Untersuchungen an Stickstoff—Jod-Verbindungen. VII. Das IR-Spektrum des Stickstofftrijodid-1-Ammoniaks im Bereich der N–J-Grundschwingungen und Kraftkonstanten der N–J-Bindungen

Studies on nitrogen iodine compounds. VII. The IR spectrum of nitrogen triiodide-1 ammonia in the range of N—I fundamental vibrations and the valence force constants of the N—I bonds New infrared spectra in the region 33—600 cm^?1 of ¹⁴NI₃ · ¹⁴NH₃, ¹⁵NI₃ · ¹⁵NH₃ and ¹⁴NI₃ · pyridine, respectively, have been obtained. In addition, the infrared spectrum of ¹⁴NI₃ · ¹⁴ND₃, which has been prepared for the first time, was obtained. All absorption frequencies can be coordinated on the ground of the molecule model for the NI₃ scaffold with 5 atoms Z₂XY₂ of the symmetry C_2v which has been proved by X ray examination. A set of force constants has been calculated by approximation. The various nitrogeniodine valence force constants are discussed.     

Die Kristallstruktur von Stickstofftrijodid-1-Pyridin NJ3 · C5H5N

The Crystal Structure of Nitrogen Triiodide-1-Pyridine NI₃ · C₅H₅N The crystal structure of NI₃ · C₅H₅N like “Nitrogen Triiodide” NI₃ · NH₃ contains NI₄ tetrahedra as essential structure elements. The tetrahedra are connected by common corners, forming indefinite chains. The pyridine molecule is bonded by its lone electron pair to one of the two iodine atoms that do not participate in the connection of the tetrahedra. Different from NI₃ · NH₃ there are very weak intermolecular interactions between iodine atoms of neighbouring chains.     

Untersuchungen an Stickstoff-Jod-Verbindungen. IX. Präparative und infrarotspektroskopische Untersuchungen an Jod-Komplexen von N-Jodmethylaminen

Studies of Nitrogen Iodine Compounds. IX. Preparation and I. R. Investigations of Iodine Complexes of N-Iodine Methylamines [CH₃NI₂]₂ · I₂, [(CH₃)₂NI]₂ · I₂ and (CH₃)₂NI · I₂, have been prepared. The IR-spectra have been obtained in the region 33–4000 cm^?1. The spectra can be coordinated on the ground of a molecule model with 5 atoms Z₂XYW of the symmetry C_s and are compared to that of CH₃NI₂. The structures of the compounds are proposed to be monomolecular.     

Synthese und Kristallstruktur der Monoammoniakate von Lithiumhalogeniden: LiBr·NH3 und LiI·NH3

Syntheses and Crystal Structures of the Monoammoniates of Lithium Halides: LiBr·NH₃ and LiI·NH₃ Crystals of LiBr·NH₃ and LiI·NH₃ sufficient in size and quality for X‐ray structure determinations were obtained in autoclaves by the reaction of Li with NH₄Br and LiH with NH₄I at 523 K and 423 K respectively. Lattice constants obtained from X‐ray single crystal data are: LiBr·NH₃: P2₁/n, a = 7, 077(2)Å, b = 7, 026(2)Å, c = 7, 490(2)Å β = 114, 84(3)°, Z = 4 LiI·NH₃: P2₁, a = 4, 493(1)Å, b = 6, 077(1)Å, c = 7, 512(2)Å β = 107, 15(3)°, Z = 2 The ammoniates contain different structural building units. Both of them contain layers of connected tetrahedra Li(NH₃)X_3/3 with X = Br, I. Tetrahedra‐double units with a common Br‐Br edge occur, whilst for the iodide all tetrahedra are exclusively vertex connected to puckered layers. IR‐ and Raman‐spectroscopic measurements show, that only weak H‐bridges N‐H···X are present and that the NH₃‐ligands are in fixed positions at room temperature.     

