Die Kristallstruktur der Verbindung SbCl2F3

SbCl₂F₃ crystallizes in the monoclinic space group P 2₁/n (lattice parameters see above). The crystal structure has been determined by PATTERSON methods and refined three-dimensionally by the method of least squares. The structure is ionic and consists of tetrahedral SbCl cations and anions. In these anions pair of octahedrally coordinated Sb-atoms are linked by a fluorine bridge. A new interpretation of the IR and RAMAN spectra and a discussion of the character of the bonds of the fluorine atoms are given.     

Bildungsweise und Schwingungsspektren von Antimontetrachlorid-isocyanat [SbCl4NCO]2 und -cyanurat [SbCl4NCO]3

Formation and Vibrational Spectra of Antimony Tetrachloride Isocyanate [SbCl₄NCO]₂ and Cyanurate [SbCl₄NCO]₃ [SbCl₄NCO]₂ was obtained from K[SbCl₅NCO] and SbCl₅ in liquid SO₂. In solution it is only stable at lower temperatures (?20°C); at room temperatures or above irreversible rearrangement to [SbCl₄NCO]₃ takes place. At higher temperatures this also occurs in the solid state, so that both compounds seen to have the same melting point of 208°C. In the molten state decomposition takes place, SbCl₃ being a main product. According to its i. r. and Raman spectrum, [SbCl₄NCO]₂ is an isocyanate with bridging N-atoms. I. r. and Raman spectrum of [SbCl₄NCO]₃ show it to be a derivative of cyanuric acid. Mass spectral data of both compounds are reported.     

NQR-Untersuchungen an Addukten des SbCl3 und SbCl5. 35Cl- und 121,123Sb-NQR-spektroskopische Untersuchungen der Wechselwirkung zwischen SbCl3 bzw. SbCl5 und Phosphoryl- sowie Thiophosphorylchloriden

NQR Studies on Adducts of SbCl₃ and SbCl₅. ³⁵Cl- and ^121,123Sb-NQR Spectroscopic Studies of the Interaction between SbCl₃ or SbCl₅ and Phosphoryl or Thiophosphoryl Chlorides The complex formation between SbCl₃ and SbCl₅, respectively, and the chlorides POCl₃, P₂O₃Cl₄, and P₂OS₂Cl₄ has been studied by NQR spectroscopy. The formation of the adducts SbCl₃ · 2 POCl₃ and SbCl₅ · P₂OS₂Cl₄ has been proved. Based on its ³⁵Cl-NQR spectrum for the latter compound the constitution of a hexachloro antimonate P₂OS₂Cl₃⁺SbCl₆^? is assumed.     

Mechanismus der Polymerisation von 1,3-Dioxolan mit (C2H5)3O-, SbCl6 und SbCl5

Ohne Zusammenfassung     

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.     

Phosphaniminato-Komplexe des Antimons. Die Kristallstrukturen von [Sb2Cl5(NPMe3)2][SbCl6] · CH3CN und [SbCl(NPPh3)]2[SbCl6]2 · 6 CH3CN

Phosphorane Iminato Complexes of Antimony. The Crystal Structures of [Sb₂Cl₅(NPMe₃)₂][SbCl₆] · CH₃CN and [SbCl(NPPh₃)]₂[SbCl₆]₂ · 6 CH₃CN The title compounds are formed by reaction of antimony pentachloride in acetonitrile solution with the phosphorane iminato complexes SbCl₂(NPMe₃) and SbCl₂(NPPh₃), respectively, which themselves are synthesized by reaction of antimony trichloride with Me₃SiNPR₃ (R = Me, Ph). The complexionic compounds are characterized by ¹²¹Sb Mössbauer spectroscopy and by crystal structure determinations. [Sb₂Cl₅(NPMe₃)₂][SbCl₆] · CH₃CN: Space group P4₁, Z = 4, 3 698 observed unique reflections, R = 0.022. Lattice dimensions at ?60°C: a = b = 1 056.0(1), c = 2 709.6(2) pm. The structure consists of SbCl₆^? ions and cations [Sb₂Cl₅(NPMe₃)₂(CH₃CN)]⁺, in which one Sb^III atom and one Sb^V atom are bridged by the N atoms of the phosphorane iminato ligands. [SbCl(NPPh₃)]₂[SbCl₆]₂ · 6 CH₃CN: Space group P1 , Z = 2, 5 958 observed unique reflections, R = 0.033. Lattice dimensions at ?60°C: a = 989.4(11), b = 1 273(1), c = 1 396(1) pm, α = 78.33(7), β = 77.27(8)°, γ = 86.62(8)°. The structure consists of SbCl₆^? ions and centrosymmetric cations [SbCl(NPPh₃)(CH₃CN)₂]₂²⁺, in which the antimony atoms are bridged by the N atoms of the phosphorane iminato ligands.     

