The Reactions of Zn(CF3)Br · 2 CH3CN with Phenol,Pentafluorophenol, their Potassium and Ammonium Salts

Triphenoxymethane, tris(pentafluorophenoxy)methane, phenyl(difluoromethyl)ethers, and tetrakis(pentafluorophenoxy)ethene were prepared via carbenoid reactions of Zn(CF₃)Br · 2 CH₃CN and the corresponding phenol or the potassium or ammonium salts in the presence of the auxiliary acid BF₃ · O(CH₃)₂. The products were identified by their melting and boiling points and in part by their NMR and mass spectra as well as elemental analysis.     

Synthesen und NMR‐Untersuchungen von Salzen mit den neuen Anionen [PtXn(CF3)6‐n]2— (n = 0 ‐ 5, X = F,OH, Cl,CN) und die Kristallstrukturanalyse von K2[(CF3)2F2Pt(μ‐OH)2PtF2(CF3)2]·2H2O

Syntheses and NMR Spectroscopic Ivestigations of Salts containing the Novel Anions [PtX_n(CF₃)_6‐n]^2— (n = 0 ‐ 5, X = F, OH, Cl, CN) and Crystal Structure of K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O The first syntheses of trifluoromethyl‐complexes of platinum through fluorination of cyanoplatinates are reported. The fluorination of tetracyanoplatinates(II), K₂[Pt(CN)₄], and hexacyanoplatinates(IV), K₂[Pt(CN)₆], with ClF in anhydrous HF leads after working up of the products to K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O. The structure of the salt is determined by a X‐ray structure analysis, P2₁/c (Nr. 14), a = 11.391(2), b = 11.565(2), c = 13.391(3)Å, β = 90.32(3)°, Z = 4, R₁ = 0.0326 (I > 2σ(I)). The reaction of [Bu₄N]₂[Pt(CN)₄] with ClF in CH₂Cl₂ generates mainly cis‐[Bu₄N]₂[PtCl₂(CF₃)₄] and fac‐[Bu₄N]₂[PtCl₃(CF₃)₃], but in contrast that of [Bu₄N]₂[Pt(CN)₆] with ClF in CH₂Cl₂ results cis‐[Bu₄N]₂[PtX₂(CF₃)₄], [Bu₄N]₂[PtX(CF₃)₅] (X = F, Cl) and [Bu₄N]₂[Pt(CF₃)₆]. In the products [Bu₄N]₂[PtX_n(CF₃)_6‐n] (X = F, Cl, n = 0—3) it is possibel to exchange the fluoro‐ligands into chloro‐ and cyano‐ligands by treatment with (CH₃)₃SiCl und (CH₃)₃SiCN at 50 °C. With continuing warming the trifluoromethyl‐ligands are exchanged by chloro‐ and cyano‐ligands, while as intermediates CF₂Cl and CF₂CN ligands are formed. The identity of the new trifluoromethyl‐platinates is proved by ¹⁹⁵Pt‐ and ¹⁹F‐NMR‐spectroscopy.     

Attempted Abstraction of the Halogenides in (HNEt3)[Re(CH3CN)2Cl4] and Crystal Structures of cis‐[Re(CH3CN)2Cl4]·CH3CN and cis‐[Re(NHC(OCH3)CH3)2Cl4]

The abstraction of the halogenide ligands in [Re(CH₃CN)₂Cl₄]^? should result in a solvent‐only stabilized Re^III complex. The reactions of salts of [Re(CH₃CN)₂Cl₄]^? with silver(I) and thallium(I) salts were investigated and the solid‐state structures of cis‐[Re(CH₃CN)₂Cl₄]·CH₃CN and cis‐[Re(NHC(OCH₃)CH₃)₂Cl₄] are described.     

