Ammonia chemical ionization mass spectrometry of alcohols: Structural,stereochemical, molecular-size and temperature effects

Ammonia chemical ionization (CI) mass spectra of various open-chain, cyclic and unsaturated C₅- to C₁₀-alcohols were obtained at source temperatures ranging from 60° to 250°C. The reactivity of the ammonia adduct ion MNH and its fragmentation channels are characteristic for substrate structure. Although strongly temperature-dependent, the spectra give nevertheless information on the OH-group environment as well as on the C-skeleton at any source temperature. Primary, secondary and tertiary alcohols as well as allylic and simple olefinic alcohols can be distinguished by their spectra, which show ammonium adduct ions [MNH₄]⁺, adduct dehydrogenation ions [MNH₄-H₂], ammonium substitution ions [MNH₄-H₂O]⁺ and [M-OH]⁺-ions as the main characteristic peaks. Moreover, konfigurational assignments of stereoisomeric alcohols are possible for larger substrate-size and source-temperature ranges than with isobutane CI mass spectrometry. Homologous M NH-ions show molecular-size control of fragmentation and linear MNH-ions are less stable than branched isomers due to incomplete energy randomization.     

L'action de l'ammoniac sur l'hydroxyde de cadmium et la stabilité des complexes en milieu aqueux

The solubility of precipitated Cd(OH)₂ was determined at 25°C in 1 M NaClO₄, as a function of pH and of the ammonia content of the solutions. Formation constants were obtained for the following hydroxo, ammine and hydroxo-ammine complexes: CdOH⁺, Cd(OH)₂, Cd(OH), CdNH, Cd(NH₃), Cd(NH₃), Cd(NH₃) and Cd(OH)₂NH₃. The solubility product of the hydroxide was also calculated. The presence of polynuclear species was investigated by titrimetric determinations of the hydrogen ion concentration at constant metal concentration.     

Synthese und Struktur eines Caesium-tetraimidophosphat-diamids,Cs5[P(NH)4](NH2)2 = Cs3[P(NH)4] · 2 CsNH2

Synthesis and Crystal Structure of a Cesium-tetraimidophosphate-diamide, Cs₅[P(NH)₄](NH₂)₂ = Cs₃[P(NH)₄] · 2 CsNH₂ Well crystallized Cesium-tetraimidophosphate-diamide is obtained by the reaction of CsNH₂ with P₃N₅ in autoclaves at 673 K within three days. X-ray single crystal investigations led to the following data

• Ccca, Z = 4, a = 8.192(5) Å, b = 20.472(5) Å,
• c = 8.252(3) Å
• Z(F) ≥3σ(F) = 916, Z(Var.) = 32, R/R_w=1 = 0.017/0.021

The compound contains the hitherto unknown anion [P(NH)₄]^3?.     

Synthesis,Structure, and Decomposition of (NH4)2[Mo6Cl14] · H2O

(NH₄)₂[Mo₆Cl₁₄] · H₂O ( 1 ) was prepared from reactions of MoCl₂ in ethanol with aqueous NH₄Cl solution. It crystallizes in the monoclinic space group I2/a (no. 15), Z = 4 with a = 912.3(1), b = 1491.2(2), c = 1724.8(2) pm, β = 92.25(1)°; R1 = 0.023 (based on F values) and wR2 = 0.059 (based on F² values), for all measured X‐ray reflections. The structure of the cluster anion can be given as [(Mo₆Cl)Cl]^2– (i = inner, a = outer ligands). Thermal stability studies show that 1 loses crystal water followed by the loss of NH₄Cl above 350 °C to yield MoCl₂. The water‐free compound (NH₄)₂[Mo₆Cl₁₄] ( 2 ) was synthesized by solid state reaction of MoCl₂ and NH₄Cl in a sealed quartz ampoule at 270 °C. No single‐crystals could be obtained. Decompositions of 1 and 2 under nitrogen and argon exhibited the loss of NH₄Cl at about 350 °C. Decomposition under NH₃ resulted in the formation of MoN and Mo₂N at 540 °C and 720 °C, respectively.     