Darstellung,Eigenschaften und Schwingungsspektren von K[SbCl5N3], K[SbCl5NCO] und K[SbCl5CN]

Preparation, Properties and Vibrational Spectra of K[SbCl₅N₃], K[SbCl₅NCO] and K[SbCl₅CN]. KaN₃, KNCO and KCN react in liquid SO₂ with stoichiometric amounts of SbCl₅ yielding K[SbCl₅N₃] K[SbCl₅NCO], and K[SbCl₅CN], respectively. NaN₃ and SbCl₅ form Na[SbCl₅N₃] which contains impurities of Na[SbCl₆]. With more SbCl₅ (SbCl₄N₃)₂ is obtained from K[SbCl₅N₃] and (SbCl₄NCO)₂ from K[SbCl₅NCO], [BCl₂N₃]₃ is formed from K[SbCl₅N₃] and BCl₃. The vibrational spectra of the pentachloro-pseudohalo-antimonates can be assigned with a model of C_4v symmetry for the direct neighborhood of the Sb atoms.     

Mechanism of Polymerization of 1, 3-Dioxolane Initiated by (C2H5)3 O+SbCl6 and SbCl5

The kinetics of polymerization of 1, 3-dioxolane (DiOX) initiated by (C₂H₅)₃O⁺SbCl₆ and SbCl₅ has been studied and the elementary stages of the process have been considered. The polymerization of DiOX by (C₂H₅)₃O⁺SbCl₆-is shown to proceed at a steady rate to high conversion. A constant concentration of active centers in the system is maintained due to the equal rates of decomposition of active centers and disproportionation. The nonsteady-state character of DiOX polymerization initiated by SbCl₅is associated with a relatively lower stability of the counter-ion SbCl₅ OR^? compared with SbCl₆. The initiation of DiOX polymerization by (C₂H₅)₃O⁺SbCl₆ proceeds without hydride-transfer reactions, and the concentration of active centers in the system is determined not by processes taking place in the initiation stage, but by the existence of a definite kind of equilibrium with the participation of active centers.     

Synthese und Kristallstruktur des ionischen Tellurnitridchlorids [Te3N2Cl5(SbCl5)]+SbCl6−

Synthesis and Crystal Structure of the Ionic Tellurium Nitride Chloride[Te₃N₂Cl₅(SbCl₅)]⁺SbCl₆^? The title compound has been prepared by the reaction of Te₂NCl₅ with antimony pentachloride in CH₂Cl₂ suspension. It is characterized by IR spectroscopy and by a crystal structure determination. Space group P2₁/c, Z = 4, lattice dimensions at ?70°C: a = 1535.6, b = 1259.5, c = 1572.4 pm, β = 109.30°, R = 0.031. The compound forms an ionic pair with the central group of a (TeNCl)₂ molecule in which the tellurium atoms are linked by the nitrogen atoms to give a planar Te₂N₂ four-membered ring. One of the nitrogen atoms is coordinated by a TeCl₃⁺ unit, the other one by an antimony pentachloride molecule. According to the IR spectra a structure like [Te₂N₂Cl₂(TeCl₄)₂] is proposed for Te₂NCl₅.     

