Cu3SbSe3: Synthese und Kristallstruktur

The Crystal Structure of Cu₃SbSe₃ The hitherto unknown crystal structure of Cu₃SbSe₃ has been determined from single crystals. The compound crystallizes in the orthorhombic system, space group Pnma (No. 62), with a = 7.9865(8), b = 10.6138(9) and c = 6.8372(7) Å, V = 579.6(1) ų, Z = 4. Most remarkable feature of the structure are groups of three cis-edge-sharing tetrahedra [Cu₃Se₈] which are interlinked to a threedimensional arrangement by SbSe₃-units. In contrast to Cu₃SbS₃ in the temperature range from ?180 to 25°C no hints for a phase transition could be detected by means of X-ray- and thermoanalytical methods.     

(LiI)2Li3SbS3: A mixed Alkali Metal Halide Thioantimonate with a novel Tetrahedron Network

(LiI)₂Li₃SbS₃ was prepared by solid‐state reaction of stoichiometric amounts of LiI, Li, Sb, and S in the ratio 2 : 3 : 1 : 3. The product is air and moisture sensitive. The crystal structure was determined from single crystals at room temperature. Colourless to pale yellow (LiI)₂Li₃SbS₃ crystallizes in the orthorhombic system, space group Pnnm (no. 58) with a = 10.436(1)Å, b = 13.509(1)Å, c = 7.530(1)Å, V = 1061.6(1)ų, and Z = 4 (data at 20 °C). The crystal structure of (LiI)₂Li₃SbS₃ is closely related to that of (CuI)₂Cu₃SbS₃ and (AgI)₂Ag₃SbS₃, at least for the positions of I, Sb, and S. Thus, iodine forms an eutactic arrangement which resembles the structure of hexagonal diamond. [SbS₃]^3— units are embedded in this framework in a way that the sulphur atoms of two adjacent trigonal pyramids form distorted octahedral voids. The lithium ions are tetrahedrally coordinated and fully ordered within the anionic framework. The three‐dimensional connectivities in (LiI)₂Li₃SbS₃ are significantly different from the homologous copper and silver compound due to the bonding necessities of Li and slightly different radii of the monovalent cations. Thus, a novel three‐dimensional network of edge sharing tetrahedra is observed in (LiI)₂Li₃SbS₃. It exhibits strands of eight‐membered rings of edge sharing tetrahedra which are linked by common vertices and cross linked by double tetrahedra.     

Syntheses,Structures, and Properties of New Quaternary Gold-Chalcogenides: K2Au2Ge2S6, K2Au2Sn2Se6, and Cs2Au2SnS4

The new compounds K₂Au₂Ge₂S₆ ( 1 ), K₂Au₂Sn₂Se₆ ( 2 ), and Cs₂Au₂SnS₄ ( 3 ) have been synthesized through direct reaction of the elements with a molten polyalkalithiogermanate(stannate) flux at 650, 550, and 400 °C, respectively. Their crystal structures have been determined by single crystal X-ray diffraction techniques. 1 crystallizes in the monoclinic space group P2₁/n with a = 10.633(2) Å, b = 11.127(2) Å, c = 11.303(2) Å, β = 115,37(3)°, V = 1208,2(3) ų and Z = 4, final R(Rw) = 0.045(0.106). 2 crystallizes in the tetragonal space group P4/mcc with a = 8.251(1) Å, c = 19.961(4) Å, V = 1358,9(4) ų and Z = 4, final R(Rw) = 0.040(0.076). 3 crystallizes in the orthorhombic space group Fddd with a = 6.143(1) Å, b = 14.296(3) Å, c = 24.578(5) Å, V = 2158.4(7) ų and Z = 4, final R(Rw) = 0.039(0.095). The structures of 1 , 2 , and 3 consist of infinite, one-dimensional anionic chains containing X₂Q₆^4– units linked by Au⁺ ions and charge balancing K⁺/Cs⁺ ions situated between the chains. All compounds were investigated with differential thermal analysis, FT-IR, and solid state UV/VIS diffuse reflectance spectroscopy.     

