Die Reaktion von Trithiazylchlorid mit Titantetrachlorid Die Kristallstruktur von (S4N5)2[Ti2Cl10]

Reaction of Trithiazyl Chloride with Titanium Tetrachloride. Crystal Structure of (S₄N₅)₂[Ti₂Cl₁₀] In the reaction of trithiazyl chloride with titanium tetrachloride, chlorine is abstracted and the brown-yellow adduct TiCl₄(N₂S₂) is obtained. In this compound — according to its i.r. spectrum — a N₂S₂ ring is bonded to the titanium via the N atoms, thus forming a polymer. As a by-product, brown crystalline (S₄N₅)₂[Ti₂Cl₁₀] forms. Its crystal structure was determined and refined with X-ray diffraction data (R = 0.042 for 812 reflexions). It crystallizes in the monoclinic space group P2₁/c with two formula units per unit cell. The lattice constants are a = 670, b = 1 633, c = 1108 pm, β = 97.24°. The structure consists of S₄N₅^⊕ cations, which are nearly equal to those in [S₄N₅]Cl, and [Ti₂Cl₁₀]^2? anions, which are nearly identical with those in (PCl₄)₂[Ti₂Cl₁₀].     

Die Reaktionen von Eisen(III)-chlorid mit Trithiazylchlorid. Die Kristallstruktur von [S4N4Cl]+[FeCl4]⊖

Reactions of Iron Trichloride with Trithyazyl Chloride. Crystal Structure of [S₄N₄Cl]⁺[FeCl₄]^? Iron trichloride reacts with (NSCl)₃ yielding S₄N₄[FeCl₄]₂, S₃N₃Cl₂[FeCl₄] or S₄N₄Cl[FeCl₄], depending on the reaction conditions. The i.r. spectra prove the presence of [FeCl₄]^? ions for all three compounds. The ⁵⁷Fe-Mössbauer spectra show a slight quadrupole splitting at 80 K for S₃N₃Cl₂[FeCl₄] (ΔE^Q = 0.42 mm · s^?1) and S₄N₄Cl[FeCl₄] (ΔE^Q = 0.23 mm · s^?1), which indicates a slight deformation of the FeCl₄^? tetrahedra. The crystal structure of S₄N₄Cl[FeCl₄] was determined and refined with X-ray diffraction data (2549 independent reflexions, R = 0.026). S₄N₄Cl[FeCl₄] crystallizes in the triclinic space group P1 with two formula units per unit cell. The lattice constants are a = 712, b = 911, c = 1006 pm, α = 76.5°, β = 83.8° and γ = 80.5°. The structure consists of the so far unknown [S₄N₄Cl]^⊕ cations and slightly deformed FeCl₄^? ions. The [S₄N₄Cl]^⊕ ion consists of a S₄N₄ ring built up of two nearly planar S₃N₂ fragments having a dihedral angle of 136°. The average SN bond length is 157 pm, the SCI bond length 214 pm.     

Reaktionen von Oxiden der Elemente der V. Hauptgruppe mit Trithiazylchlorid Kristallstruktur von (S5N5)4[As8Cl28] · 2 S4N4

Reactions of Element Oxides of the Fifth Main Group with Trithiazyl Chloride. Crystal Structure of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄ Whereas P₄O₁₀ does not react with (NSCl)₃, the oxides As₂O₃, Sb₂O₃, and Bi₂O₃ react under formation of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄, S₅N₅[SbCl₆] and a mixture of S₄N₅[BiCl₄] and S₄N₄Cl[BiCl₄], respectively. The products were characterized by their IR spectra. The crystal structure of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄ was determined by means of X-ray diffraction (1168 independent observed reflexions, R = 0.059). Crystal data: tetragonal, space group P4 2₁c, Z = 2, a = 1596.6, c = 1520.1 pm. The compound consists of planar S₅N₅^⊕ cations, octameric anions [As₈Cl₂₈]^4? and S₄N₄ molecules. The S₅N₅^⊕ ions and the S₄N₄ molecules show positional disorder, which very probably is of dynamical type for the S₅N₅^⊕ ion. The [As₈Cl₂₈]^4? ions can be described as a (so far unknown) [As₄Cl₁₆]^4? ion with cubane-like structure (As? Cl bridging distances between 286 and 305 pm) to which four AsCl₃ molecules are attached via chloro bridges with As? Cl bond lengths between 314 and 328 pm.     

