built up of Cu_nCl_n chains which are connected by π-bonding bidentate AA · H⁺ …? ON(O)O …? H⁺ · AA units. For comparision with the above complex the structure of [AA · H⁺]Picr^? (Picr^? = picrate anion) is also reported.     

Crystal Structures of Benzenselenonylamides C6H5SeO2NXY,X, Y = H,CH3, at 120 K. Twinned structure of C6H5SeO2NH2

The X-ray structures at 120 K of C₆H₅SeO₂N(CH₃)₂ ( 1 ) and C₆H₅SeO₂NHCH₃ ( 2 ) were determined from single crystal data, the structure of C₆H₅SeO₂NH₂ ( 3 ) was determined from a twin. The structure of ( 1 ) is composed of isolated molecules, that of ( 2 ) of dimers via H-bonds and the structure of ( 3 ) forms infinite chains. The Se? N lengths are 1.815(2) Å for ( 1 ), 1.791(2) Å for ( 2 ), and 1.781(6) Å for ( 3 ).     

Crystal and molecular structure of bis(N,N-dipropyl-N′-diphenoxythiophosphoryl-thioureato) nickel(II) [(C6H5O)2P(S)NC(S)N(C3H7)2]2Ni

The Ni complex [C₆H₅O₂P(S)N(C₃H₇₂]₂Ni is monoclinic, space group P2₁/n with a = 8.890(3), b = 21.692(5), c = 11.670(4) Å, β = 108.35(5)°, V = 2136(1) ų, F(000) = 916, M_r = 534.01, Z = 2, D_m = 1.318, D_x = 1.358 Mg m^?3, graphite monochromatized MoKα ^? radiation, π = 0.7107 Å, μ = 0.76 mm^?1, T = 293 K. The structure was solved by a heavy atom method and refined to R = 0.044 for 3095 independent reflexions. The Ni atom lies in the centre of symmetry and is coordinated by four S atoms of the two molecules of the ligand in a planar arrangement. Ni? S bond lengths are 2.205 and 2.226 Å resp., the angles S? Ni? S are 97.65 and 82.35° resp.     

Untersuchungen über S?H …︁ S-Wasserstoffbrücken Die Kristallstruktur der Diphenyldithiophosphinsäure bei 140 und 293 K

Die Kristallstruktur der Diphenyldithiophosphinsäure (C₆H₅)₂P(S)SH wurde röntgenographisch bei tiefer Temperatur und Normaltemperatur aus Einkristalldiffraktometerdaten bestimmt und bis zu R-Werten von 0,037 (140 K, (sin Θ)/λ < 0,81 Å^?1) und 0,035 (293 K, (sin Θ)/λ < 0,64 Å^?1) verfeinert. Die Verbindung kristallisiert in der monoklinen Raumgruppe P2₁/c mit den bei 140 K (in Klammern: 293 K) gemessenen Gitterkonstanten a = 9,824(3) (9,887), b = 10,061(3) (10,175), c = 14,342(4) (14,433) Å, β = 122,08(3) (121,73)° und V = 1201,1 (1234,9) ų, Z - 4. Im Kristall sind individuelle Moleküle über fast lineare S? H…?S-Wasserstoffbrückenbindungen zu schraubenförmig gewundenen Ketten verknüpft. Bei 140 K beträgt der S…?S-Abstand innerhalb der Brücke 3,790(1) Å; die weiteren geometrischen Daten der Wasserstoffbrücke sind: d(S? H): 1,25(2), d(S…?H): 2,56(2), d(P? S): 2,077(1), d(P?S): 1,954(1) Å, ? (S? H…?S): 169,5(14), ? (P? S…?S): 98,87(2), ? (P?S…?S): 96,65(2)°. Investigations on Compounds Containing S? H…?S Hydrogen Bonds. Crystal Structure of Diphenyldithiophosphinic Acid at 140 and 293 K The crystal structure of diphenyldithiophosphinic acid (C₆H₅)₂P(S)SH was determined from X-ray diffraction data collected at 140 and 293 K and was refined to R factors of 0.037 (140 K, (sin Θ)/λ < 0.81 Å^?1) and 0.035 (293 K, (sin Θ)/λ < 0.64 Å^?1) respectively. The compound crystallizes in the monoclinic space group P2₁/c with unit cell parameters at 140 K (in parentheses: at 293 K): a = 9.824(3) (9.887), b = 10.061(3) (10.175), c = 14.342(4) (14.433) Å, β = 122.08(3) (121.73)° and V = 1201.1 (1234.9) ų, Z = 4. In the crystalline state individual molecules are linked together by nearly linear S? H…?S hydrogen bonds so that endless helical chains are formed. At 140 K the S…?S distance within the hydrogen bond is 3.790(1) Å; the other distances and angles associated with the bridge are: d(S? H): 1,25(2), d(S…?H): 2,56(2), d(P? S): 2,077(1), d(P?S): 1.954(1) Å, ? (S? H…?S): 169.5(14), ? (P? S…?S): 98.87(2), ? (P? S…?S): 96.65(2)°.     