Synthesis,Characterization, and Crystal Structures of [N(CH3)4]2[B12H12] and [N(CH3)4]2[B12H12] · CH3CN

Bis(tetramethylammonium) dodecahydrododecaborate, [(CH₃)₄N]₂[B₁₂H₁₂], and bis(tetramethylammonium) dodecahydrododecaborate acetonitrile, [(CH₃)₄N]₂[B₁₂H₁₂] · CH₃CN, were synthesized and characterized via Infrared, ¹H and ¹¹B NMR spectroscopy. [(CH₃)₄N]₂[B₁₂H₁₂] crystallizes isopunctual to the alkali metal dodecaborates. The crystal structure of [(CH₃)₄N]₂[B₁₂H₁₂] · CH₃CN was determined from single crystal data and refined in the orthorhombic crystal system (Pcmn, no. 62, a = 898.68(8), b = 1312.85(9) c = 1994.5(1) pm, R(|F| , 4σ) = 5.9%, wR(F²) = 18.3%). Here, the geometry of the dodecaborate anion is that of an almost ideal icosahedron, less distorted than most other dodecaborates known. By low‐temperature Guinier‐Simon diffractometry phase transitions were detected for [(CH₃)₄N]₂[B₁₂H₁₂] and [(CH₃)₄N]₂[B₁₂H₁₂] · CH₃CN at –70 and –15 °C, respectively.     

Die Chlorooxoarsenate(III) (PPh4)2[As4O2Cl10] · 2 CH3CN und (PPh4)2[As2OCl6] · 3 CH3CN

The Chlorooxoarsenates(III) (PPh₄)₂[As₄O₂Cl₁₀] · 2 CH₃CN and (PPh₄)₂[As₂OCl₆] · 3 CH₃CN (PPh₄)₂[As₂Cl₈] can be prepared from As₂O₃, SOCl₂ and PPh₄Cl in acetonitrile. Its oxidation with chlorine yields PPh₄[AsCl₆]. This was also obtained directly from arsenic, chlorine and PPh₄Cl, (PPh₄)₂[As₄O₂Cl₁₀] · 2 CH₃CN being a side product; the latter was obtained with high yield from AsCl₃, As₂O₃ and PPh₄Cl in acetonitrile. By addition of PPh₄Cl it was converted to (PPh₄)₂[As₂OCl₆] · 3 CH₃CN. According to their X-ray crystal structure analyses, both crystallize in the triclinic space group P 1. The [As₄O₂Cl₁₀]^2– ion can be regarded as a centrosymmetric association product of two Cl₂AsOAsCl₂ molecules and two Cl^– ions, each Cl^– ion being coordinated with all four As atoms. In the [As₂OCl₆]^2– ion the As atoms are linked via the O atom and two Cl atoms.     

Synthesis and Crystal Structure of Copper(II) Trifluoroacetates,Cu2(CF3COO)4 · 2 CH3CN and Cu(CF3COO)2(H2O)4

Cu₂(CF₃COO)₄ · 2 CH₃CN ( I ) and Cu(CF₃COO)₂(H₂O)₄ ( II ) have been prepared by concentrating of acetonitrile and aqueous solutions respectively. According to X-ray data, the complex I consists of binuclear molecules with Cu–O 1.969 Å, Cu–N 2.114 Å. The Cu…Cu distance was found to be 2.766 Å, one of the longest for dimeric structures, apparently, due to the high acidity of trifluoroacetic acid. The coordination environment of Cu atom in II can be described as 4 + 2: 2 Cu–O (H₂O) 1.937 Å, 2 Cu–O (CF₃COO) 1.985 Å, 2 Cu–O (H₂O) 2.447 Å. The mononuclear structure is stabilized by formation of two intra- and six intermolecular hydrogen bonds.     