Die Kristallstruktur von (AsPh4)2[W2NCl10]

Crystal Structure of (AsPh₄)₂[W₂NCl₁₀] The title compound is formed by a slow reaction of AsPh₄[WNCl₄] in acetonitrile solution in form of dark brown crystals. The crystal structure was solved by X-ray diffraction methods (R = 4.7%; 1461 observed, independent reflexions). (AsPh₄)₂[W₂NCl₁₀] crystallizes in the monoclinic space group P2₁/n with two formula units per unit cell. The structure consists of AsPh₄^θ and [W₂NCl₁₀]^2θ ions. The tungsten atoms with oxidation numbers five and six respectively, are linked by a linear, asymmetric nitrido bridge (r WN = 171 and 203 pm). The trans-effect of the W? N-multiple bonds causes a significant difference between axial (W? Cl_ax 243 pm) and equatorial (mean W? Cl_eq 230 pm) bond lengths.     

Die Reaktionen von Dimethylsulfoxid mit Molybdäntetrabromid und Molybdändibromid-dinitrosyl Die Kristallstruktur von [MoBr2(NO)2(OSMe2)2]

Reactions of Dimethyl Sulfoxide with Molybdenum Tetrabromide and Molybdenum Dibromide Dinitrosyl. Crystal Structure of [MoBr₂(NO)₂(OSMe₂)₂] In the cold molybdenum tetrabromide reacts with an equivalent amount of dimethyl sulfoxide forming the solvate [MoBr₄(OSMe₂)₂]; excess dimethyl sulfoxide yields [MoO₂Br₂(OSMe₂)₂] which is also obtained by other methods. Molybdenum dibromidedinitrosyl forms the solvate [MoBr₂(NO)₂(OSMe₂)₂] in the reaction with dimethyl sulfoxide. According to the i.r. spectra all complexes display O-coordination of the OSMe₂ molecules. [MoBr₂(NO)₂(OSMe₂)₂] crystallizes monoclinic in the space group P2₁/c with four formula units per unit cell. The cell dimensions are a = 1236, b = 892, c = 1305 pm, β = 95.2°. 1662 independent observed reflexions were used for refinement; R = 3.8%. The molybdenum atoms are six-coordinated, the O atoms of the dimethyl sulfoxide molecules are in trans-position to the nitrosyl ligands, which form linear groups Mo? N? O.     

Azidocuprate(II). Die Kristallstruktur von (PPh4)2[Cu2(N3)6]

Azidocuprates(II). Crystal Structure of (PPh₄)₂[Cu₂(N₃)₆] (PPh₄)₂[Cu(N₃)₄] and (PPh₄)₂[Cu₂(N₃)₆], which is already known, are prepared from the corresponding chloro cuprates and excess silver azide in dichloro methane suspension. The azido cuprates form nonexplosive brown crystals of low sensitivity to moisture and are characterized by i.r. spectroscopy. (PPh₄)₂[Cu₂(N₃)₆] was submitted to a X-ray crystallographic structural analysis (4284 observed, independent reflexions, R = 0.034). The compound crystallizes triclinic in the space group P1 with one formula unit per unit cell. The lattice parameters are a = 1047.4 pm; b = 1131.1 pm; c = 1179.4 pm; α = 101.26°; β = 109.31°; γ = 103.42°. The compound consists of PPh₄^⊕ cations and centrosymmetric anions [Cu₂(N₃)₆]^2?, which meet D_2h-symmetry fairly well. In the anions the copper atoms are linked to a planar Cu₂N₂ four-membered ring by the N α atoms of two azide groups. The other azido ligands are bonded terminally and complete coordination number 4 at the Cu atoms which show planar geometry.     

Die Kristallstruktur von CsTcO4 [1]

The Crystal Structure of CsTcO₄ CsTcO₄ crystallizes orthorhombic with a = 5.72₇, b = 5.92₁ and c = 14.34 Å. Z = 4, space group Pnma (Nr. 62, I.T.). The metal positions were refined by single crystal data, the oxygen positions first determined: the CsTcO₄ structure is a slight distortion of the scheelite arrangement (parameters: see text). The MADELUNG Part of Lattice Energy, MAPLE, ?Mean Effective Ionic Radii”?, MEIR, and Effective Coordination Numbers, ECoN, are calculated and discussed.     