Darstellung sowie Kristall- und Molekülstruktur von 2 (C6H5)3PO · (COOH)2

Preparation, Crystal and Molecular Structure of 2 (C₆H₅)₃PO · (COOH)₂ 2(C₆H₅)₃PO · (COOH)₂ crystallizes from a solution of oxalic acid and (C₆H₅)₃PO in methanol. Crystal data: space group P2₁/c (monoclinic) with a = 907.4(2), b = 1035.4(3), c = 1797.9(8) pm, β = 75.20(1)° and Z = 2; d (calc./obs.) = 1.27/1.31 g cm^?;3; V_cell = 1633.1 × 10⁶ pm³. The structure was determined by direct methods from 3006 independent reflections and has been refined by full matrix least squares to R = 0.049. In the compound one molecule of trans-oxalic acid and two symmetrically dependent (C₆H₅)₃PO units are linked by short O…?H–O bridges distances and angles see above.     

Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H3O)2[(UO2)2(SO4)3­(H2O)]·7H2O and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O,and a Uranyl Selenate‐Selenite [C5H6N][(UO2)(SeO4)(HSeO3)]

Two uranyl sulfate hydrates, (H₃O)₂[(UO₂)₂(SO₄)₃(H₂O)] · 7H₂O (NDUS) and (H₃O)₂[(UO₂)₂(SO₄)₃(H₂O)] · 4H₂O (NDUS1), and one uranyl selenate‐selenite [C₅H₆N][(UO₂)(SeO₄)(HSeO₃)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L ‐cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P2₁/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4) Å, β = 112.778(1)°, V = 2153.52(9) ų,Z = 4, the tetragonal space group P4₃2₁2, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) ų, Z = 8, and in the monoclinic space group P2₁/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) ų, Z = 4, respectively.The structural units of NDUS and NDUS1 are two‐dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two‐dimensional uranyl selenate‐selenite sheets with a U/Se ratio of 1/2. In‐situ reaction of the L ‐cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H₃O⁺ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C₅H₆N⁺ cations result from the cyclization of the carboxyl groups of L ‐cystine, balancing the charge of the sheets.     

Complexation of the 2, 4, 6‐Triallyloxy‐1, 3, 5‐triazine with Copper(I,II) Chlorides. Syntheses and Crystal Structures of [CuCl2·2C3N3(OC3H5)3], [Cu7Cl8·2C3N3(OC3H5)3], and [Cu8Cl8·2C3N3(OC3H5)3]·2C2H5OH