Fluoroborates by Cleavage of Trimethylamine‐bis(trifluoromethyl)boranes with NEt3 × 3 HF. Structures of C6F5(CF3)2B · NMe3, K[C6H5CH2(CF3)2BF], and K[C6H5(CF3)2BF]

Trimethylamine‐bis(trifluoromethyl)boranes R(CF₃)₂B · NMe₃ (R = cis/trans‐CF₃CF=CF ( 1/2 ), HC≡C ( 3 ), H₂C=CH ( 4 ), C₂H₅ ( 5 ), C₆H₅CH₂ ( 6 ), C₆F₅ ( 7 ), C₆H₅ ( 8 )) react with NEt₃ × 3 HF depending on the nature of R at 155–200 °C under replacement of the trimethylamine ligand to form the corresponding fluoro‐bis(trifluoromethyl)borates [R(CF₃)₂BF]^– ( 1 a/2 a – 8 a ). The structures of 7 , K[C₆H₅CH₂(CF₃)₂BF] ( K‐6 a ), and K[C₆H₅(CF₃)₂BF] ( K‐8 a ) have been investigated by single‐crystal X‐ray diffraction. In 7 the CF₃ groups make short repulsive contacts with NMe₃ and C₆F₅ entities – the B–CF₃ bonds being unusually long. The B–F bond lengths of K‐6 a and K‐8 a (1.446(3) and 1.452(2) Å, respectively) are long for a fluoroborate.     

Kristallstruktur und Schwingungsspektrum von (H2NPPh3)2[SnCl6]·2CH3CN

Crystal Structure and Vibrational Spectrum of (H₂NPPh₃)₂[SnCl₆]·2CH₃CN Single crystals of (H₂NPPh₃)₂[SnCl₆]·2CH₃CN ( 1 ) were obtained by oxidative addition of tin(II) chloride with N‐chloro‐triphenylphosphanimine in acetonitrile in the presence of water. 1 is characterized by IR and Raman spectroscopy as well as by a single crystal structure determination: Space group , Z = 2, lattice dimensions at 193 K: a = 1029.6(1), b = 1441.0(2), c = 1446.1(2) pm, α = 90.91(1)°, β = 92.21(1)°, γ = 92.98(1)°, R₁ = 0.0332. 1 forms an ionic structure with two different site positions of the [SnCl₆]^2? ions. One of them is surrounded by four N‐hydrogen atoms of four (H₂NPPh₃)⁺ ions, four CH₃CN molecules form N–H···N≡C–CH₃ contacts with the other four N‐hydrogen atoms of the cations. Thus, 1 can be written as [(H₂NPPh₃)₄(CH₃CN)₄(SnCl₆)]²⁺[SnCl₆]^2?.     

[Mo2(O2C–CH3)4 · 1/2 {(CH2)6N4} · 1/2 CH2Cl2] – ein Donor‐Akzeptor‐Komplex mit supramolekularer Struktur

[Mo₂(O₂C–CH₃)₄ · ¹/₂ {(CH₂)₆N₄} · ¹/₂ CH₂Cl₂] – a Donor‐Acceptor Complex with Supramolecular Structure Yellow single crystals of [Mo₂(O₂C–CH₃)₄ · ¹/₂ {(CH₂)₆N₄} · ¹/₂ CH₂Cl₂] ( 1 ) have been obtained by the reaction of the silylated phosphaneimine Me₃SiNPEt₃ with [Mo₂(O₂C–CH₃)₄] in dichloromethane solution. 1 forms a three‐dimensional network with linear N–Mo:Mo–N and tetrahedral (CH₂)₆N₄Mo₄ moieties, which is topologically related with the PtS type. Space group P4₂/nnm, Z = 4, lattice dimensions at –70 °C: a = b = 1121.7(1), c = 1395.0(3) pm, R₁ = 0.0413.     