Die Kristallstruktur von Zr(Sn,Sb)2

Ohne Zusammenfassung     

Die Kristallstruktur von AgIIF[AgIIIF4]

Crystal structure of Ag^IIF[Ag^IIIF4] For the first time dark brown single crystals of mixedvalent AgF[AgF₄] were isolated under solvothermal conditions out of anhydrous HF/F₂. The compound crystallizes in a new type of structure, triclinic with a = 499.9(2) pm, b = 1108.7(5) pm, c = 735.7(3) pm, α = 90.05(3)°, β = 106.54(4)°, γ = 90.18(4)°, spcgr. P1¯ — C_i¹ (No. 2) and Z = 4.     

Synthese und Kristallstruktur von (PPh4)2[Mo2Cl10]

Synthesis and Crystal Structure of (PPh₄)₂[Mo₂Cl₁₀] The title compound is obtained in the reaction of [MoCl₄(Ph? C?C? Ph)]₂ with tetraphenylphosphonium chloride in dichloro methane, forming brown crystals. It is characterized by the i.r. spectrum and a crystal structure analysis by the aid of X-ray diffraction data. The complex crystallizes triclinic in the space group P1 with one formula unit per unit cell. The cell dimensions are a = 1122 pm, b = 1137 pm, c = 1283 pm; α = 63.4°, β = 69.1°, γ = 86.5°. The crystal structure determination (2959 observed, independent reflexions, R = 4.5%) shows the constants of the unit cell to consist of on centrosymmetric anion, two cations and one disordered molecule of dichloro methane. The distance Mo? Mo in the anion is 380 pm, which excludes direct magnetic interaction between the molybdenum atoms.     

Die Kristallstruktur von B(OC2H4)3N

Zusammenfassung B(OC₂H₄)₃N kristallisiert in der Raumgruppe P ca2₁ mit den Gitterkonstantena=11,46,b=6,62,c=9,79 Å undZ=4. Die Struktur konnte mit direkten Methoden und mit sukzessivenFouriersynthesen aufgeklärt werden [570 F(hkl), R=9,8%]. Bor befindet sich in tetraedrischer Umgebung von Sauerstoff (B–O 1,431, 1,432, 1,475 Å) und Stickstoff (B–N 1,693 Å). In der Struktur bestehen zwischen den Komplexen keine Wasserstoffbrücken.

---

The crystal structure ofB(OC ₂H₄)₃ N. Triethanolamine complexes, IV

B(OC₂H₄)₃N crystallizes in space group P ca2₁ with cell dimensionsa=11.46,b=6.62,c=9.79 Å andZ=4. The structure has been solved by direct methods and byFourier syntheses [570 F(hkl), R=9.8%]. Boron is tetrahedrally surrounded by oxygen (B–O 1.431, 1.432, 1.475 Å) and nitrogen atoms (B–N 1.693 Å). In the structure no hydrogen bonds exist between the complexes.

---

---

Mit 3 Abbildungen     

Reaktionen von Zinnchloriden mit Polysulfiden. Die Kristallstrukturen von (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O] und (PPh4)2[SnCl6] · S8 · 2CH3CN

Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh₄)₂[SnCl₂(S₆)₂], (PPh₄)₂[Sn₄Cl₄S₅(S₃)O], and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN . The reaction of PPh₄[SnCl₃] with Na₂S₄ in acetonitrile in the presence of small amounts of water yields (PPh₄)₂[Sn₄Cl₄S₅(S₃)O] and minor amounts of (PPh₄)₂[SnCl₂(S₆)₂], PPh₄Cl · 2S₈ and (PPh₄)₂[SnCl₆]. SnCl₄ is partially reduced by (PPh₄)₂S_x, PPh₄[SnCl₃] and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN being produced. According to the X-ray crystal structure determination the [Sn₄Cl₄S₅(S₃)O]^2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S₃ group. In the [SnCl₂(S₆)₂]^2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S₆ groups. Octahedral [SnCl₆]^2? ions and S₈ molecules in the crown conformation are present in (PPh₄)₄[SnCl₆] · S₈ · 2CH₃CN.     

