Die Kristallstruktur des W3CoB3 und der dazu isotypen Phasen Mo3CoB3, Mo3NiB3 und W3NiB3

Zusammenfassung Mo₃CoB₃, Mo₃NiB₃, W₃CoB₃ und W₃NiB₃ kristallisieren in einem eigenen Typ (W₃CoB₃-Struktur). Das trigonal prismatische Bauelement [T ₆B]^* ist zu Ketten vereinigt, wobei B₃-Gruppen entstehen. Die Phasen sind vermutlich Bor-reicher als obiger Formel entspricht.

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The crystal structure of W₃CoB₃ and the isotypic phases Mo₃CoB₃, Mo₃NiB₃, and W₃NiB₃

Mo₃CoB₃, Mo₃NiB₃, W₃CoB₃, and W₃NiB₃ were found to possess a new type of crystal structure (W₃CoB₃-structure type). Trigonal prismatic groups [T ₆B]^* are linked together forming chains in such a way that B₃-groups occur. These borides do probably exist with a larger amount of boron as to compared with the formula.

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Mit 2 Abbildungen     

K3BiSe3, Rb3BiSe3 und Cs3BiSe3 – Substitutionsvarianten des Th3P4-Typs

K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃ – Derivatives of the Th₃P₄ Structure Type The compounds K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃ were synthesized by heating mixtures of Bi₂O₃ and the respective alkalicarbonate in a stream of hydrogen saturated by selenium at 850°C. Thin crystals of the compounds appear red in transmitted light. They crystallize isostructural with Na₃AsS₃, space group P2₁3, lattice constants a = 9.771(5) Å, a = 10.161(3) Å, and a = 10.587(5) Å for K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃, respectively. The Na₃AsS₃ structure type is a derivative of the Th₃P₄ structure type.     

Die Akzeptoreigenschaften von AsCl3, AsBr3, asJ3, SbCl3, SbBr3 und SbJ3

Zusammenfassung Es wurden die Enthalpien der Reaktionen von AsCl₃, AsBr₃, AsJ₃, SbCl₃, SbBr₃ und SbJ₃ mit Tributylphosphat, N,N-Dimethylacetamid und Hexamethylphosphorsäuretriamid bestimmt. Das Verhalten der Addukte bei Gegenwart eines Überschusses der Donoren wird beschrieben.

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Acceptor properties of AsCl₃, AsBr₃, AsI₃, SbCl₃, SbBr₃, and SbI₃

The enthalpies of the reactions of AsCl₃, AsBr₃, AsI₃, SbCl₃, SbBr₃ and SbI₃ with tributylphosphate, N,N-dimethylacetamide and hexamethylphosphoric acid triamide were measured. The behavior of the adducts in the presence of excess donor molecules is described.

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Mit 5 Abbildungen     

K3SbSe3, Rb3SbSe3 und Cs3SbSe3 – Synthese und Kristallstruktur

K₃SbSe₃, Rb₃SbSe₃, and Cs₃SbSe₃ – Synthesis and Crystal Structure The compounds K₃SbSe₃, Rb₃SbSe₃ and Cs₃SbSe₃ were synthesized by heating mixtures of Sb₂O₃ and an alkalicarbonate in a stream of hydrogen saturated by selenium in a temperature range between 750 °C and 800 °C. The compounds crystallize isostructural with Na₃AsS₃. A comparison of atomic distances and bond angles with those of the isostructural arsenic and bismuth compounds shows the effect of lone pairs.     

A comparison of local structures in crystalline P(EO)3LiCF3SO3 and glyme-LiCF3SO3 systems

The newly discovered crystal structures of CH₃(OCH₂CH₂)OCH₃(LiCF₃SO₃)₂, monoglyme:(LiTf)₂, and CH₃(OCH₂CH₂)₃OCH₃(LiCF₃SO₃)₂, triglyme:(LiTf)₂, are briefly described. The coordination of lithium cations and the CF₃SO₃⁻ anions in these structures is compared with the cation and anion coordination in the crystalline phase of high molecular weight P(EO)₃LiCF₃SO₃. Comparison is also made with the previously reported crystalline phase of CH₃(OCH₂CH₂)₂OCH₃LiCF₃SO₃, diglyme:LiTf. A tendency to form trans-gauche-trans conformations for the bond order -O-C-C-O- is noted in adjacent ethylene oxide sequences interacting with a five-coordinate lithium ion.     