Solvothermal Synthesis and Crystal Structures of Two Thioantimonate(V) Compounds with the [SbS4]3— Anion Acting as a Monodentate Ligand: [Mn(C6H18N4)(C6H19N4)]SbS4 and [Mn(C6H14N2)3]2[Mn(C6H14N2)2(SbS4)2]·6H2O

The two novel thioantimonate(V) compounds [Mn(C₆H₁₈N₄)(C₆H₁₉N₄)]SbS₄ ( I ) and [Mn(C₆H₁₄N₂)₃][Mn(C₆H₁₄N₂)₂(SbS₄)₂]·6H₂O ( II ) were synthesized under solvothermal conditions by reacting elemental Mn, Sb and S in the stoichiometric ratio in 5 ml tris(2‐aminoethyl)amine (tren) at 140 °C or chxn (trans‐1, 2‐diaminocyclohexane, aqueous solution 50 %) at 130 °C. Compound I crystallises in the triclinic space group P1¯, a = 9.578(2), b = 11.541(2), c = 12.297(2)Å, α = 62.55(1), β = 85.75(1), γ = 89.44(1)°, V = 1202.6(4)ų, Z = 2, and II in the monoclinic space group C2/c, a = 32.611(2), b = 13.680(1), c = 19.997(1)Å, β = 117.237(5)°, V = 7931.7(8)ų, Z = 4. In I the Mn²⁺ cation is surrounded by one tetradentate tren molecule, one protonated tren acting as a monodentate ligand and a monodentate [SbS₄]^3— anion yielding a distorted octahedral environment. In II one unique Mn²⁺ ion is in an octahedral environment of three bidentate chxn molecules and the second independent Mn²⁺ ion is coordinated by two chxn ligands and two monodentate [SbS₄]^3— units leading to a distorted octahedral surrounding. The compounds were investigated and characterized with thermal and spectroscopic methods.     

Palladium(II) Complexes with the Mixed‐Donor Ligand CH3S‐(CH2)3‐PPh2 Crystal Structures of [PdCl2{CH3S‐(CH2)3‐PPh2}n](n = 1, 2)

The phosphorus‐sulfur ligand 1‐(methylthio)‐3‐(diphenylphosphino)‐propane (S‐P3) has been synthesized and characterized by ¹H NMR and ¹³C NMR. Reactions of S‐P3 with [PdCl₂(PhCN)₂] afforded the complexes [PdCl₂(S‐P3)] ( I ) and [PdCl₂(S‐P3)₂] ( II ), in which S‐P3 acts as a bidentate and monodentate ligand, respectively. Compound I crystallizes in monoclinic space group P2₁/n (No. 14) with cell dimensions: a = 8.589(3), b = 15.051(3), c = 17.100(3)Å, β = 102.91(2)°, V = 2154.7(9)ų, Z = 4. Likewise, compound II crystallizes in monoclinic space group P2₁/n (No. 14) with a = 9.993(5), b = 8.613(4), c = 18.721(5)Å, β = 90.18(3)°, V = 1611.3(12)ų, Z = 2. Compound II has a trans square planar configuration with only the P‐site of the ligand bonded to the palladium atom.     

Synthese,Struktur und Reaktionen von Vanadiumsäureestern VO(OR)3: Umesterung und Reaktion mit Oxalsäure

Synthesis, Structure, and Reactions of Vanadium Acid Esters VO(OR)₃: Transesterification and Reaction with Oxalic Acid The reaction of tert.‐Butyl Vanadate VO(O‐tert.Bu)₃ ( 1 ) with H₂C₂O₄ in the primary alcohols ethanol and propanol results in the formation of (ROH)(RO)₂OV^V(C₂O₄)V^VO(OR)₂(HOR) (with R = C₂H₅ 2 and R = C₃H₇ 3 ). Compounds 2 and 3 are the first structurally characterized neutral, binuclear oxo‐oxalato‐complexes with pentavalent vanadium. The two vanadium atoms are connected by a bisbidentate oxalate group. The {VO₆} coordination at each vanadium site is completed by a terminal oxo group, an alcohol ligand and two alcoxide groups. The binuclear molecules are connected to chains by hydrogen bonding. In the case of 2 a reversible isomorphic phase transition in the temperature range of –90 °C to –130 °C is observed. From methanolic solution the polymeric Methyl Vanadate [VO(OMe)₃] ( 4 ) was obtained by transesterification. A report on the crystal structures of 1 , 2 and 3 as well as a redetermination of the structure of 4 is given. Crystal data: 1, orthorhombic, Cmc2₁, a = 16.61(2) Å, b = 9.274(6) Å, c = 10.784(7) Å, V = 1662(2) ų, Z = 4, d_c = 1.144 gcm^–1; 2 (–90 ° C) , monoclinic, I2/a, a = 33.502(4) Å, b = 7.193(1) Å, c = 15.903(2) Å und β = 143.060(3)°, V = 2303(1) ų, Z = 4, d_c = 1.425 gcm^–1; 2 (–130 ° C) , monoclinic, I2/a, a = 33.274(4) Å, b = 7.161(1) Å, c = 47.554(5) Å, β = 142.798(2)°, V = 6851(1) ų, Z = 12, d_c = 1.438 gcm^–1; 3 , triklinic, P1, a = 9.017(5) Å, b = 9.754(5) Å, c = 16.359(9) Å, α = 94.87(2)°, β = 93.34(2)°, γ = 90.42(2)°, V = 1431(1) ų, Z = 2, d_c = 1.340 gcm^–1; 4 , triklinic, P1, a = 8.443(2) Å, b = 8.545(2) Å, c = 9.665(2) Å, α = 103.202(5)°, β = 96.476(5)°, γ = 112.730(4)°, V = 610.2(2)ų, Z = 4, d_c = 1.742 gcm^–1.     