Die Kristallstruktur von Na4CoO4[1]

The Crystal Structure of Na₄CoO₄ According to X-Ray investigations on single crystals, Na₄CoO₄ crystallizes triclinic (P1, a = 8.64₈, b = 5.70₂, c = 6.40₀ Å, α = 123.9°, β = 98.1°, γ = 99.2°). There are almost tetrahedral CoO₄-groups; sodium is coordinated by four or five O^2?.     

Über die Reaktionen von N-Chloracetonimin mit Molybdänpentachlorid und Wolframhexachlorid Die Kristallstruktur von Me2CNH2[MoOCl4]

Reactions of N-Chloroacetoneimine with Molybdenum Pentachloride and Tungsten Hexachloride. Crystal Structure of Me₂C?NH₂[MoOCl₄] WCl₆ reacts with N-chloroacetoneimine under elimination of chlorine and formation of pentachloro-isopropylideneimino-tungsten(VI), Cl₅W?N?CMe₂, a brown-black crystal powder, which was characterized by i.r. spectroscopy. MoCl₅ reacts in a similar way, although only a product mixture can be obtained. Partial hydrolysis of this mixture yields isopropylideneiminium-tetrachlorooxomolybdate(V), Me₂C?NH₂⁺[MoOCl₄]^?, of which the crystal structure was determined (2323 unique observed reflexions, R = 0.049). Space group P2₁/c, Z = 4, a = 878.6, b = 907.2, c = 1252.2 pm, β = 91.29°. The compound consists of Me₂C?NH₂⁺ ions with a planar arrangement of the skeletal atoms and a CN bond length of 126.7 pm and of dimeric, centrosymmetric anions [MoOCl₄]₂^2? having Mo atoms linked via asymmetric chloro bridges (MoCl distances 238.4 and 307.6 pm). The longer Mo? Cl contacts are located in the trans-positions of the terminal oxoligands (MoO distance 164 pm).     

Reaktionen von Diorganogallium(indium)fluoriden. Die Kristallstruktur von Mes2InF

Reaction of Diorganogallium(indium) Fluorides. The Crystal Structure of Mes₂InF Mes₂GaF ( 1 ) reacts with t-BuNH₂ at 20°C to the amine adduct [Mes₂Ga(F)(t-BuNH₂)] ( 2 ). Treatment of 1 with H₂S gives after a redox reaction γ-S₈-Sulfur (Muthmanns' Sulfur) ( 3 ) as the only isolated product. When i-Pr₂InF ( 4 ) is reacted with [SnCl₂(dioxane)] in toluene at 70°C one yields after workup [i-PrInCl₂(dioxane)] ( 5 ), which is formed after ligand exchange and reaction with dioxane. 2 and 5 were investigated by NMR-, IR- and MS-techniques. In addition, 2 · 2,5 THF, 3, 5 and Mes₂InF were characterized by an X-ray structure determination. According to that 2 · 2,5 THF contains dimeres, associated by hydrogen brigdes, while 5 possesses a polymeric structure with bridging dioxane molecules. 3 forms eightmembered rings with C ₂-symmetry. Me₂InF is a trimer in the solid state with an In₃F₃-backbone.     

Die Reaktion von Trichlornitromethan mit Eisencarbonylen Kristallstruktur von (PPh4)2[Fe2OCl6] · 2 CH2Cl2

Reaction of Trichloronitro Methane with Iron Carbonyls. Crystal Structure of (PPh₄)₂[Fe₂OCl₆] · 2 CH₂Cl₂ Trichloronitro methane reacts with Fe₂(CO)₉ or Fe₃(CO)₁₂ forming NO[FeOCl₂] which is composed of Nitrosyl ions and polymeric [FeOCl₂]^?. The reaction of NO[FeOCl₂] with POCl₃ affords Fe(O₂PCl₂)₃; with tetraphenyl phosphoniumchloride it forms the complex (PPh₄)₂[Fe₂OCl₆] which is soluble in CH₂Cl₂. The oxochloro ferrates are characterized by the aid of ⁵⁷Fe-Mössbauer spectra and by i.r. spectra. A single crystal of (PPh₄)₂[Fe₂OCl₆] · 2 CH₂Cl₂ was used to carry out a structural investigation by means of X-ray diffraction data (space group P1 , Z = 1, a = 1157.2(2), b = 1363.8(3), c = 1140.3(2) pm, α = 109.22(1)°, β = 95.23(1)°, γ = 67.24(2)°, R = 0.052 for 3814 reflexions with F₀ > 3σ). The [Cl₃Fe? O? FeCl₃]^2?-anion is found to have a centre of symmetry and thus, in accordance with the i.r. spectra, contains a linear bridge. High thermal parameters of the bridging oxygen atom and the chlorine ligands, however, allow interpretations as orientation disorder of slightly bent anions.     