3, 3, 3-Trifluoropropyl(methyl)cyclosiloxanes

The influence of the number of 3, 3, 3-trifluoropropyl(methyl)siloxane links (Φ/Φ) in the cyclotetrasiloxanes Φ_mD_4-m, where D represents the dimethylsiloxane link and m=0–4, on the rearrangement of these compounds in acetone solution under the action of sodium siloxanolate has been studied. The rearrangement takes place with the formation of a linear polysiloxane the degradation of which yields, in addition to the initial ring, cyclosiloxanes with a different structure. The rate of rearrangement of Φ_mD_4-m and of the formation of a linear polysiloxane rises with an increase in m from 0 to 3. The equilibrium concentration of the linear polysiloxane formed from Φ_mD_4-m is inversely proportional to m. Results have been obtained on the kinetics of the formation of the cyclosiloxanes Φ_mD_n, where m=0–5, n=0–5, and m+n=3–6, in the rearrangement of the rings ΦD₃, Φ₂D₂, Φ₃D, and Φ₄. The reactivity of the siloxane links rises in the sequence ～ (CH₃)₂Si-O-Si(CH₃)₂ ～<～ (CF₃CH₂CH₂)-(CH₃) Si-O-Si(CH₃)₂ ～<(CF₃CH₂CH₂) (CH₃)Si-O-Si(CH₃) (CH₂CH₂CF₃) ～. Because of the negative inductive effect transferred through the siloxane links, the 3, 3, 3-trifluoropropyl groups strongly activate the siloxane ring with respect to nucleophiiic reagents.     

Die Perthioborate RbBS3, TIBS3 und TI3B3S10

The Perthioborates RbBS₃, TIBS₃, and Tl₃B₃S₁₀ . RbBS₃ (P2₁/c, a=7.082(2) Å, b=11.863(4) Å, c=5.794(2) Å, β=106.54(2)°) was prepared as colourless, plate-shaped crystals by reaction of stoichiometric amounts of rubidium sulfide, boron, and sulfur at 600°C and subsequent annealing. TlBS₃ (P2₁/c, a=6.874(3) Å, b=11.739(3) Å, c=5.775(2) Å, β=113.08(2)°) which is isotypic with RbBS₃ was synthesized from a sample of the composition Tl₂S · 2 B₂S₃. The glassy product which was obtained after 7 h at 850°C was annealed in a two zone furnace for 400 h at 400→350°C. Yellow crystals of TlBS₃ formed at the warmer side of the furnace. Tl₃B₃S₁₀ (P1 , a=6.828(2) Å, b=7.713(2) Å, c=13.769(5) Å, α=104.32(2)°, β=94.03(3)°, γ=94.69(2)°) was prepared as yellow plates from stoichiometric amounts of thallium sulfide, boron, and sulfur at 850°C and subsequent annealing. All compounds contain tetrahedrally coordinated boron. The crystal structures consist of polymeric anion chains. In the case of RbBS₃ and TlBS₃ nonplanar five-membered B₂S₃ rings are spirocyclically connected via the boron atoms. To obtain the anionic structure of Tl₃B₃S₁₀ every third B₂S₃ ring of the polymeric chains of MBS₃ is to be substituted by a six-membered B(S₂)₂B ring.     

Na3AsSe3 und K3AsSe3 – Darstellung und Kristallstruktur

Na₃AsSe₃ and K₃AsSe₃ – Synthesis and Crystal Structure The compounds Na₃AsSe₃ and K₃AsSe₃ were synthesized by heating mixtures of As₂O₃ and the respective alkalicarbonate in a stream of hydrogen saturated by selenium at 750 °C. The structures were determined from X-ray single-crystal diffractometer data. Both compounds crystallize isostructural with Na₃AsS₃, space group P2₁3, Z = 4, lattice constants a = 8,925 (1) Å for Na₃AsSe₃ and a = 9,710(1) Å for K₃AsSe₃.     