Preparation and crystal structures of two salts with the 5‐nitrotetrazolate anion

Tetraphenylphosphonium 5‐nitrotetrazolate ( 2 ) was prepared by metathesis of sodium 5‐nitrotetrazolate dihydrate ( 1 ; NaNT) with tetraphenylphosphonium chloride in acetone. The new compound was fully characterized by vibrational (IR, Raman) and NMR (¹H, ¹³C, and ¹⁴N) spectroscopies, elemental analysis, and mass spectrometry. Attempted synthesis of 2‐methyl‐5‐nitrotetrazole (2‐MeNT) by methylation of 1 with dimethylsulfate at reflux from acetonitrile failed, and crystals of an explosive compound with the formula (NaNT)₂(H₂O)₂CH₃CN ( 3 ), NT = 5‐nitrotetrazolate, formed. X‐ray diffraction techniques were used to determine the crystal structure of 2 and 3 . Compound 2 crystallizes in the orthorhombic space group P2₁2₁2₁ with four molecules in the unit cell and unit cell parameters a = 7.7413(4) Å, b = 13.624(1) Å, c = 21.252(1) Å, and V = 2241.5(2) ų, whereas 3 crystallizes in the orthorhombic space group Ama2 with four formula unit in the unit cell and unit cell parameters a = 14.805(6) Å, b = 9.908(4) Å, c = 8.940(3) Å, and V = 1311.4(1) ų. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:35–44, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20509     

Four New Thioantimonates(III) with the General Formula [TM(tren)]Sb4S7 (TM = Mn,Fe, Co,Zn) with the Transition Metal as Part of a Thioantimonate(III) Network Synthesized under Solvothermal Conditions and Tuning of the Optical Band Gap by the Transition Metal Cation

Four new thioantimonate(III) compounds with the general formula [TM(tren)]Sb₄S₇, TM = Mn 1 , Fe 2 , Co 3 and Zn 4 , were synthesized under solvothermal conditions by reacting elemental TM, Sb and S in an aqueous solution of tren (tren = tris(2‐aminoethyl)amine). All compounds crystallize in the monoclinic space group P2₁/n with four formula units in the unit cell. Single crystal X‐ray analyses of 1 [a = 8.008(2), b = 10.626(2), c = 25.991(5) Å, β = 90.71(3)°, V = 2211.4(8) ų], 2 [a = 8.0030(2), b = 10.5619(2), c = 25.955(5) Å, β = 90.809(3)°, V = 2193.69(8) ų], 3 [a = 7.962(2), b = 10.541(2), c = 25.897(5) Å, β = 90.90(3)°, V = 2173.0(8) ų] and 4 [a = 7.978(2), b = 10.625(2), c = 25.901(5) Å, β = 90.75(3)°, V = 2195.2(8) ų] reveal that the compounds are isostructural. The [Sb₄S₇]^2‐ anions are composed of three SbS₃ trigonal pyramids and one SbS₄ unit as primary building units (PBU). The PBUs share common edges and corners to form semicubes (Sb₃S₄) which may be regarded as secondary building units (SBU). The SBUs and SbS₃ pyramids are joined in an alternating fashion yielding the equation/tex2gif-stack-1.gif[Sb₄S₇^‐] anionic chain which is directed along [100]. Weaker Sb‐S bonding interactions between neighbored chains lead to the formation of layers within the (001) plane which contain pockets that are occupied by the cations. The TM²⁺ ions are in a trigonal bipyramidal environment of four N atoms of the tren ligand and one S atom of the thioantimonate(III) anion. The optical band gaps depend on the TM²⁺ ion and amount to 3.11 eV for 1 , 2.04 eV for 2 , 2.45 eV for 3 , and 2.60 eV for 4 .     