Synthese und Kristallstruktur von Mangan(II)‐ und Zinkamid,Mn(NH2)2 und Zn(NH2)2

Synthesis and Crystal Structure of Manganese(II) and Zinc Amides, Mn(NH₂)₂ and Zn(NH₂)₂ Metal powders of manganese resp. zinc react with supercritical ammonia in autoclaves in the presence of a mineralizer Na₂Mn(NH₂)₄ resp. Na₂Zn(NH₂)₄_.0.5NH₃ to well crystallized ruby‐red Mn(NH₂)₂ (p(NH₃) = 100 bar, T = 130°C, 10 d) resp. colourless Zn(NH₂)₂ (p(NH₃) = 3.8 kbar, T = 250°C, 60 d). The structures including all H‐positions were solved by x‐ray single crystal data: Mn(NH₂)₂: I4₁/acd, Z = 32, a = 10.185(6) Å, c = 20.349(7) Å, N(F_o) with F > 3σ (F) = 313, N(parameter) = 45, R/R_w = 0.038/0.043. Zn(NH₂)₂: I4₁/acd, Z = 32, a = 9.973(3) Å, c = 19.644(5) Å, N(F_o) with F > 3σ (F) = 489, N(parameter) = 45, R/R_w = 0.038/0.043. Both compounds crystallize isotypic with Mg(NH₂)₂ [1] resp. Be(NH₂)₂ [2]. Nitrogen of the amide ions is distorted cubic close packed. One quarter of tetrahedral voids is occupied by Mn²⁺‐ resp. Zn²⁺‐ions in such an ordered way that units M₄(NH₂)₆(NH₂)_4/2 occur. The H‐atoms of the anions have such an orientation that the distance to neighboured cations is optimum.     

Tetraammin-Lithium-Kationen zur Stabilisierung phenylsubstituierter Zintl-Anionen: Die Verbindung [Li(NH3)4]2[Sn2Ph4]

Tetraammine Lithium Cations Stabilizing Phenylsubstituted Zintl-Anions: The Compound [Li(NH₃)₄]₂[Sn₂Ph₄] Ruby-red, brittle single crystals of [Li(NH₃)₄]₂[Sn₂Ph₄] were synthesized by the reaction of diphenyltin dichloride and metallic lithium in liquid ammonia at ?35°C. The structure was determined from X-ray singlecrystal diffractometer data: Space group, P1 , Z = 1, a = 9.462(2) Å, b = 9.727(2) Å, c = 11.232(2) Å, α = 66.22(3)°, β = 85.78(3)°, γ = 61.83(3)°, R₁ (F ? 4σF) = 5.13%, wR₂ (F₀² ? 4σF) = 10.5%, N(F ? 4σF) = 779, N(Var.) = 163. The compound contains to Sb₂Ph₄ isosteric centres [Sn₂Ph₄]^2? as anions which are connected to rods by lithium cations in distorted tetrahedral coordination by ammonia. These rods are arranged parallel to one another in the b,c-plane, but stacked along [100].     

The crystal structure of tris (ethylenediamine), cobalt(III) hexacyanoferrate(III)dihydrate,Co(C2H8N2)3[Fe(CN)6] · 2H2O

The crystal structure of the title compound has been determined from three dimensional x-ray data obtained by the multiple film method. The space group is P2_l/n and the cell dimensions are: a = 14.90, b = 16.84, c = 8.38 Å; β = 93.5° Z = 4. The structure is formed by discrete Co (en) and Fe(CN) ions, both of which have an octahedral configuration. The Fe(CN) ions are approximately octahedrally surrounded by the Co (en) ions while arrangement of Fe (CN) ions around the Co(en) ions completely differs from an octahedron. The mean Fe? C and Co? C dustances are 1.91 and 2.01 Å, respectively. The water molecules do not play an important role in the structure and all distances between oxygen and other atoms indicate the presence of very weak hydrogen bonds. The salts M (en)₃ Q(CN)₆ · H₂O, where M = Co and Cr and Q = Cr, Mn, Fe and Co, are all isomorphous.     