Untersuchungen an Polyhalogeniden. XVI. Darstellung und Kristallstrukturen der Bipyridiniumpolyiodide Bipy · HIn mit n = 3, 5 und 7

Studies on Polyhalides. 16. Preparation and Crystal Structures of Bipyridiniumpolyiodides Bipy · HI_n with n = 3, 5, and 7 With simply protonated α,α′-Bipyridyl Bipy · H⁺ a triiodide Bipy · HI₃, a pentaiodide Bipy · HI₅ and a heptaiodide Bipy · HI₇ may be prepared in the presence of iodide ions I^? and dependent of the iodine I₂ content. Bipyridiniumtriiodide C₁₀H₉N₂I₃ crystallizes at room temperature monoclinically in P2₁/n with a = 1 122.8(1) pm, b = 1 072.7(1) pm, c = 1 200.2(3) pm, β = 98.02(2)° and Z = 4. The crystal structure is built up from mixed cationic and anionic layers. Bipyridiniumpentaiodide C₁₀H₉N₂I₅ crystallizes at room temperature monoclinically in P2₁/c with a = 887.3(5) pm, b = 2 527.9(12) pm, c = 830.7(3) pm, β = 106.78(5)° and Z = 4. The crystal structure contains triiodide ions I₃^? till now uniquely connected by iodine molecules I₂ in a trigonal planar way. Bipyridiniumheptaiodide C₁₀H₉N₂I₇ crystallizes at room temperature triclinically in P&1macr; with a = 713.1(3) pm, b = 1 007.9(3) pm, c = 1 464,8(4) pm, α = 81.07(3)°, β = 89.92(3)°, γ = 82.77(3)° and Z = 2. The crystal structure contains a V-shaped pentaiodide ion I₅^? completed by an iodine molecule I₂ to a trigonal pyramidally shaped heptaiodide ion I₇^? and at the same time connected to a zigzag chain.     

Zur Frage der Richtigkeit und Genauigkeit von Analysen im aquatischen Bereich

Zusammenfassung Bei Analysen im aquatischen Bereich kommen Wasserproben verschiedenster Art (in bezug auf Vielfalt und Konzentration der Inhaltsstoffe) ebenso wie unbelebte und belebte Schwebestoffe bzw. Sedimente und niedere und höhere Pflanzen- und Tierformen zur Untersuchung. Für die Genauigkeit und Richtigkeit der abschließenden Untersuchungsergebnisse sind nicht nur die meist auf mehrere signifikante Zahlenstellen genauen Resultate der eigentlichen Analyse, sondern auch die ebenso relevanten, aber oft nur annähernd abschätzbaren milieubedingten Faktoren wie die räumliche und zeitliche Homogenität des Untersuchungsmediums oder rasch ablaufende biochemische Reaktionen zu berücksichtigen.Es soll unbedingt vermieden werden, durch Angabe von zu vielen, durch Multiplikation erhaltenen Ziffernstellen, den Eindruck einer größeren als der tatsächlich erreichbaren Genauigkeit zu erwecken.Als praktisches Beispiel werden Untersuchungen des Schwermetallgehaltes im Sediment eines Flußstauraumes erläutert.

---

On the problem of precision and accuracy of analyses in the field of aquatic environment

Summary Analytical investigations in the field of the aquatic environment comprise vastly different materials like aqueous samples (varying in diversity and concentration of solutes), non-animate and animate disperserd matter as well as lower and higher plant and animal species.Precision and accuracy of the final results depend not only on the analytical procedure proper — usually obtained with a precision of some significant digits — but also on various intrinsic factors like spatial and temporal gross homogeneity and rapid biochemical reactions.It should be carefully avoided to pretend a degree of accuracy better than actually available by stating figures obtained by multiplication only. Investigations of the heavy metal content of river impoudment sediments are described and discussed as an example.