Syntheses and Crystal Structures of the Novel Ternary Thioborates Na3BS3, K3BS3, and Rb3BS3

The orthothioborates Na₃BS₃, K₃BS₃ and Rb₃BS₃ were prepared from the metal sulfides, amorphous boron and sulfur in solid state reactions at temperatures between 923 and 973 K. In a systematic study on the structural cation influence on this type of ternary compounds, the crystal structures were determined by single crystal X‐ray diffraction experiments. Na₃BS₃ crystallizes in the monoclinic space group C2/c (No. 15) with a = 11.853(14) Å, b = 6.664(10) Å, c = 8.406(10) Å, β = 118.18(2)° and Z = 4. K₃BS₃ and Rb₃BS₃ are monoclinic, space group P2₁/c (No. 14) with a = 10.061(3) Å, b = 6.210(2) Å, c = 12.538(3) Å, β = 112.97(2) and a = 10.215(3) Å, b = 6.407(1) Å, c = 13.069(6) Å, β = 103.64(5)°, Z = 4. The potassium and rubidium compounds are not isotypic. All three compounds contain isolated [BS₃]^3– anions with boron in a trigonal‐planar coordination. The sodium cations in Na₃BS₃ are located between layers of orthothioborate anions, in the case of K₃BS₃ and Rb₃BS₃ stacks of [BS₃]^3– entities are connected via the corresponding cations. X‐ray powder patterns were measured and compared to calculated ones obtained from single crystal X‐ray structure determinations.     

Dimethylarsenazid (CH3)2AsN3, Dimethylwismutazid (CH3)2BiN3 und Dimethylthalliumzid (CH3)2TiN3

The reaction of (CH₃)₂AsJ and AgN₃ yields (CH₃)₂AsN₃; a colourless liquid (b. p. 136°C) which dissolves as a monomeric in benzene. (CH₃)₂BiN₃ is precipitated in form of colourless needles (dec. temp. 150°C) from an etherical solution of Bi(CH₃)₃ and HN₃. According to its vibrational and mass spectra the molecules are not associated although the (CH₃)₂BiN₃ is not soluble; dipole association of this polar molecules is assumed for the crystal structure. (CH₃)₂TlN₃ can be obtained from TI(CH₃)₃ and ClN₃ as well as from (CH₃)₂TlOH and HN₃ in form of colourless needles and leaves (dec. temp. 245°C). According to its vibrational spectra it has an ionic structure, (CH₃? Tl? CH₃)⁺N^?₃.     

Untersuchungen an Stickstoff-Jod-Verbindungen. X. Das Infrarotspektrum von Stickstofftrijodid-3-Ammoniak NJ3 · 3NH3 und Stickstofftrijodid-3-Deuteroammoniak NJ3 · 3ND3 im Bereich der N-J-Grundschwingungen

Studies on Nitrogen Iodine Compounds. X. The IR Spectra of NI₃ · 3NH₃ and NI₃ · 3ND₃ in the Region of N? I Fundamental Vibrations The IR spectra of NI₃ · 3 NH₃ and NI₃ · 3 ND₃ are similar to those of (NI₃ · NH₃)_n and (NI₃ · ND₃)_n, respectively. Especially the positions of the N? I vibrations are identical. From these results it is allowed to conclude that NI₃ · 3 NH₃ shows a N? I scaffold similar to the well known N? I scaffold of (NI₃ · NH₃)_n.     