Thermische Zersetzung und Lösungskalorimetrie von Ammoniumsamariumbromiden

Thermal Decomposition and Solution Calorimetry of Ammonium Samarium Bromides The ternary pure phases on the line SmBr₃—NH₄Br in the thermodynamically equilibrium have been synthesized by solid state reactions and characterized by X‐ray powderdiffraction. The existence of a new phase (NH₄)₃SmBr₆ was demonstrated beside the known phases (NH₄)₂SmBr₅ and NH₄Sm₂Br₇. The decomposition equilibria of the ammonium samarium bromides have been investigated by total pressure measurements and the thermodynamical data of the solid phase complexes derived from the decompostion functions. The standard enthalpies of solution in 4n HBr (aq.) of the ternary phases, SmBr₃ and Sm₂O₃, were measured and on the basis of these values and known data the standard enthalpies of ammonium samarium bromides were derived. The phase diagram is constructed on the basis of DTA measurements. Data from total pressure measurements: ΔH((NH₄)₃SmBr_{6, f, 298}) = —400, 0 ± 6, 5 kcal/mol S°((NH₄)₃SmBr_{6, f, 298}) = 146, 9 ± 8 cal/K · mol ΔH((NH₄)₂SmBr_{5, f, 298}) = —340, 6 ± 5, 0 kcal/mol S°((NH₄)₂SmBr_{5, f, 298}) = 106, 0 ± 6 cal/K · mol Δ(NH₄Sm₂Br_{7, f, 298}) = —479, 4 ± 6, 0 kcal/mol S°(NH₄Sm₂Br_{7, f, 298}) = 119, 5 ± 7 cal/K · mol Data from solution calorimetry: ΔH(SmBr_{3, f, 298}) = —204, 4 ± 1, 8 kcal/mol ΔH((NH₄)₃SmBr_{6, f, 298}) = —400, 7 ± 3, 2 kcal/mol ΔH((NH₄)₂SmBr_{5, f, 298}) = —339, 6 ± 2, 6 kcal/mol ΔH(NH₄Sm₂Br_{7, f, 298}) = —475, 6 ± 4, 4 kcal/mol     

Cs5[Na{W4N10}]: The first framework nitridotungstate(VI)

Cs₅[Na{W₄N₁₀}] was prepared from a mixture of NaNH₂, CsNH₂ and tungsten powder (molar ration 1 : 10 : 4) at 700°C in autoclaves. After the reaction is finished the nitride is embedded in an alkali metal matrix. Dark red crystals were isolated by washing out the alkali metal with liquid ammonia at room temperature. The structure of Cs₅[Na{W₄N₁₀}] was solved by X-ray single crystal data: I4₁ (No. 80), Z = 4, a = 13.926(3) Å, c = 8.723(3) Å, Z(F) ≥ 3σ(F) = 1535, Z(Variables) = 63, R/R_w = 0.040/0.052. The compound is highly sensitive against moisture giving oxotungstates and ammonia. It contains a framework of tetrahedra [WNN_3/2^1.5?]. Sodium shares four terminal nitrogen ligands. Including sodium a distorted, β-cristobalite type arrangement [Na{W₄N₁₀}^5?] results. It contains caesium in all interstices formed by twelve nitrogen ligands in so-called Friauf polyhedra.     

L'action de l'ammoniac sur l'oxyde cuivrique. et les hydroxo-complexes de cuivre (II)

Using a new mathematical treatment, the nature and stability constants of the simple and mixed complex-species of copper(II) with hydroxyde and ammonia as ligands have been determined. The solubility curves of CuO in heterogeneous equilibrium have been identified in function of pH only and in function of pH and pNH_3tot at 25° and unit ionic strength (NaClO₄). The predominent species in the relatively dilute system limited by the ionic strength are [Cu²⁺], [Cu(OH)₂], [Cu(OH)], [Cu(OH)], [Cu(NH₃)], [Cu(NH₃)], [Cu(NH₃)], [Cu(NH₃) (OH)⁺], [Cu(NH₃)₃(OH)⁺] and [Cu(NH₃)₂(OH)₂].     

Lithiumtriamidostannat(II), Li[Sn(NH2)3] – Synthese und Kristallstruktur

Lithium Triamidostannate(II), Li[Sn(NH₂)₃] – Synthesis and Crystal Structure Rusty-red glistening, transparent crystals of Li[Sn(NH₂)₃] were obtained by reaction of metallic lithium with tetraphenyl tin in liquid ammonia at 110 °C. The structure was determined from X-ray single-crystal diffractometer data: Space group P 2₁/n, Z = 4, a = 8.0419(9) Å, b = 7.1718(8) Å, c = 8.5085(7) Å, β = 90.763(8)°, R₁ (F _o ≥ 4σ(F _o)) = 2.8%, wR₂ (F ≥ 2σ(F )) = 5.3%, N(F ≥ 2σ(F )) = 1932, N(Var.) = 65. The crystal structure contains trigonal pyramidal complex anions [Sn(NH₂)₃]^– with tin at the apex, which are connected to layers of sequence A B A B … by lithium in tetrahedra-double units [Li(NH₂)_2/2(NH₂)₂]₂.     