Interaction of copper(II) chloride with 2, 4, 6‐triallyloxy‐1, 3, 5‐triazine leads to formation of copper(II) complex [CuCl₂·2C₃N₃(OC₃H₅)₃] ( I ). Electrochemical reduction of I produces the mixed‐valence Cu^{I, II} π, σ‐complex of [Cu₇Cl₈·2C₃N₃(OC₃H₅)₃] ( II ). Final reduction produces [Cu₈Cl₈·2C₃N₃(OC₃H₅)₃]·2C₂H₅OH copper(I) π‐complex ( III ). Low‐temperature X‐ray structure investigation of all three compounds has been performed: I : space group P1¯, a = 8.9565(6), b = 9.0114(6), c = 9.7291(7) Å, α = 64.873(7), β = 80.661(6), γ = 89.131(6)°, V = 700.2(2) ų, Z = 1, R = 0.0302 for 2893 reflections. II : space group P1¯, a = 11.698(2), b = 11.162(1), c = 8.106(1) Å, α = 93.635(9), β = 84.24(1), γ = 89.395(8)°, V = 962.0(5) ų, Z = 1, R = 0.0465 for 6111 reflections. III : space group P1¯, a = 8.7853(9), b = 10.3602(9), c = 12.851(1) Å, α = 99.351(8), β = 105.516(9), γ = 89.395(8), V = 1111.4(4) ų, Z = 1, R = 0.0454 for 4470 reflections. Structure of I contains isolated [CuCl₂·2C₃N₃(OC₃H₅)₃] units. The isolated fragment of I fulfils in the structure of II bridging function connecting two hexagonal prismatic‐like cores Cu₆Cl₆, whereas isolated Cu₆Cl₆(CuCl)₂ prismatic derivative appears in III . Coordination behaviour of the 2, 4, 6‐triallyloxy‐1, 3, 5‐triazine moiety is different in all the compounds. In I ligand moiety binds to the only copper(II) atom through the nitrogen atom of the triazine ring. In II ligand is coordinated to the Cu^II‐atom through the N atom and to two Cu^I ones through the two allylic groups. In III all allylic groups and nitrogen atom are coordinated by four metal centers. The presence of three allyl arms promotes an acting in II and III structures the bridging function of the ligand moiety. On the other hand, space separation of allyl groups enables a formation of large complicated inorganic clusters.     

Piaselenol—Piaselenolium—Pentaiodid (C6H4N2Se · C6H5N2Se+I3− · I2), eine Struktur mit Polyiodid-schichten

Piaselenole—Piaselenolium—Pentaiodide (C₆H₄N₂Se · C₆H₅N₂Se⁺ I₃^? · I₂), a Structure with Polyiodide Layers The title compound crystallizes in the monoclinic space group P2₁/n with a = 9.320(3), b = 13.812(2), c = 17.159(3) Å, β = 96.11(2)°, V = 2196.3 ų, Z = 4. There occur no isolated I^5? anions but layer-shaped polyiodide aggregates built up by linear, asymmetric I₃^? anions and I₂ molecules. Almost linear triiodide chains are connected by I₂ molecules in a novel type of arrangement to form slightly puckered layers. The polyiodide layers contain several substructures known from other examples. The piaselenole and its conjugated acid, the piaselenolium cation, form a ribbon-like quasi-polymer in which the two components are alternating. They are connected in turns by a linear NH? N hydrogen bridge (N? N: 2.844 Å) and by a so called (SeN)₂-connectivity parallelogram, in which Se? N bonds and Se? N contacts are adjacent. Here we found a very short Se? N contact distance of 2.691 Å. The bond distances of piaselenole (Se? N: 1.787(3) Å, N? C: 1.318(5) Å, C? C: 1.453(8) Å) and also the angles are equal or similar to those occuring in other 1,2,5-selenadiazoles. The protonation of one N in the SeN₂ unit results in a loss of symmetry and significant changes in bonding distances and angles.     