Crystal Structure of the Menshutkin Complex Benzene · 2SbCl3

Crystals of benzene · 2 SbCl₃, grown from the melt, are triclinic with space group P1 , two formula units per unit cell and lattice constants a = 816.5, b = 821.1,c = 1183.3 pm, α = 94.22, β = 94.00, γ = 108.55° at 295 K. The benzene molecule and the two SbCl₃ molecules are in general positions and form a molecular complex. The distances between the ring plane and the Sb atoms on opposite sides are 330 and 322 pm, similar to the π…Sb interactions in other Menshutkin complexes. Taking into account additional intermolecular contacts of the type Sb…Cl both Sb atoms have a deformed pentagonal-bipyramidal coordination with the benzene molecule in an axial position each. The SbCl₃ molecules form corrugated layers.     

Synthese,Kristallstruktur und 121Sb-Mößbauer-Spektrum von [SbCl2(18-Krone-6)]+SbCl6−

Synthesis, Crystal Structure, and ¹²Sb-Mössbauer Spectrum of [SbCl₂(18-Crown-6)]⁺SbCl₆^? The title compound, which has been prepared by the reaction of antimony trichloride and antimony pentachloride in the presence of 18-crown-6 in acetonitrile solution, is characterized by its ¹²¹Sb-Mössbauer spectrum and by an X-ray structure determination. Space group P2₁, Z = 2, 2439 observed unique reflections, R = 0.045, wR = 0.043. Lattice dimensions at ?80°C: a = 780.6(7), b = 1297.5(9), c = 1 278.5(10) pm, β = 100.56(7)°. The structure of [SbCl₂(18-crown-6)]⁺SbCl₆^? contains cations in which the antimony atom in the first coordination sphere is surrounded in a ?-trigonal-bipyramidal fashion by two oxygen atoms of the crown ether in axial position as well as in the equatorial position by the two chlorine atoms and the lone electron pair.     

Die Kristall- und MolekularStruktur von Antimontetrachloridazid (SbCl4N3)2

Antimony tetrachloride azide (SbCl₄N₃)₂ crystallizes in the monoclinic space group P2₁/n; the lattice parameters are: a = 8.051, b = 9.353, c = 10.124 Å; β = 93.75°; Z = 2. The crystal structure was solved with the aid of a Patterson synthesis and was refined by the method of least-squares to R = 4.9% for the 922 observed reflexions. The structure is built up from centrosymmetrical (SbCl₄N₃)₂ molecules (idealized point symmetry 2/m) which are arranged in the way of a body centered lattice. The linear azido groups are inclined against the planar (Sb–αN)₂ ring of the molecule by an angle of 24°. Each Sb atom is coordinated by two N and four Cl atoms in a distorted octahedral arrangement.     

Die Gasphasenintercalation von Graphit durch SbCl4F

Gas Phase Intercalation of Graphite by SbCl₄F Gas Phase Intercalation of Graphite by SbCl₄F using a two-zone technique is a method to prepare intercalation compounds of different stage index n in temperature range between 120 and 140°C. The reaction is a process of successive decrease of stage index. Increasing the reaction time, i. e. concentration, regions of pure stages alternate with two-phase regions. Intercalation compounds were characterized by X-ray technique, EPMA, and chemical methods. The compounds are stable in ordinary air, with aqueous HCl as well as KOH only pentavalent but not any trivalent antimony can be removed. The identity periods along c-axis in pure stages are I_c = 9.33 Å (n = 1), 12.72 Å (n = 2), 16.06 Å (n = 3) and 19.40 Å (n = 4). A (√7 × √ 7) 19.1° in-plane structure of intercalants was found. The uptake curve of mass with time reveals a discontinuity connected with formation of stage 2. Concave shape of curve during starting period at 120 and 125°C will be interpreted as a consequence of an induction time. From X-ray and EPMA studies it may be concluded that nucleation at the prismatic crystal edges controls the kinetics of reaction. Assuming a first order kinetics of filling the vacant sites, the same activation energy in case of formation of stage 1 and stage 2 have been determined approximately (97 and 102 kJ/mol).     