Darstellung,Eigenschaften und Kristallstruktur von Na3[Yb(NH2)6]

Preparation, properties, and crystal structure of Na₃[Yb(NH₂)₆] Na₃[Yb(NH₂)₆] was prepared by the reaction of Na and Yb in the atomic ration 3:1 with ammonia at 150°C and 200 atm as a light grey microcrystalline powder. Colourless single crystals were obtained at 180°C and ～6000 atm. It decomposes rapidly at temperature above 140°C. At 250°C NaNH₂ nd a nitride phase results which crystallizes in the Nacl lattice type with a = 4.86 Å. Na₃[Yb(NH₂)₆] crystallizes orthorhombically with the lattice spacings a = 6.492 Å, b = 12.24 Å, and c = 21.33 Å with 8 formula units per unit cell. The space group is D–Pbca (No.61). The amide ions have a distorted close-packed arrangement with the layer sequence ABAC in the direction [010]. Ytterbium occupies on sixth, sodium one half of the octahedral interstices.     

Darstellung und Struktur eines Ammoniumdiamidodioxophosphats(V), NH4PO2(NH2)2

Synthesis and Structure of an Ammonium Diamidodioxophosphate(V), NH₄PO₂(NH₂)₂ The ammonolysis of P₃N₅ under ammonothermal conditions (T = 400°C, p(NH₃) = 6 kbar, 14 d in autoclaves) in the presence of small definite amounts of water leads to the formation of NH₄PO₂(NH₂)₂. The structure was solved by single crystal X-ray methods. NH₄PO₂(NH₂)₂: P2₁/c (Nr. 14), a = 6.886(1) Å, b = 8.366(2) Å, c = 9.151(2) Å, β = 111.78(3)°, Z = 4, R₁/wR₂ = 0.026/0.072, Z(F > 2σ(F)) = 1183, N(variables) = 87. In NH₄PO₂(NH₂)₂ the anions [PO₂(NH₂)₂]^? are linked to chains by N? H …? N and N? H …? O bridge bonds. The ammonium ions are located between these chains and are donors for N? H …? O bridge bonds which connect the chains three-dimensionally.     

Oxofluorovanadates(V). IV. Dioxotetrafluorovanadates

Preparation and properties of the salts of the series MVO₂F₄, where M = NH, Na⁺, K⁺, 1/2 Ni²⁺, and 1/3 [Co(NH₃)₆]³⁺ are described. Molecular conductivity of Na₃VO₂F₄ at different dilutions indicates that Na₃VO₂F₄ dissociates into 3 Na⁺ and VOaF ions. Ion exchange study of (NH₄)₃VO₂F₄ solution through cation exchange resin (H⁺ form) suggests that the corresponding acid decomposes partly to vanadium pentoxide. Reaction between (NH₄)₃VO₂F₄ with BaCl₂ and AgNO₃ solutions shows the formation of BaVO₂F₃ and AgVO₃ respectively. Thermogravimetric study of (NH₄)₃VO₂F₄ shows the formation of impure vanadium pentoxide as the ultimate product on heating up to 450°C. X-ray powder diffraction data are given for (NH₄)₃VO₂F₄ and Na₃VO₂F₄.     

Sulfoximid und Sulfoximidium-Salze – Strukturen und H?Brückenbindungen

Sulfoximide and Sulfoximidium Salts – Structures and Hydrogen Bonding In the solid state dimethylsulfoximide ( 1 ) (orthorhombic; space group Pbca; a = 577.8, b = 931.2 and c = 1645.6 pm) makes intermolecular N? H ? N hydrogen bonds. The hydrogen halide salts (CH₃)₂S(O)NH₂⁺Hal^? (( 2 ), Hal^??Cl^?; ( 4 ), Hal^??Br^?) reacts with metal halides to yield (CH₃)₂S(O)NH₂⁺MHal with the complex anions (( 5 ), MHal?SbCl₄^?; ( 6 ), MHal?SbCl₅^2?; ( 7 ), MHal?SbCl₆^?; ( 8 ), MHal?SbBr₅^2?; ( 9 ), MHal?AlCl₄^?). 2 crystallizes from ethanol (96%) as [(CH₃)₂S(O)NH₂⁺Cl^?]₂ · H₂O ( 3 ). The structures of 3 (monoclinic; space group P2₁/c; a = 917.0, b = 1344.7, c = 1080.8 pm and β = 103.8°; Z = 10), 4 (orthorhombic; space group Pbcn; a = 1028.9, b = 1132.6, c = 1074.1 pm; Z = 8) and 6 (monoclinic; space group C2/c; a = 2041.1, b = 1101.4, c = 3365.6 pm and β = 153.8°; Z = 8) are determined by X-ray analysis. In 6 Sb is coordinated in a distorted octahedra by 6 Cl in three short (mean 245,5 pm; SbCl₃) and three long distances (291 to 299 pm; Cl^?). Two of the chloride ions connect the Sb atoms to infinite Sb …? Cl …? Sb chains. Except for 7 and 9 there are bridges between the NH₂ groups and the halide ions. The NH valence vibrations are discussed in view of hydrogen bonding.     