Crystal and molecular structure of cis- and trans-2,4-dihydroxy-2,4-dimethylcyclohexanetrans-1-acetic acid γ-lactone

During the transformation process of limonene to tetrahydrofuran derivatives, the title compounds (±)-( 4 ) have been obtained as crystalline products and subjected to X-ray analysis. The crystals of trans-( 4 ) are orthorhombic, space group P2₁2₁2₁, with the lattice constants a = 7.0445(5) Å, b = 10.0908(4) Å, c = 14.0309(6) Å; the absolute configuration at atoms C1, C2, and C4 is R_c1, S_c2, and R_c4, respectively. The isomeric form cis-( 4 ) crystallizes in the monoclinic system, space group P2₁, with the following unit-cell parameters: a = 10.8275(4) Å, b = 8.6994(5) Å, c = 16.4722(6) Å, β = 106.515(3)°. The asymmetric part of the unit cell of cis-( 4 ) contains three independent molecules. Each of these three molecules has the identical absolute configuration at all centers of chirality: S_c1, S_c2, and R_c4. © John Wiley & Sons, Inc.     

A New Type of Divalent Europium Compound MEuPO4 (M = K,Rb, Cs), its Synthesis,Crystal Structure,and Properties

Phosphates MEuPO₄ with M = K, Rb, and Cs were synthesized by the reduction of EuPO₄ with alkali metal vapour under 1 Pa of argon pressure at 260–530°C in sealed tantalum or niobium lined glass tubes. All the compounds belong to the β-K₂SO₄ orthorhombic structure with a = 7.359(3), b = 9.630(4), c = 5.569(2) Å, V = 394.7(2) ų for KEuPO₄, a = 7.462(3), b = 9.797(3), c = 5.649(2) Å, V = 413.0(2) ų for RbEuPO₄ and a = 7.889(2), b = 10.099(2), c = 5.820(4) Å, V = 463.6(2) ų for CsEuPO₄. Samples are stable and not hygroscopic in air at room temperature but hydrolyse to Eu₅(PO₄)₃OH, hexagonal, a = 9.764(2), c = 7.262(2) Å, on heating in water and decompose to Eu₃(PO₄)₂, hexagonal, a = 5.393(1), c = 19.838(3) Å, under argon at ca. 600°C. All the five compounds are paramagnetic.     

X‐ray Investigation and Coordination Behaviour of the 1,3‐Diallylbenzimidazolium Cation in [C13H15N2]+2 [CuCl2.58Br1.42]2– and [C13H15N2]+[Cu2Cl0.67Br2.33]– Complexes

By means of alternating current electrochemical synthesis crystals of [C₁₃H₁₅N₂]⁺₂[CuCl_2.58Br_1.42]^– ( I ) and [C₁₃H₁₅N₂]⁺[Cu₂Cl_0.67Br_2.33]^– ( II ) have been obtained and structurally characterized. Compound I crystallizes in the orthorhombic system, space group Fddd, a = 7.828(1) Å, b = 26.402(2) Å, c = 28.595(3) Å, D_c = 1.4995(5) g/cm³, Z = 8, R = 0.067 for 2157 reflections. The CuX₄^2– tetrahedra are connected with the organic cations through an electrostatic interaction. Crystals of II are monoclinic, space group P2₁/c, a = 9.2293(8) Å, b = 22.1332(9) Å, c = 9.2939(9) Å, β = 118.021(4)°, D_c = 2.1251(5) g/cm³, Z = 4, R = 0.042 for 2858 reflections. A tetrahedral environment of the Cu1 atom involves four halide atoms, whereas Cu2 possesses a trigonal‐pyramidal coordination with the C=C‐bond and three halide atoms.     