Strukturbestimmung der Verbindung SbCl4OCH3

SbCl₄OCH₃ crystallizes monoclinic, space group P2₁/n. After solving the projection along [100], x-coordinates were determined by the method of linear structure factor equations. The crystal structure is built up from (SbCl₄OCH₃)₂ units; pairs of octahedrally coordinated antimon atoms are linked by oxygen bridges.     

Kronenetherkomplexe von Blei(II). Die Kristallstrukturen von [PbCl(18-Krone-6)][SbCl6], [Pb(18-Krone-6)(CH3CN)3][SbCl6]2, and [Pb(15-Krone-5)2][SbCl6]2

Crown Ether Complexes of Lead(II). The Crystal Structures of [PbCl(18-Krone-6)][SbCl₆], [Pb(18-Krone-6)(CH₃CN)₃][SbCl₆]₂ und [Pb(15-Krone-5)₂][SbCl₆]₂ . [PbCl(18-crown-6)][SbCl₆] has been prepared in low yield besides [Pb(CH₃)₂(18-crown-6)][SbCl₆]₂ by the reaction of Pb(CH₃)₂Cl₂ with antimony pentachloride in acetonitrile solution in the presence of 18-crown-6, forming pale-yellow crystals. The other two title compounds are formed as colourless crystals by the reaction of PbCl₂ with antimony pentachloride in acetonitrile solutions in the presence of 18-crown-6 and 15-crown-5, respectively. The complexes were characterized by IR spectroscopy and by crystal structure determinations. [PbCl(18-crown-6)][SbCl₆]: Space group P2₁/c, Z = 8, 5 003 observed unique reflections, R = 0.046. Lattice dimensions at - 80°C: a = 1 386.9; b = 1 642.7; c = 2 172.1 pm, β = 92.95°. The lead atom in the cation [PbCl(18-crown-6)]⁺ is surrounded in an almost hexagonal-planar construction by the six oxygen atoms of the crown ether and an axially oriented Cl atom. [Pb(18-crown-6)(CH₃CN)₃][SbCl₆]₂: Space group P1 , Z = 2, 6 128 observed unique reflections, R = 0.076. Lattice dimensions at - 70°C: a = 1 228.0; b = 1 422.9; c = 1 463.2 pm, α = 69.08°; β = 65.71°; γ = 64.51°. In the cation [Pb(18-crown-6)(CH₃CN)₃]²⁺ the lead atom is coordinated by the six oxygen atoms of the crown ether and by the three nitrogen atoms of the acetonitrile molecules. The structure determination is restricted by disorder. [Pb( 15-crown-5)₂][SbCI₆]₂: Space group P6₃/m, Z = 6, 5 857 observed unique reflections, R = 0.059. Lattice dimensions at -70°C: a = b = 2 198.5; c = 1499.4 pm, α = β = 90°, γ = 120°. In the cation [Pb(l5-crown-5)₂]² the lead atom is sandwich-like coordinated by the ten oxygen atoms of the two crown ether molecules. The structure determination is restricted by disorder.     

Colloidal hydrolysis products of SbCl3 in acidic solutions

 The hydrolysis of SbCl₃ in hydrochloric acid solution (2.0 mol dm^-3 HCl) at 0 °C yields an amor-phous product consisting of uniform spherical particles (d∼0.5 μm), which on continuous aging at the same temperature transform to larger crystals, indicated by XRD to be Sb₄O₅Cl₂. In contrast, in the same solution kept at 25 °C crystalline particles of the same composition form directly after an induction period and then grow with time. The final products, obtained at 0 °C and 25 °C consist of aggregated subunits. These powders on calcination in nitrogen are converted to Sb₂O₃ and in air to Sb₂O₄. Received: 23 June 1997 Accepted: 1 July 1997