Synthesen und Schwingungsspektren der homoleptischen Acetonitrilkomplex-Kationen [Au(NCCH3)2]+, [Pd(NCCH3)4]2+, [Pt(NCCH3)4]2+ und des Adduktes CH3CN · SbF5. Kristallstrukturen der Salze [M(NCCH3)4][SbF6]2 · CH3CN,M = Pd,Pt

The Syntheses and Vibrational Spectra of the Homoleptic Metal Acetonitrile Cations [Au(NCCH₃)₂]⁺, [Pd(NCCH₃)₄]²⁺, [Pt(NCCH₃)₄]²⁺, and the Adduct CH₃CN · SbF₅. The Crystal and Molecular Structures of [M(NCCH₃)₄][SbF₆]₂ · CH₃CN, M = Pd or Pt Solvolyses of the homoleptic metal carbonyl salts [M(CO)₄][Sb₂F₁₁]₂, M = Pd or Pt, in acetonitrile leads at 50 °C both to complete ligand exchange for the cations as well as to a conversion of the di-octahedral anion [Sb₂F₁₁]^– into [SbF₆]^– and the molecular adduct CH₃CN · SbF₅ according to: [M(CO)₄][Sb₂F₁₁]₂ + 7 CH₃CN → [M(NCCH₃)₄][SbF₆]₂ · CH₃CN + 2 CH₃CN · SbF₅ + 4 CO M = Pd, Pt The monosolvated [M(NCCH₃)₄][SbF₆]₂ · CH₃CN are obtained as single crystals from solution and are structurally characterized by single crystal x-ray diffraction. Both salts are isostructural. The cations are square planar but the N–C–C-sceletial groups of the ligands depart slightly from linearity. The new acetonitrile complexes as well as [Au(NCCH₃)₂][SbF₆] and the adduct CH₃CN · SbF₅ are completely characterized by vibrational spectroscopy.     

Darstellung,Kristallstruktur und Schwingungsspektren von cis‐(CH2Py2)[ReBr4Py2]2 · (CH3)2CO

Synthesis, Crystal Structure, and Vibrational Spectra of cis ‐(CH₂Py₂)[ReBr₄Py₂]₂ · (CH₃)₂CO By reaction of (n‐Bu₄N)₂[ReBr₆] with pyridine and (n‐Bu₄N)BH₄ in dichloromethane halogeno‐pyridine‐rhenium(III)complexes are formed and purified by chromatography. X‐ray structure determination on a single crystal has been performed of cis‐(CH₂Py₂)[ReBr₄Py₂]₂ · (CH₃)₂CO (monoclinic, space group P2₁/c, a = 15.0690(9), b = 8.3337(8), c = 35.588(4) Å, β = 96.409(7), Z = 4). Based on the molecular parameters of the X‐ray structure determination and assuming C₂ point symmetry for the anion cis‐[ReBr₄Py₂]^– the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are in the Br–Re–Br axis f_d(ReBr) = 1.49, in the asymmetrically coordinated N′–Re–Br ^· axes f_d(ReBr ^· ) = 1.03 und f_d(ReN′) = 2.52 mdyn/Å.     

Synthese,Schwingungsspektren und Kristallstrukturen der Nitratoargentate (Ph4P)[Ag(NO3)2(CH3CN)]·CH3CN und (Ph4P)[Ag2(NO3)3]

Synthesis, Vibrational Spectra, and Crystal Structures of the Nitrato Argentates (Ph₄P)[Ag(NO₃)₂(CH₃CN)]·CH₃CN and (Ph₄P)[Ag₂(NO₃)₃] Tetraphenylphosphonium bromide reacts in acetonitril suspension with excess silver nitrate to give (Ph₄P)[Ag(NO₃)₂(CH₃CN)]·CH₃CN ( 1 ), whereas (Ph₄P)[Ag₂(NO₃)₃] ( 2 ) is obtained in a long‐time reaction from (Ph₄P)Br and excess AgNO₃ in dichloromethane suspension. Both complexes were characterized by vibrational spectroscopy (IR, Raman) and by single crystal structure determinations. 1 : Space group P2₁/c, Z = 4, lattice dimensions at 193 K: a = 1781.5(3), b = 724.8(1), c = 2224.2(3) pm, β = 96.83(1)°, R₁ = 0.0348. 1 contains isolated complex units [Ag(NO₃)₂(CH₃CN)]^?, in which the silver atom is coordinated by the chelating nitrate groups and by the nitrogen atom of the solvated CH₃CN molecule with a short Ag—N distance of 220.7(4) pm. 2 : Space group I2, Z = 4, lattice dimensions at 193 K: a = 1753.4(4), b = 701.7(1), c = 2105.5(4) pm, R₁ = 0.072. In the polymeric anions [Ag₂(NO₃)₃]^? each silver atom is coordinated in a chelating manner by one nitrate group and by two oxygen atoms of two bridging nitrate ions. In addition, each silver atom forms a weak π‐bonding contact with a phenyl group of the (Ph₄P)⁺ ions with shortest Ag···C separations of 266 and 299 pm, respectively, indicating a (4+1) coordination of silver atoms.     