Synthesis,Crystal Structure and Magnetic Property of Diiron Complex [Fe(phen)3][Fe2OCl6]·2CH3CN

A new diiron complex has been synthesized and characterized by X‐ray single crystal structural analysis: [Fe^II(phen)₃][Fe^III₂OCl₆]·2CH₃CN. The complex crystallizes in the monoclinic system, space group C2/c, with lattice parameters a = 21.162(4) Å, b = 15.168(3) Å, c = 14.812(3) Å, β= 112.71 (3)°, V = 4385.8(15) ų, Dx = 1.543 Mg/m³, Z = 4. The corresponding variable temperature susceptibility measurement shows that there exists an antiferromagnetic interaction in the complex.     

Preparation of Aluminum Alkoxides and Crystal Structures of [Al{(S)-(-)-μ-OC(H)(CH3)C(Ph)2OH}Cl2]2·2Et2O and [(μ-O(CH2)2OPh)AlMe2]2

The reaction of (S)-(-)-1, l-diphenyl-propane-1,2-diol with AlCl₃ in diethyl ether furnishes the product [Al((S)-(-)-μ₂-OC(H)(Me)C(Ph)₂OH)Cl₂]₂ 1, which decomposes slowly above 25 °C. Complex 1·2Et₂O Crystallizes in the non-centrosymmetric monoclinic space group P2₁ with a=10.591(1) Å, b=16.718(1) Å, c = 12.156(2) Å, β=99.30(2)°, V = 2124.1(3) Å₃, z = 4, R = 4.67%, Rw=4.84%, GoF=1.14. The structure of 1 shows a dimer feature, which is hydrogen bonded to two diethyl ether molecules. In the reaction of 2-phenoxyethanol with AlMe₃, the dimeric [(μ-O(CH₂)₂OPh)AlMe₂]₂ is obtained in high yield. 2 crystallizes in the monoclinic space group P2₁/c with a = 7.398(2) Å, b = 7.376(2) Å, c = 20.710(2) Å, β = 90.56(2)°, v = 1129.9(4) ų, z=4, R=5.70%, Rw=7.15%, GoF=1.59.     

Synthesis,Crystal Structure,and Properties of HfM′P (M′ = Fe,Co, Ni) in comparison to ZrNiP

The new phosphides HfM′P (M′ = Fe, Co, Ni) have been synthesized by arc melting of HfP and the corresponding 3 d metal, and subsequent annealing at 1400°C. The lattice constants vary from a = 6.247(2) Å, b = 3.7177(6) Å, c = 7.137(2) Å, V = 165.74(8) ų for HfFeP, a = 6.295(3) Å, b = 3.668(2) Å, c = 7.175(4) Å, V = 165.7(2) ų for HfCoP to a = 6.240(3) Å, b = 3.716(2) Å, c = 7.135(2) Å, V = 165.4(2) ų (HfNiP) in the orthorhombic space group Pnma. Although ZrNiP occurs only in the Ni₂In structure type, all three Hf phosphides crystallize in the Co₂Si structure type, isotypic to ZrFeP and ZrCoP. The structural differences between HfNiP and ZrNiP can be explained by the preference of Hf for structures with more metal-metal bonds rather than by size effects.     

Synthesis and Crystal Structure of KCuGd2S4: A Threedimensional Framework with Isolated Channels

The reaction of K₂S₅, Cu, Gd, and S in a 2 : 1 : 2 : 4 molar ratio at 450 °C yields yellow-orange needle-like cuboids of the new quaternary compound KCuGd₂S₄. The crystal structure represents a novel three-dimensional structure type of quaternary rare earth chalcogenides with alkali metal. The compound crystallizes in the orthorhombic space group Cmcm (No. 63) with a = 3.9921(1) Å, b = 13.523(3) Å, c = 13.802(3) Å, V = 745.1(3) ų, Z = 4. In the structure GdS₆ octahedra and CuS₄ tetrahedra are joined by common edges and corners forming corrugated layers parallel to (010). The GdS₆ octahedra are connected via common edges in the third dimension thus leading to the formation of a three-dimensional tunnel structure. The potassium cations are confined within the pentagonal shaped channels and are surrounded by eight sulfide anions each.     

LiBSe3: A NOVEL PERSELENOBORATE WITH POLYMERIC ANION NETWORK

We now report the synthesis and crystal structure of LiBSe₃, a new perselenoborate with anionic layers. LiBSe₃ crystallizes in the orthorhombic space group Pca2₁ (No. 29), a = 12.770(3) Å, b = 5.777(2) Å, c = 10.726(2) Å.     