Schwingungsspektren und Kraftkonstanten der Übergangsreihen OP (CH3)3–OP(OCH3)3 und SP(CH3)3–SP(OCH3)3

Vibrational Spectra and Force Constants of the Series OP(CH₃)₃? OP(OCH₃)₃ and SP(CH₃)₃? SP(OCH₃)₃ The vibrational spectra of OP(CH₃)₂(OCH₃), OP(CH₃)(OCH₃)₂, SP(CH₃)₂(OCH₃), and SP(CH₃)(OCH₃)₂, are recorded and assigned to the normal vibration. The valence force constants are calculated by a simplified force field. The results are disscussed for both series and compared with former results.     

Syntheses and Crystal Structures of BaAgTbS3, BaCuGdTe3, BaCuTbTe3, BaAgTbTe3, and CsAgUTe3

Five new quaternary chalcogenides of the 1113 family, namely BaAgTbS₃, BaCuGdTe₃, BaCuTbTe₃, BaAgTbTe₃, and CsAgUTe₃, were synthesized by the reactions of the elements at 1173–1273 K. For CsAgUTe₃ CsCl flux was used. Their crystal structures were determined by single‐crystal X‐ray diffraction studies. The sulfide BaAgTbS₃ crystallizes in the BaAgErS₃ structure type in the monoclinic space group C³,_2h‐C2/m, whereas the tellurides BaCuGdTe₃, BaCuTbTe₃, BaAgTbTe₃, and CsAgUTe₃ crystallize in the KCuZrS₃ structure type in the orthorhombic space group D¹_,2⁷_,h‐Cmcm. The BaAgTbS₃ structure consists of edge‐sharing [TbS₆^9–] octahedra and [AgS₅^9–] trigonal pyramids. The connectivity of these polyhedra creates channels that are occupied by Ba atoms. The telluride structure features ²_∞[MLnTe₃^2–] layers for BaCuGdTe₃, BaCuTbTe₃, BaAgTbTe₃, and ²_∞[AgUTe₃^1–] layers for CsAgUTe₃. These layers comprise [MTe₄] tetrahedra and [LnTe₆] or [UTe₆] octahedra. Ba or Cs atoms separate these layers. As there are no short Q ··· Q (Q = S or Te) interactions these compounds achieve charge balance as Ba²⁺M⁺Ln³⁺(Q^2–)₃ (Q = S and Te) and Cs⁺Ag⁺U⁴⁺(Te^2–)₃.     

Tetraazadibora[3, 3]paracyclophane

Starting from the para‐phenylenediamine derivative HN(SiMe₃)‐C₆H₄‐NH(SiMe₃), a lithiation and subsequent borylation give [(MeO)₂B]N(SiMe₃)‐C₆H₄‐N(SiMe₃)[B(OMe)₂] ( 1 ), the hydridation of which yields Li₂[(H₃B)N(SiMe₃)‐C₆H₄‐N(SiMe₃)(BH₃)] ( 2 ). Applying ZrCl₄ upon 2 initiates a condensation to give the title compound [‐N(SiMe₃)‐p‐C₆H₄‐N(SiMe₃)‐BH‐]₂, a hetero[3, 3]paracyclophane with two N‐B‐N chains that connect the para‐phenylene units. The product 3 crystallizes in the orthorhombic space group P2₁2₁2₁.     

The Lewis basicity of the [Pt3(μ-CO)3(PR3)3] clusters and the X-ray crystal structure of [{ZnI2}{Pt3(μ-CO)3(PPh(i-Pr)2)3}]

The cluster compounds [Pt₃(μ-CO)₃(PR₃)₃] act as Lewis bases towards the metal halides of Group XI, MX, Group XII, MX₂, and Group XIII, MX₃, to form cluster compounds of the composition [{MX_n}{Pt₃(μ-CO)₃(PR₃)₃}]. The X-ray crystal structure, NMR and IR data are given for the compound [{ZnI}{Pt₃(μ-CO)₃(PPh(i-Pr)₂)₃}].     

Interaction in Systems Ln2O3-CsPO3 and Ln2O3- UO3-CPO3

Abstract

The systems Ln₂O₃-CsPO₃ and Ln₂O₃-UO₃-CsPO₃ were investigated and three sets of compounds A, B, C were isolated.     