---

---

Herrn Prof. Dr. H. Weisz zum 60. Geburtstag gewidmet     

Über die Reaktion von Phosphorpentachlorid mit BF3 · NH3

Phosphorus pentachloride reacts with BF₃ · NH₃ to give [Cl₃P?N? PCl₃][BCl₄](Va). Mechanism of formation and chemical behaviour to SO₂ and H₂S are described, followed by a presentation and discussion of the ³¹P, ¹⁹F, and ¹¹B NMR spectra of the adducts formed by P₂NOCl₅ and BF₃, BCl₃, and PF₅, respectively.     

Untersuchungen an Salzhydraten. V. Die Schwingungsspektren und die thermische Zersetzung von LiBO2 · nH2O

The Vibrational Spectra and The Thermal Decomposition of LiBO₂ · nH₂O The vibrational spectra and thermogravimetric data of the hydrates of LiBO₂ are reported and the coordination of the H₂O molecules is discussed. The water molecules of the D₂O compounds separate at slightly higher temperatures as those of the H₂O compounds.     

Untersuchungen an Hydriden im Bereich der η-Phase Ti4Fe2O

Alloys of titanium and iron with varying oxygen content in the above mentioned phase take up considerable amounts of hydrogen. It will be shown, that hydriding and dehydriding can be processed in a reversible way. The hydrides have been investigated by X-ray, metallography, and NMR. Susceptibility and vapour pressure measurements have been performed The arrangement of the hydrogen atoms in the host lattice will be discussed.

     

Vergleich der Kristallstrukturen der Tetraammoniakate von Lithiumhalogeniden,LiBr·4NH3 und LiI·4NH3, mit der Struktur von Tetramethylammoniumiodid,N(CH3)4I

A Comparison of the Crystal Structures of the Tetraammoniates of Lithium Halides, LiBr·4NH₃ and LiI·4NH₃, with the Structure of Tetramethylammonium Iodide, N(CH₃)₄I Crystals of the tetraammoniates of LiBr and LiI sufficient in size for X‐ray structure determinations were obtained by slow evaporation of NH₃ at room temperature from a clear solution of the halides in liquid ammonia. The compounds crystallize in the space group Pnma (No. 62) with four formula units in the unit cell: LiBr·4NH₃: a = 11.947(5)Å, b = 7.047(4)Å, c = 9.472(3)Å LiI·4NH₃: a = 12.646(3)Å, b = 7.302 (1)Å, c = 9.790(2)Å For N(CH₃)₄I the structure was now successfully solved including the hydrogen positions of the methyl groups. N(CH₃)₄I: P4/nmm (No. 129), Z = 2, a = 7.948(1)Å, c = 5.738(1)Å The ammoniates of LiBr and LiI crystallize isotypic in a strongly distorted arrangement of the CsCl motif. Even N(CH₃)₄I has an CsCl‐like structure. Both structure types differ mainly in their orientation of the [Li(NH₃)₄]⁺ — resp. [N(CH₃)₄]⁺ — cations with respect to the surrounding “cube” of anions.     

Metall-Schwefelstickstoff-Verbindungen. 17. Die Verbindungen HgN2S · NH3 und 2Hg(NH3)2I2 · S4N4

Metal Sulphur Nitrogen Compounds. 17. Compounds HgN₂S · NH₃ and Hg(NH₃)₂I₂ · S₄N₄ The crystal and molecular structures of the known compounds HgN₂S · NH₃ and of the new inclusion compound 2Hg(NH₃)₂I₂ · S₄N₄ are reported. HgN₂S · NH₃ is orthorhombic, space group Pbca with a = 5.548, b = 10.158, c = 14.919 Å, Z = 8. In the dimeric molecules two Hg atoms are bridged to form eight-membered rings . In addition, each Hg is coordinated by an NH₃ molecule and by an N atom of an adjacent ring. This results in a two-dimensional network. 2Hg(NH₃)₂I₂ · S₄N₄ is tetragonal, space group P4₂/nmc, a = 8.948, c = 13.188 Å, Z = 2. It is an inclusion compound with S₄N₄ molecules in the holes of the lattice of the large Hg(NH₃)₂I₂ tetrahedra.     