Amine‐Templated Uranyl Selenates with Layered Structures. I Structural Diversity of Sheets with a U:Se ratio of 1:2

Crystals of four amine‐templated layered uranyl selenates, [C₂H₁₀N₂][(UO₂)(SeO₄)₂(H₂O)](H₂O) ( 1 ), [CH₆N₃]₂[(UO₂)(SeO₄)₂(H₂O)](H₂O)_1.5 ( 2 ), [C₄H₁₂N]₂[(UO₂)(SeO₄)₂(H₂O)] ( 3 ), and [CH₆N₃]₃[(UO₂)₂(SeO₄)₂(H(SeO₄)₂)](H₂O)₂ ( 4 ) were prepared by evaporation from aqueous solution of uranyl nitrate, selenic acid and the respective amine. The structures of all four compounds have been solved by direct methods. The structures of 1 (monoclinic, C2/c, a = 11.787(2), b = 7.7007(10), c = 16.600(3) Å, β = 102.016(14)°, V = 1473.7(4) ų, R₁ = 0.037 for 1743 unique observed reflections), 2 (monoclinic, C2/c, a = 37.314(4), b = 7.1771(6), c = 13.2054(14) Å, β = 109.267(8)°, V = 3338.4(6) ų, R₁ = 0.088 for 3005 unique observed reflections) and 3 (monoclinic, C2/c, a = 27.212(10), b = 7.372(3), c = 23.113(7) Å, β = 117.75(2)°, V = 4103(3) ų, R₁ = 0.073 for 2111 unique observed reflections) are based on sheets of the composition [(UO₂)(SeO₄)₂(H₂O)]^2? consisting of pentagonal [UO₇]^8? pentagonal bipyramids linked via [SeO₄]^2? tetrahedra. The sheets have the same chemical composition but different topologies. The structure of 4 (orthorhombic, P2₁2₁2₁, a = 10.7261(9), b = 13.918(2), c = 18.321(2) Å, V = 2735.1(5) ų, R₁ = 0.050 for 5683 unique observed reflections) contains [(UO₂)₂(SeO₄)₂(H(SeO₄)₂)]^3? sheets parallel to (001). In all four structures, the layers are connected via protonated amine and H₂O molecules.     

Molybdänhalogenidcluster mit zwei terminalen Alkoholatliganden: Synthese und Kristallstrukturen von (C18H36N2O6Na)2[Mo6Cl12(OCH3)2] und (C18H36N2O6Na)2[Mo6Cl12(OC15H11)2] · 2C4H6O3

Molybdenum(II) Halide Clusters with two Alcoholate Ligands: Syntheses and Crystal Structures of (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OCH₃)₂] and (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OC₁₅H₁₁)₂] · 2C₄H₆O₃ . Reaction of Mo₆Cl₁₂ with two equivalents of sodium methoxide in the presence of 2,2,2-crypt yields (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OCH₃)₂] ( 1 ), which can be converted to (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OC₁₅H₁₁)₂] · 2C₄H₆O₃ ( 2 ) by metathesis with 9-Anthracenemethanole in propylene carbonate. As confirmed by X-ray single crystal structure determination ( 1 : C2/m, a=25.513(8) Å, b=13.001(3) Å, c=10.128(3) Å, β=100.204(12)°; : C2/c, a=15.580(5) Å, b=22.337(5) Å, c=27.143(8) Å, β=98.756(10)°) the compounds contain anionic cluster units [Mo₆ClCl(OR^a)₂]^2? with two alcoholate ligands in terminal trans positions ( 1 : d(Mo—Mo) 2.597(2) Å to 2.610(2) Å, d(Mo—Clⁱ) 2.471(3) Å to 2.493(4) Å, d(Mo—Cl^a) 2.417(8) Å and 2.427(8) Å, d(Mo—O) 2.006(13) Å; 2 : d(Mo—Mo) 2.599(3) Å to 2.628(3), d(Mo—Clⁱ) 2.468(8) Å to 2.506(7) Å, d(Mo—Cl^a) 2.444(8) Å and 2.445(7) Å, d(Mo—O) 2.012(19) Å).     