2‐Imino‐3‐allyl‐benzothiazole as a π‐Ligand: Synthesis and Crystal Structure of [(CuCl)C10H10SN2], [C10H11SN2+]2[Cu2Cl4]2−, and [C10H11SN2+]2[Cu2Br4]2− π‐Compounds

The reaction of 2‐amino‐benzothiazole with allyl bromide resulted in a mixture of 2‐imino‐3‐allyl‐benzothiazole and 2‐imino‐3‐allyl‐benzothiazolium bromide.Using such a mixture and copper(II) chloride in acetonitrile solution in alternating‐current electrochemical synthesis crystals of the [(CuCl)C₁₀H₁₀SN₂] ( I ) have been obtained. The same procedure, performed in ethanol solution, has led to formation of [C₁₀H₁₁SN₂⁺]₂[Cu₂Cl₄]^2? ( II ). In the same manner the bromine derivative [C₁₀H₁₁SN₂⁺]₂[Cu₂Br₄]^2? ( III ) has been synthesized. All three compounds were X‐ray structurally investigated. I :monoclinic space group P2₁/n, a = 13.789(6), b = 6.297(3), c = 13.830(6) Å, β = 112.975(4)°, V = 1105.6 (9) ų, Z = 4 for CuCl·C₁₀H₁₀ SN₂ composition. Compounds II and III are isomorphous and crystallize in triclinic space group. II a = 7.377(3), b = 8.506(3), c = 9.998(4) Å, α = 79.892(10)°, β = 82.704(13)°, γ = 78.206(12)°, V = 601.9(4) ų, Z = 1. III a = 7.329(2), b = 8.766(3), c = 10.265(3) Å, α = 79.253(9)°, β = 82.625(9)°, γ = 77.963(9)°, V = 630.9(3) ų, Z = 1. In the structure I [(CuCl)C₁₀H₁₀SN₂] building blocks are bound into infinitive spiral‐like chains via strong N‐H..Cl hydrogen bonds. In the zwitter‐ionic II and III compounds copper and halide atoms form centrosymmetric [Cu₂X₄]^2? anions, which are interconnected via N‐H..X hydrogen bonds into infinite butterfly‐like chains. The strongest Cu‐(C=C) π‐interaction has been observed in structure I , where copper possesses coordination number 3. Increasing copper coordination number to 4 in II as well as replacing chlorine atoms by bromine ones in III suppresses markedly this interaction.     

Another Example for the Ability of the $\rm SbS^{3-}_{3}$ Anion to act as a Bidentate Ligand: Solvothermal Synthesis,Crystal Structure,Calculated and Experimental Raman Spectra of [Cr(tren)SbS3]·H2O

The new charge neutral complex [Cr(tren)SbS₃]·H₂O was synthesized under solvothermal conditions applying CrCl₃·6H₂O, Sb₂S₃, and S as starting material in an aqueous tren solution (tren = tris(2‐aminoethyl)amine)). The compound crystallizes in the non‐centrosymmetric space group P2₁2₁2₁ with a = 8.7779(15), b = 10.7122(17), c = 15.4286(18) Å, V = 1450.8(4) ų. In the structure the Cr³⁺ ion is surrounded by four N atoms of the amine molecules and by two S atoms of a trigonal pyramidal [SbS₃]^3? group, i.e., the latter acts as a bidentate ligand. A three‐dimensional network is formed via hydrogen bonds between the complexes and water molecules. The main resonances in the Raman spectrum can be explained on the basis of calculated data. The most intense band is due to the Sb‐S stretching vibration. The thermal properties were investigated by DTA‐TG measurements. On heating [Cr(tren)SbS₃]·H₂O decomposes in two distinct steps. The first step corresponds to the removal of the water molecules and the second step to the loss of the tren ligand.     