Thionitrosylkomplexe des Osmiums. Die Kristallstruktur von AsPh4[OsCl4(NS)2Cl]

Thionitrosyl Complexes of Osmium. Crystal Structure of AsPh₄[OsCl₄(NS)₂Cl] The reaction of osmium pentachloride with trithiazyl chloride (NSCl)₃ yields the thiazylchloride complex [OsCl₄(NSCl)₂], from which the thionitrosyl complex AsPh₄[OsCl₄(NS)₂Cl] is obtained by reaction with AsPh₄Cl in CH₂Cl₂. From this, the neutral thionitrosyl complex [OsCl₄(NS)₂] forms by chloride abstraction with gallium trichloride. The crystal structure of AsPh₄[OsCl₄(NS)₂Cl] was determined and refined with the aid of X-ray diffraction data (R = 0.033, 2161 reflexions). It crystallizes in the monoclinic space group P2₁/c with four formula units per unit cell. The lattice constants are a = 1735, b = 1058, c = 1578 pm and β 95.64°. In the [OsCl₄(NS)₂Cl]^? ion the osmium is octahedrally coordinated by four Cl atoms and two NS groups in a cis arrangement. The NS groups are essentially linear with the bond lengths Os?N 184 pm and N?S 146 pm. Loosely attached to one of the S atoms there is a Cl atom (S? Cl distance 228 pm); in the crystal it statistically belongs to both S atoms with an occupation probability of one half, and it cannot be decided whether there is a dynamical fluctuation between the S atoms or a static positional disorder. However, according to the i.r. spectrum the dynamical model seems more probable.     

Synthese und Kristallstruktur von [N(Hex)4][Cu2(CN)3]

Synthesis and Crystal Structure of [N(Hex)₄] [Cu₂(CN)₃] [N(Hex)₄][Cu₂(CN)₃] has been prepared by solvothermal reaction of CuCN with Tetra‐n‐hexylammoniumiodide in acetone. The crystal structure is built up by condensed (CuCN)₆ and (CuCN)₇ rings, forming a zeolith type cyanocuprate(I) framework [Cu₂(CN)₃^—]. Space group R3; α = 44.482(6), c = 21.283(4) Å, V = 36471(9) ų; Z = 9.     

Synthese und Koordination von 2-Acetylimino-1,3-dimethylimidazolin. Die Kristallstruktur von [Cu4I4(C7H11N3O)2] [1]

Synthesis and Coordination of 2-Acetylimino-1,3-dimethylimidazoline. The Crystal Structure of [Cu₄I₄(C₇H₁₁N₃O)₂] 2-Acetylimino–1,3-dimethylimidazoline ( 2 , ImNAc) obtained from 1,3-dimethyl-2-iminoimidazoline ( 1 ) and acetyl chloride forms with CuI the stepped cubane type complex [Cu₄I₄(ImNAc)₂] ( 3 ); the X-ray structure of 3 is reported.     

Die Kristallstruktur von Antimontetrachlorid-cyanurat [SbCl4NCO]3

The Crystal Structure of Antimony Tetrachloride Cyanurate [SbCl₄NCO]₃ [SbCl₄NCO]₃ crystallizes in the hexagonal space group P6₃/m with two formula units per unit cell; the lattice parameters are a = 1167 and c = 995 pm. The crystal structure was solved with X-ray diffraction data by means of a Patterson and a Fourier Synthesis and was refined by the method of least-squares to a reliability index of R = 3.6% for the 863 observed reflexions. The structure consists of [SbCl₄NCO]₃ molecules having the point symmetry 6 . The molecule is a derivate of cyanuric acid in a way such that each Sb atom is bonded in chelate manner by one N and one O atom; together with 4 Cl atoms the antimony attains a distorted octahedral coordination. The packing density in the crystal is not optimal, there exist cavities.