Crystallization studies of poly(trimethylene terephthalate) using thermal analysis and far‐infrared spectroscopy

Crystallization of poly(trimethylene terephthalate) (PTT) by annealing was examined using density measurement, differential scanning calorimetry, and far‐infrared spectroscopy (FIR). Crystallinity, measured by density, increased slowly up to the T_a of 185 °C and increases rapidly once T_a exceeds 185 °C. It was found that thermally induced crystallization is mainly temperature‐dependent above T_a = 185 °C and temperature‐ and time‐dependent below T_a = 60 °C. Two melting transitions, T and T, were observed for those samples annealed above 120 °C. No significant change in T was observed as a function of T_a while T showed strong dependency on T_a. Digital subtraction of the amorphous contribution from the semicrystalline FIR spectra provided characteristic spectra of amorphous and crystalline PTT. The bands at 373, 282, and 92 cm^?1 were assigned to the crystalline phase, while the bands at 525, 406, and 351 cm^?1 were attributed to the amorphous phase. It was shown that FIR spectroscopy can be used as a means to estimate the degree of crystallinity of PTT. The band ratio of 373 and 501 cm^?1 was plotted against crystallinity measured by density and reasonably good correlation was obtained. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1675–1682, 2007     

The Crystal Structure of the NH4NCS Complex of Nonactin

The NH₄NCS complex of the macrotetrolide antibiotic nonactin crystallizes in the space group P1 , a = 12.565, b = 13.115, c = 14.999 Å, α= 91.22, β= 90.10, γ= 104.97°. The X-ray crystal structure analysis shows that the NH ion is coordinated by hydrogen bonds to the four ether oxygen atoms (NH … O, 2.86 Å). These four atoms and the four carbonyl oxygen atoms (N … O, 3.08 Å) enclose the NH ion in a somewhat distorted cube.     

Na2Mn(NH2)4: Ein neuer Schichtenstrukturtyp

Na₂Mn(NH₂)₄: A New Type of Layered Structure The structure of Na₂Mn(NH₂)₄ was solved by X-ray single crystal data including H-positions: P2₁/c, Z = 4, a = 6.331(1) Å, b = 14.542(3) Å, c = 7.212(1) Å, β = 116.29(1)°, Z(F ≥ 3σ = (F)) = 1343, Z(parameters) = 96, R/R_W = 0.023/0.029. The compound crystallizes in a new type of structure. Within layered blocks the amide ions are arranged with the motif of a hexagonal closest packing of spheres. Within these blocks alternating layers contain sodium in all octahedral sites and manganese in an ordered way in a quarter of tetrahedral sites.     

RbLi(NH2)2, a Rubidium Amido Lithiate Investigated by X‐Ray and Neutron Diffraction

RbLi(NH₂)₂ and the fully deuterated compound are obtained in autoclaves by the reaction of RbNH₂/RbND₂ and Li metal in supercritical NH₃/ND₃ (470 K, 220 Mpa, 41 d). X‐ray single crystal and neutron powder diffraction led to a new type of crystal structure closely related to the ThCr₂Si₂type. It is an orthorhombic distorted variant with an ordered half occupation by lithium on tetrahedral sites of puckered 4⁴ nets of amide ions to{[Li(NH₂)_1/1(NH₂)_3/3]} units and fully filled up sites of CN = 8 by Rb. The compound crystallizes in the space group Pnma with Z = 4 and a = 7.772 (2)Å, b = 3.843 (1)Å, c = 11.583 (2)Å. It contains an unexpected hydrogen bridge bonding system between crystallographic different amide ions.     

Proof of the Existence of a Linear,Centrosymmetric Polyiodide Ion I: the crystal structure of Cu(NH3)4 I4

Tetrammine-copper(II)-tetraiodide Cu(NH₃)₄I₄ crystallizes in the monoclinic space group C 2/m. The crystal structure has been determined from X-ray diffractometer data and refined to R_w = 2.2%. Four coplanar nitrogen atoms and two axial iodine atoms form an octahedral coordination around Cu(II) with a pronounced 4 + 2 tetragonal distortion. A connection of the Cu(II) atoms by linear, centrosymmetric I polyiodide ions results in infinite chains of [Cu(NH₃) I]-units. The central I-I-bond distance in I is 2.802(1) Å; a considerable amount of I-I bonding is indicated by the distance of 3.342(1) Å found for the terminal bonds. These intramolecular bond distances correspond to calculated I-I-bond orders of 0.80 and 0.43.