Tetraphenylphosphonium-trichloroplumbat(II), PPh4PbCl3 · CH3CN

Tetraphenylphosphonium Trichloroplumbate(II), PPh₄PbCl₃ · CH₃CN PPh₄PbCl₃ · CH₃CN was obtained by reaction of PbCl₂ and PPh₄Cl in acetonitrile. It was also formed along with (PPh₄)₂Se₂Cl₆ when PbSe was treated with chlorine in the presence of PPh₄Cl. Its crystal structure was determined by X-ray diffraction (R = 0.029 for 4186 reflections). The triclinic crystals contain PbCl₃^– ions that are associated to polymer chains. Each Pb atom has distorted square pyramidal coordination; the pyramids share two opposite basal edges. The chloro bridges are rather asymmetrical.     

Die Kristallstruktur der hydratisierten Cyanokomplexe NMe4MnII[(Mn, Cr)III(CN)6] · 3 H2O und NMe4Cd[MIII(CN)6] · 3 H2O (MIII = Fe,Co): Verwandte des Berliner Blaus

The Crystal Structure of the Hydrated Cyano Complexes NMe₄Mn^II[(Mn, Cr)^III(CN)₆] · 3 H₂O and NMe₄Cd[M^III(CN)₆] · 3 H₂O (M^III = Fe, Co): Compounds Related to Prussian Blue The crystal structures of the isotypic tetragonal compounds (space group I4, Z = 10) NMe₄Mn^II · [(Mn, Cr)^III(CN)₆] · 3 H₂O (a = 1653.2(4), c = 1728.8(6) pm), NMe₄Cd[Fe(CN)₆] · 3 H₂O (a = 1642.7(1), c = 1733.1(1) pm) and NMe₄Cd[Co(CN)₆] · 3 H₂O (a = 1632.1(2), c = 1722.4(3) pm) were determined by X‐rays. They exhibit ⊥ c cyanobridged layers of octahedra [M^III(CN)₆] and [M^IIN₄(OH₂)₂], which punctually are interconnected also || c to yield altogether a spaceous framework. The M^II atoms at the positions linking into the third dimension are only five‐coordinated and form square pyramids [M^IIN₅] with angles N–M^II–N near 104° and distances of Mn–N: 1 × 214, 4 × 219 pm; Cd–N: 1 × 220 resp. 222, 4 × 226 resp. 228 pm. Further details and structural relations within the family of Prussian Blue are reported and discussed.     

Two novel bis­(2,9‐dimeth­yl‐1,10‐phenanthroline)copper(I) complexes: [Cu(dmp)2]2(PF6)2·0.5(bpmh)·CH3CN and [Cu(dmp)2][N(CN)2]