Ternäre Phasen des Lithiums mit Kupfer und Phosphor

1. The system Li? Cu? P was investigated by phase analysis. The samples were prepared at 500–600°C. The resulting ternary phases were characterized mainly by x-ray investigation. 2. At 560°C the range of homogeneity of Cu ₃ P lies between 25.6–26.7 atomic % P. Cu₃P forms a high-temperature (HT) modifikation, which crystallizes in a hexagonal subcell of the low-temperature (TT) modification (Z = 6): a = 4.09, c = 7.19 Å, c/a = 1.76; Z = 2 at 560°C. The intensities of the HT-powder pattern could be explained by a model in the space group P3 ml—D³_3d, which was deduced from TT-Cu₃P. 3. Li ₂ CuP , which can be derived from Li₃P, crystallizes hexagonally with a = 16.18, c = 7.724 Å; c/a = 0.477; Z = 32. In the structure, copper occupies the Li position with lowest number and coordination. 4. LiCu ₂ P also crystallizes hexagonally with a = 12.08, c = 7.39 Å; c/a = 0.71; Z = 18. In the direction [001] there is a disordered superlattice. The lattice constants of the high-temperature modification of LiCu₂P, which are related to those of HT-Cu₃P, at 520°C are: a = 4.08, c = 7.44 Å; c/a = 1.82; Z = 2. The interpretation of the intensities of the powder patterns did not result in a plain model related to HT-Cu₃P when calculated for the space group P3 m1—D³_3d. 5. LiCu ₂ P ₂ crystallizes tetragonally with a = 3.887, c = 9.554 Å; c/a = 2.46; Z = 2. The structure determination gave the D1₃-type lattice. The space group is No. 139 I4/mmm—D¹⁷_4h, the atoms occupy the following positions: 2 Li in (2a), 4 Cu in (4d) and 4 P in (4e) with z = 0.388. The compound shows P₂ groups parallel to [001] with a P? P distance of 2.14 Å. 6. Li _1,75 Cu _1,25 P ₂ crystallizes orthorhombically with a = 3.874, b = 12.668, c = 8.743 Å; Z = 6. The crystal structure has been determined. The atoms occupy the following positions within the space group No. 71 Immm—D¹⁵_2h: 2 Li in (2a), 4 Li in (4g) with y = 0.27, 4 Li in (4j) with z = 0.33, 7.5 Cu in (8l) with y = 0.127 and z = 0.267, 8 P in (8l) with y = 0.352 and z = 0.377, and 4 P in (4h) with y = 0.085. This structure, too, is dominated by the occurence of P₂ groups, which are oriented as well parallel [001] as parallel [010].     

Synthese und Struktur neuer Natriumhydrogensulfate Na(H3O)(HSO4)2; Na2(HSO4)2(H2SO4) und Na(HSO4)(H2SO4)2

Synthesis and Structure of New Sodium Hydrogen Sulfates Na(H₃O)(HSO₄)₂, Na₂(HSO₄)₂(H₂SO₄), and Na(HSO₄)(H₂SO₄)₂ Three acidic sodium sulfates have been synthesized from the system sodium sulfate/sulfuric acid and have been crystallographically characterized. Na(H₃O)(HSO₄)₂ ( A ) crystallizes in the space group P2₁/c with the unit cell parameters a = 6.974(2), b = 13.086(2), c = 8.080(3) Å, α = 105.90(4)°, V = 709.1 Å3, Z = 4. Na₂(HSO₄)₂(H₂SO₄) ( B ) is orthorhombic (space group Pna2₁) with the unit cell parameters a = 9.970(2), b = 6.951(1), c = 13.949(3) Å, V = 966.7 ų and Z = 4. Na(HSO₄)(H₂SO₄)₂ ( C ) crystallizes in the triclinic space group P1 with the unit cell parameters a = 5.084(1), b = 8.746(1), c = 11.765(3) Å, α = 68.86(2)°, β = 88.44(2)°, γ = 88.97(2)°, V = 487.8 Å3 and Z = 2. All three compounds contain SO₄ tetrahedra as HSO₄^? anions and additionally in B and C in form of H₂SO₄ molecules. The ratio H:SO₄ determines the connectivity degree in the hydrogen bond system. In A , there are zigzag chains and dimers additionally connected via oxonium ions. Complex chains consisting of cyclic trimers (two HSO₄^? and one H₂SO₄) are present in B . In structure C , several parallel chains are connected to columns due to the greater content of H₂SO₄. Sodium cations show a distorted octahedral coordination by oxygen in all three structures, the NaO₆ octahedra being “isolated” (connected via SO₄ tetrahedra only) in A . Pairs of octahedra with common edge form Na₂O₁₀ dimeric units in C . Such double octahedra are connected via common corners forming zigzag chains in B .