Synthese von 3-desoxy-3-amino-vitamin D3 und 3-desoxy-3-epiamino-vitamin D3 und D2

Vitamin D₂ and D₃ are transformed with triphenylphosphane-diethylazodicarboxylate-HN₃ into the epimeric azidoderivatives 1 and 3 with inversion of the configuration at C-3. Reduction with LiAlH₄ yields 3-desoxy-3-epiamino-vitamin D₂ and D₃2 and 4, which are characterized as their acetamides 2a and 4a. Furthermore epivitamin D₃-p-nitrobenzoate 5 is produced by reaction of vitamin D₃ with triphenyl- phosphanediethylazodicarboxylate-p-nitrobenzoic acid, which yields epivitamin D₃5a after saponification. Utilizing the same method as above leads with epivitamin D₃ to 5a 3-desoxy-3-azidovitamin D₃6, which is reduced to 3-desoxy-3-amino-vitamin D₃7 by LiAlH₄ and characterized as its acetamide 7a.     

Vibrational spectra and normal co-ordinate analysis of CF3 compounds. Trimethyl(trifluoromethyl)silane,CF3Si(CH3)3 and CF3Si(CD3)3

The i.r. gas and Raman liquid spectra of CF₃Si(CH₃)₃ and CF₃Si(CD₃)₃ are reported and assigned for C_3vsymmetry. Force constants have been calculated by a combined analysis of both isotopomers yielding ƒ (SiCF₃) 2.63, ƒ (SiCH₃) 3.07 and ƒ (CF) 5.70 N cm⁻¹. The apparent weakness of the SiCF₃ bond confirms the results obtained on other CF₃ silanes and is discussed with respect to related molecules.     

Zwei Galliumfluorid-Ammoniakate: Ga(NH3)F3 und Ga(NH3)2F3

Two Gallium Fluoride Ammine Complexes: Ga(NH₃)F₃ and Ga(NH₃)₂F₃ Two gallium trifluoride ammines, Ga(NH₃)F₃ and Ga(NH₃)₂F₃, are obtained as single crystals through oxidation of gallium metal with NH₄HF₂ (Ga : NH₄HF₂ = 1 : 1.5) and NH₄F (Ga : NH₄F = 1 : 3.5), respectively, at 450 °C and 400 °C. Ga(NH₃)F₃ crystallizes with the non-centrosymmetric space group Abm2 (a = b = 544.6(2) pm, c = 986.6(4) pm) forming two-dimensional layers of [Ga(NH₃)F₅] octahedra. The addition of another NH₃ molecule in Ga(NH₃)₂F₃ (orthorhombic, Immm, a = 700.0(3) pm, b = 724.7(2) pm, c = 393.1(1) pm) leads to one-dimensional rods of [Ga(NH₃)₂F₄] octahedra running parallel [001] which are stacked in the [010] direction. Infrared spectra suggest hydrogen bonding (N–H…F) in Ga(NH₃)F₃, for Ga(NH₃)₂F₃ an unequivocal statement is not possible.     

Synthese und Kristallstruktur des ersten Oxonitridoborates — Sr3[B3O3N3]

Synthesis and Crystal Structure of the First Oxonitridoborate — Sr₃[B₃O₃N₃] The cyclotri(oxonitridoborate) Sr₃[B₃O₃N₃] was synthesized at 1450 °C as coarsely crystalline colourless crystals by the reaction of SrCO₃ with poly(boron amide imide) using a radiofrequency furnace. The structure was solved by single‐crystal X‐ray diffractometry (Sr₃[B₃O₃N₃], Z = 4, P2₁/n, a = 663.16(2), b = 786.06(2), c = 1175.90(3) pm, η = 92.393(1)°, R1= 0.0441, wR2 = 0.1075, 1081 independent reflections, 110 refined parameters). Besides Sr²⁺ there are hitherto unknown cyclic [B₃O₃N₃]^6— ions (B—N 143.7(10) — 149.1(9) pm, B—O 140.5(8) — 141.4(8) pm).