Two new salts of the cation [Cu^I(dmp)₂]⁺ (dmp is 2,9‐dimeth­yl‐1,10‐phenanthroline, C₁₄H₁₂N₂), namely bis­[bis­(2,9‐dimeth­yl‐1,10‐phenanthroline‐κ²N,N′)copper(I)] bis­(hexa­fluorophos­phate) hemi[bis­(4‐pyridylmethyl­idene)hydrazine] acetonitrile solvate, [Cu(C₁₄H₁₂N₂)₂]₂(PF₆)₂·0.5C₁₂H₁₀N₄·C₂H₃N or [Cu(dmp)₂]₂(PF₆)₂·0.5(bpmh)·CH₃CN [bpmh is bis­(4‐pyridylmethyl­idene)hydrazine, C₁₂H₁₀N₄], (I), and bis­(2,9‐dimeth­yl‐1,10‐phenanthroline‐κ²N,N′)copper(I) dicyanamide, [Cu(C₁₄H₁₂N₂)₂](C₂N₃) or [Cu(dmp)₂][N(CN)₂], (II), are reported. The Cu—N bond lengths and the distortion from idealized tetra­hedral geometry of the dmp ligands are discussed and compared with related compounds. The bpmh molecule in (I) is π–π stacked with a dmp ligand at a distance of 3.4 Å, rather than coordinated to the metal atom. The molecule lies across an inversion center in the crystal. In (II), the normally coordinated dicyanamide mol­ecule is present as an uncoordinated counter‐ion.     

Triphenylphosphinoxid (L) als Solvens und Ligand für Metallphthalocyaninate; Synthese und Struktur von [{Li(L)}2(μ‐pc)], [Li(L)4][Lipc] · Solvat, [Mg(L)pc] · Solvat und [Zn(L)pc] · Solvat

Triphenylphosphine Oxide (L) as Solvent and Ligand for Metallophthalocyaninates; Synthesis and Structure of [{Li(L)}₂(μ‐pc)], [Li(L)₄][Lipc] · Solvate, [Mg(L)pc] · Solvate, and [Zn(L)pc] · Solvate Triphenylphosphine oxide (L) coordinates to metallophthalocyaninates of Li, Mg and Zn at 300 °C. After purification and recrystallization in different solvents the very soluble and stable title compounds have been isolated and structurally characterized. In [{Li(L)}₂(μ‐pc)], the Li atom lies in a distorted tetragonal pyramid of four isoindole N atoms (N_i) at a distance varying between 2.163(5) and 2.301(5) Å, and an O atom at 1.863(5) Å. In [Li(L)₄] · [Lipc] · S, the Li atom of the cation coordinates four O atoms in a distorted tetrahedral arrangement at a distance varying from 1.887(9) to 1.953(9) Å, while the Li atom of the anion is in a quasi quadratic planar geometry of four N_i atoms (1.951(9)–1.977(9) Å) with the Li atom being displaced by 0.15 Å out of the (N_i)₄ plane. The structural data of the distorted tetragonal pyramidale Mg(N_i)₄O moiety in [Mg(L)pc] and the solvates [Mg(L)pc] · S (S = CH₂Cl₂, thf, 2py) generally do not vary significantly: Mg–N_i/2.035(3) –2.061(3) Å, Mg–O/1.955(2)–2.000(3) Å. The Mg atom is displaced by ca. 0.52 Å out of the (N_i)₄ plane towards the O atom and the Mg–O–P moiety is bent (ca. 153°). [Zn(L)pc] · S crystallizes as a mixed crystal of equal parts of the conformer with a bent (155.1(3)°) and that of a quasi linear Zn–O–P moiety (174.2(3)°). Structural data of the Zn(N_i)₄O moiety: (Zn–N_i)_av: 2.024/2.013 Å; Zn–O: 2.050(4)/2.081(4) Å; Zn–(N_i)₄: 0.40/0.33 Å. In the crystal, the Mg and Zn derivates aggregate in double layers forming pairs. The pc ligands in the triclinic complexes with good overlap of the neighbouring pc ligands are in a waving conformation, while those in the monoclinic complexes with weak overlap are in a concave conformation.     