Zu Herstellung und Konstitution der Verbindung 3 CaO · 3 GeO2 · H2O

On the Preparation and Constitution of the Compound 3 CaO · 3 GeO₂ · H₂O In the temperature range from 100–∽450°C it is possible to prepare under hydrothermal conditions from equimolar mixtures of CaO and GeO₂ the compound 3 CaGeO₃ · H₂O. By n.m.r. measurements of the solid compound it is shown, that there are only OH groups and no molecular water. It seems to be probable that this compound is a trigermanate of the formula Ca₃H₂ [Ge₃O₁₀].     

Hexamincyclotriphosphazenhemiammoniakat,P3N3(NH2)6 · 0,5 NH3, ein Produkt der Hochdruckammonolyse von weißem Phosphor

Hexaminecyclotriphosphazenehemiammoniate, P₃N₃(NH₂)₆ · 0.5 NH₃, a Product of High Pressure Ammonolysis of White Phosphorus White phosphorus gives at NH₃-pressures ≥5 kbar and temperatures above 250°C in a disproportionation reaction P₃N₃(NH₂)₆ · 0.5 NH₃; besides these products red phosphorus is formed. The yield on P₃N₃(NH₂)₆ · 0.5 NH₃ increases with T and is about 70–80% at 400°C as to the disproportionation reaction of the amount of white phosphorus. X-ray structure determination was successful on single crystals of P₃N₃(NH₂)₆ · 0.5 NH₃. Pbca, N = 8 a = 11.395(3) Å, b = 12.935(4) Å, c = 12.834(4) Å R = 0.035, R_w = 0.041 with w = 1, N (F_o²) ≥ 3σ(F_o²) = 1371, N(Var.) = 166. The molecules are connected by N? H? N-bridgebonds with 3.04 Å ≤ d(N …? N) ≤ 3,19 Å and d (N? H) = 0.87 Å. The compound is furthermore characterized by IR-data and its thermical behaviour.     

Addukte schwefelhaltiger Heteroaromaten mit SbCl3 Untersuchungen zur Bildung und Kristallstruktur von 2,2′-Dithienyl · 2 SbCl3 und Benzo[b]thiophen · 2 SbCl3

Adducts of Sulfur-containing Hetero Aromates with SbCl₃: Studies on Formation and Crystal Structure of 2,2′-Dithienyl · 2 SbCl₃ and Benzo[b]thiophene · 2 SbCl₃ Whereas the system 2,2′-dithienyl—SbCl₃ because of irreversible thermal decomposition reactions could not be studied by DTA, this method applied to the system benzo[b]thiophene—SbCl₃ yielded a quasibinary behaviour and the existence of a compound benzo[b]thiophene · 2SbCl_3. melting congruently at 71.2°C. Crystals of this adduct and that of analogue composition 2,2′-dithienyl · 2SbCl₃ were obtained from solution. Their structures were determined by X-ray diffraction as those of bπ-v complexes. They are compared with other Menshutkin complexes. The π…?Sb interactions are indicated by distances between the planes of the planar hetero aromates and the Sb atoms located in a transoid way above both single rings of 316 (dithienyl adduct) and 325 pm (benzothiophene adduct). There is no particular coordinative bond formation by the S atoms. The intermolecular linking in the SbCl₃ partial structures is described.     

Zur Darstellung und Kristallstruktur der Thiotellurite BaTeS3 · 2 H2O und (NH4)2TeS3

Preparation and Crystal Structure of the Thiotellurites BaTeS₃·2H₂O and (NH₄)₂TeS₃ The new compounds BaTeS₃ · 2 H₂O and (NH₄)₂TeS₃ have been prepared and their structures determined. According to these the anion of the trithiotelluric acid in these compounds represents a distorted trigonal TeS?pyramid. The Te? S-distances are 2.34–2.36 Å. Crystallographic data see ?Inhaltsübersicht”?.     