Darstellung und Charakterisierung der Fulleren-Kokristallisate C60 · 12 C6H12, C70 · 12 C6H12, C60 · 12 CCl4, C60 · 2 CHBr3, C60 · 2 CHCl3, C60 · 2 H2CCl2

Synthesis and Characterization of the Fullerene Co-Crystals C₆₀ · 12 C₆H₁₂, C₇₀ · 12 C₆H₁₂, C₆₀ · 12 CCl₄, C₆₀ · 2CHBr₃, C₆₀ · 2CHCl₃, C₆₀ · 2H₂CCl₂ By crystallization of fullerenes from non-polar solvents (C₆H₁₂, CCl₄, CHBr₃, CHCl₃, H₂CCl₂) compounds of the following compositions were obtained: C₆₀ · 12C₆H₁₂, C₇₀ · 12C₆H₁₂, C₆₀ · 12CCl₄, C₆₀ · 2CHCl₃, C₆₀ · 2CHBr₃ and C₆₀ · 2H₂CCl₂. Lattice parameters have been determined by X-ray diffraction of powder samples; according to single-crystal examinations on C₆₀ · 12C₆H₁₂, C₆₀ · 12CCl₄ and C₆₀ · 2CHBr₃ the fullerene is orientationally disordered. C₆₀ · 12C₆H₁₂, cubic, a = 28.167(1) Å; C₇₀ · 12C₆H₁₂, cubic, a = 28.608(2) Å; C₆₀ · 12CCl₄, cubic, a = 27.42(1) Å; C₆₀ · 2CHBr₃, hexagonal, a = 10.212(1), c = 10.209(1) Å; C₆₀ · 2CHCl₃, hexagonal, a = 10.08(1), c = 10.11(2) Å; C₆₀ · 2H₂CCl₂, tetragonal, a = 16.400(1) Å, c = 11.645(7) Å.     

Kaliumamidotrioxogermanate(IV) – Wasserstoff-Brückenbindungen in K3GeO3NH2 und K3GeO3NH2 · KNH2

Potassium Amido Trioxo Germanates(IV) – Hydrogen Bridge Bonds in K₃GeO₃NH₂ and K₃GeO₃NH₂ · KNH₂ Colorless crystals of K₃GeO₃NH₂ and of K₃GeO₃NH₂ · KNH₂ were obtained by the reaction of KNH₂ with GeO₂ in supercritical ammonia at 450°C and p = 6 kbar in high-pressure autoclaves within 15 resp. 5 days. The crystal structures of both compounds were solved by X-ray single crystal methods. K₃GeO₃NH₂: P1 , a = 6.390(1) Å, b = 6.684(1) Å, c = 7.206(1) Å, α = 96.47(1)°, β = 101.66(1)°, γ = 91.66(1)°, Z = 2, R/R_w = 0.020/0.022, N(I) ≥ 2σ(I) = 3023, N(Var.) = 82 K₃GeO₃NH₂ · KNH₂: P2₁/c, a = 10.982(6) Å, b = 6.429(1) Å, c = 12.256(8) Å, β = 106.12(1)°, Z = 4, R/R_w = 0.022/0.029, N(F) ≥ 3σ(F) = 1745, N(Var.) = 107. In K₃GeO₃NH₂ tetrahedral ions GeO₃NH₂^3? are connected to chains by N? H …? O bridge bonds with 2.18 Å ≤ d(H …? O) ≤ 2.40 Å for d(N? H) ? 1.0 Å and by potassium ions while in K₃GeO₃NH₂ · KNH₂ bridge bonds between NH₂ groups of GeO₃NH₂^3? and NH₂^? ions as acceptors occur with 2.41 Å ≤ d((N? )H …? NH₂^?) ≤ 2.61 Å for d(N? H) ? 1.0 Å.     