[{(CH3)3Si}3C–Li–C{Si(CH3)3}3][Li · 3(OC4H8)] und {(CH3)3Si}3C–Li · O=C(Si(CH3)3)2, zwei neue Addukte des Lithium‐trisylmethanids

[{(CH₃)₃Si}₃C–Li–C{Si(CH₃)₃}₃][Li · 3(OC₄H₈)] and {(CH₃)₃Si}₃C–Li · O=C(Si(CH₃)₃)₂, two New Adducts of Lithium Trisylmethanide Sublimation of (Tsi–Li) · 2 THF (Tsi = –C(Si(CH₃)₃)₃) at 180 °C and 10^–4 hPa gives (Tsi–Li) · 1.5 THF in very low yield. The X‐ray structure determination shows an almost linear [Tsi–Li–Tsi]^– anion connected by short agostic Li…C contacts with the threefold THF‐coordinated Li‐cation. Base‐free Tsi–Li, solved in toluene is decomposed by oxygen, forming the strawberry‐colored ketone O=C(SiMe₃)₂, which forms an 1 : 1 adduct with undecomposed Tsi–Li. The X‐ray structure elucidation of this compound is also discussed.     

Die Oxochlorotantalate (PPh4)2[Ta2OCl9]2 · 2 CH2Cl2, (PPh4)2[Ta2OCl10] · 2 CH3CN und (K-18-Krone-6)4[Ta4O6Cl12] · 12 CH2Cl2

The Oxochlorotantalates (PPh₄)₂[Ta₂OCl₉]₂ · 2 CH₂Cl₂, (PPh₄)₂[Ta₂OCl₁₀] · 2 CH₃CN, and (K-18-crown-6)₄[Ta₄O₆Cl₁₂] · 12 CH₂Cl₂ (K-18-crown-6)₄[Ta₄O₆Cl₁₂] · 12 CH₂Cl₂ was obtained from a reaction of tantalum pentachloride, K₂S₅ and 18-crwon-6 in dichlormethane. According to its crystal structure analysis it is tetragonal (space group I 4 2d) and contains [Ta₄O₆Cl₁₂]^4– ions that have an adamantane-like Ta₄O₆ skeleton. Each K⁺ ion is coordinated by the oxygen atoms of the crown ether molecule from one side and with three Cl atoms of one [Ta₄O₆Cl₁₂]^4– ion from the opposite side. (PPh₄)₂[Ta₂OCl₁₀] · 2 CH₃CN was a product from PPh₄Cl and TaCl₅ in acetonitrile in the presence of Na₂S₄. Its crystals are monoclinic (space group P2₁/c) and contain centrosymmetric [Ta₂OCl₁₀]^2– ions having a linear Ta–O–Ta grouping with short bonds (Ta–O 189 pm). TaCl₅ and H₂S formed a solid substance (TaSCl₃) from which a small amount of (PPh₄)₂[Ta₂OCl₉]₂ · 2 CH₂Cl₂ was obtained by the reaction with PPh₄Cl in CH₂Cl₂. The anions in the monoclinic crystals (space group P2₁/n) consist of two Ta₂OCl₉^– units which are joined by chloro bridges; each Ta₂OCl₉^– unit has a nearly linear Ta–O–Ta group with differing bond lengths (179 and 202 pm). The oxygen in the compounds probably was introduced by traces of water in the crown ether, acetonitrile or H₂S, respectively.     

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.     

[BuN(CH2CH2)3NBu]3[Pb5I16] · 4 DMF – ein Iodoplumbat mit nahezu D5h‐symmetrischem Anion

[BuN(CH₂CH₂)₃NBu]₃[Pb₅I₁₆] · 4 DMF – an Iodoplumbate Anion with approximately D _5h Symmetry The star‐shaped anion of [BuN(CH₂CH₂)₃NBu]₃‐[Pb₅I₁₆] · 4 DMF ( 1 ) consists of a cyclic arrangement of five PbI₆ octahedra sharing one common I atom in the centre of an almost planar Pb₅ ring. Compound 1 crystallizes in space group P2₁ with a = 1657.2(1), b = 2029.2(1), c = 1773.6(1) pm, β = 113.238(8)°, Z = 2.