Monoammoniates of Aluminium Halides: The Crystal Structures of AlBr3 · NH3 and AlI3 · NH3

Single crystals of AlBr₃ · NH₃ and AlI₃ · NH₃ sufficient in size for X‐ray structure determinations were obtained by evaporation/ sublimation of the respective compound from its melt. The ammoniates were synthesized by the reaction of the pure halide with NH₃ at ‐78°C and following homogenization by slowly heating the reaction mixture up to the melting points of the ammoniates (124°C and 126°C, respectively). The X‐ray structure determinations for both monoammoniates were successfully carried out for the heavy atom positions (no hydrogen atoms): AlBr₃ · NH₃: Pbca, Z = 16, a = 11.529 (5) Å, b = 12.188 (2) Å, c = 19.701 (4) Å AlI₃ · NH₃: Pbca, Z = 8, a = 13.536 (5) Å, b = 8.759 (2) Å, c = 14.348 (4) Å The structures contain tetrahedral molecules Al(NH₃)X₃ with X = Br, I. They are not isotypic. The main difference is given for the coordination of NH₃ by X^‐ from neighbouring molecules. In Al(NH₃)Br₃ one of the two crystallographically independent NH₃ ligands has 6Br^‐ and the other 7Br^‐ as neighbours whereas in Al(NH)₃I₃ only 5I^‐ surround the one kind of NH₃.     

Schwingungsspektren und Kraftkonstanten symmetrischer Kreisel. XXI [1]. Das Schwingungs-Rotationsspektrum von CF379Br und CF381Br im Bereich von v2

Vibrational Spectra and Force Constants of Symmetric Tops. XXI. Rovibrational Spectrum of CF₃⁷⁹Br and CF₃⁸¹Br in the v₂ Region The rovibrational spectrum of CF₃⁷⁹Br and of natural CF₃Br has been recorded in the region of the fundamental v₂ near 750 cm^?1 in the i.r. with a resolution of 0.04 cm^?1. From the analysis of the spectra the values of v₀, the anharmonicity constants x₂₃, x₂₅ and x₂₆ as well as B″ and B′ from the J structure have been obtained both for CF₃⁷⁹Br and CF₃⁸¹Br. v₂ displays Fermi resonance with 2v₃ which is located near 700 cm^?1.     

Das Verhalten der Oxinate von Niob, Tantal und Begleitmetallen im IR-Spektrum

Ohne Zusammenfassung     

Die Pyridinaddukte der Goldhalogenide. 2. Darstellung,Eigenschaften und Kristallstruktur von AuCl · NC5H5 und Aul · NC5H5

Pyridine Adducts of the Gold Halides. 2. Synthesis, Properties, and Crystal Structure of AuCl · NC₅H₅ and AuI · NC₅H₅ AuCl · py is formed by the reaction of AuCl · S(CH₂C₆H₅)₂ with pyridine in absolute Ethanol. AuI · py can be obtained from AuI and pyridine in toluene. Both compounds are sensitive to light and thermically instable. AuI · py decomposes already above ?30°C. AuCl · py crystallizes monoclinic with 16 formula units in the space group C2/c, AuI · py is orthorhombic with the space group Pnnm and 8 formula units per unit cell. The structures of the adducts are built up by linear Au(py)₂ and AuX₂ groups, which are linked together to tetranuclear, chainlike complexes AuX₂? Au(py)₂? Au(py)₂? AuX₂ by weak gold-gold bonds. (AuI · py)₄ forms a linear Au₄ chain and possesses nearly the symmetry D_2h. The shortest Au-Au distance being 299.0 pm. In the centrosymmetrical (AuCl · py)₄ an Au₄-zig-zag chain with Au? Au distances of 324.9 and 341.6 pm is observed. The gold-ligand bond lengths are: AuCl · py: Au? Cl = 228 pm, Au? N = 209 pm; AuI · py: Au? I = 254.4, Au? N = 202 pm. The IR spectra and the luminescence properties are discussed.