Molybdänhalogenidcluster mit sechs terminalen Alkoholatliganden: (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6CH3OH und (C18H36N2O6Na2)2[Mo6Cl8(OC6H5)6]

Molybdenum(II) Halide Clusters with six Alcoholate Ligands: (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6CH₃OH and (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] . The reaction of Na₂[Mo₆Cl₈(OCH₃)₆] and 2,2,2-crypt yields (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6 CH₃OH ( 1 ), which is converted to (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] ( 2 ) by metathesis with phenol. According to single crystal structure determinations ( 1 : P3 1c, a=14.613(3) Å, c=21.036(8) Å; 2 : P3 1c, a=15.624(1) Å, c=19.671(2) Å) the compounds contain anionic clusters [Mo₆Cl₈ⁱ(OR^a)₆]^2? ( 1 : d(Mo—Mo) 2.608(1) Å to 2.611(1) Å, d(Mo—Cl) 2.489(1) Å to 2.503(1) Å, d(Mo—O) 2.046(4) Å; 2 : d(Mo—Mo) 2.602(3) Å to 2.608(3) Å, d(Mo—Cl) 2.471(5) Å to 2.4992(5) Å, d(Mo—O) 2.091(14) Å). Electronic interactions of the halide cluster and the phenolate ligands in [Mo₆Cl₈(OC₆H₅)₆]^2? is investigated by means of UV/VIS spectroscopy and EHMO calculations.     

Synthesis and Crystal Structures of α‐ and β‐Mg2[(UO2)3(SeO4)5](H2O)16

Single crystals of α‐ and β‐Mg₂[(UO₂)₃(SeO₄)₅](H₂O)₁₆ have been synthesized by evaporation from an aqueous solution of the ionic components. The structure of α‐Mg₂[(UO₂)₃(SeO₄)₅](H₂O)₁₆ (monoclinic, C2/c, a = 19.544(3), b = 10.4783(11), c = 18.020(3) Å, β = 91.352(12)°, V = 3689.3(9) ų) has been solved by direct methods and refined to R₁ = 0.048 on the basis of 4338 unique observed reflections. The structure of β‐Mg₂[(UO₂)₃(SeO₄)₅](H₂O)₁₆ (orthorhombic, Pbcm, a = 10.3807(7), b = 22.2341(19), c = 33.739(5) Å, V = 7787.2(14) ų) has been solved by direct methods and refined to R₁ = 0.107 on the basis of 3621 unique observed reflections. The structures of α‐ and β‐Mg₂[(UO₂)₃(SeO₄)₅](H₂O)₁₆ are based upon sheets with the chemical composition [(UO₂)₃(SeO₄)₅]^4‐. The sheets are formed by corner sharing between pentagonal bipyramids [UO₇]^8‐ and SeO₄^2‐ tetrahedra. In the α‐modification, the [(UO₂)₃(SeO₄)₅]^4‐ sheets are more or less planar and run parallel to (001). In the structure of the β‐modification, the uranyl selenate sheets are strongly corrugated and oriented parallel to (010). The [Mg(H₂O)₆]²⁺ polyhedra reside in the interlayers and provide three‐dimensional linkage of the uranyl selenate sheets via hydrogen bonding. In addition to H₂O groups attached to Mg²⁺ cations, both structures also contain H₂O molecules that are not bonded to any cation. The [(UO₂)₃(SeO₄)₅]^4‐ sheets in the structures of α‐ and β‐Mg₂[(UO₂)₃(SeO₄)₅](H₂O)₁₆ represent two different structural isomers. The sequences of the orientations of the tetrahedra within the sheets can be described by their orientational matrices with their shortened forms ( ddudd □ /uu □ uud ) and ( dd □ dd □ uu □ uu □ /uuduumdduddm ) for α‐ and β‐Mg₂[(UO₂)₃(SeO₄)₅](H₂O)₁₆, respectively. A short review on the isomerism of [(UO₂)₃(TO₄)₅]^4‐ sheets (T = S, Cr, Se, Mo) is given.