Reaktionen von MoNCl3 und WNCl3 mit elementarem Fluor. Kristallstrukturen von [MoO2F2(THF)2] und [WF4(NCl)(CH3CN)]

Reactions of MoNCl₃ and WNCl₃ with Elemental Fluorine. Crystal Structures of [MoO₂F₂(THF)₂] and [WF₄(NCl)(CH₃CN)] The nitrido chlorides MoNCl₃ and WNCl₃ as well as WCl₄(NCl) react with elemental fluorine forming the N-chloro imido complexes MoF₄(NCl) and WF₄(NCl), which were characterized by IR spectroscopy. With tetrahydrofurane MoF₄(NCl) reacts to give [MoF₄(NCl)(THF)], which in THF solution slowly converts into [MoO₂F₂(THF)₂]. From WF₄(NCl) with acetonitrile the complex [WF₄(NCl)(CH₃CN)] is obtained. Both donor acceptor complexes were characterized by crystal structure determinations. [MoO₂F₂(THF)₂] : Space group P2₁/n, Z = 4, structure solution with 1823 unique reflections, R = 0.033 for reflections with I > 2σ(I). Lattice dimensions at ?40°C: a = 636.2, b = 1119.5, c = 1625.2 pm; β = 93.92(1)º. The compound has a monomeric molecular structure with the fluorine atoms in trans-position to one another and with the oxygen atoms of the THF molecules in trans to the oxo ligands. [WF₄(NCl)(CH₃CN)] : Space group P2₁/m, Z = 2, structure solution with 1119 unique reflections, R = 0.038 for reflections with I > 2σ(I). Lattice dimensions at 20°C: a = 511.7, b = 714.9, c = 1002.5 pm; β = 102.59(10)º. The compound has a monomeric molecular structure in which the nitrogen atom of the acetonitrile molecule coordinates in trans-position to the N-chloro imido group W?N? Cl. The structural parameters of this group are WN = 172.2 pm, NCl = 161.1 pm, WNCl = 178.6º.     

Synthese und Kristallstruktur des μ-Dinitridosulfato(II)-Komplexes [Na-15-Krone-5]2[μ-(NSN)(MoF5)2]

Synthesis and Crystal Structure of the μ-Dinitridosulfate(II) Complex [Na-15-crown-5]₂[μ-(NSN)(MoF₅)₂] The title compound is formed at room temperature by the reaction of [MoCl₄(NSCl)]₂ with the equivalent amount NaF in acetonitrile in presence of the crown ether 15-crown-5. It forms black, moisture-sensitive crystals that were characterized by an X-ray structure determination (1 756 unique observed reflexions, R = 0.073). Crystal data (19°C): a = 965.5, b = 3 219, c = 1 161.1 pm, β = 95.42°; space group P2₁/n, Z = 4. The structure consists of ion triples in which the [Na-15-crown-5]⁺ ions are associated with the [μ-(NSN)(MoF₅)₂]^2? ions via Na…?F contacts of 215 to 265 pm length. Each of the two MoF₅ units of the anion is linked with one of the N atoms of the dinitridosulfate(II) group; bond angle NSN 103°, MoN bond lengths 172 pm.     

Synthese und Kristallstruktur des Nitridokomplexes [Na-15-Krone-5]2[MoNF4]2 · 2 CH3CN

Synthesis and Crystal Structure of the Nitrido Complex [Na-15-crown-5]₂[MoNF₄]₂ · 2 CH₃CN The title compound is synthesized by the reaction of [MoCl₄(NSCl)]₂ with excess NaF in boiling acetonitrile in the presence of the crown ether 15-crown-5. [Na-15-crown-5]₂[MoNF₄]₂ · 2 CH₃CN forms yellow crystals, which were characterized by an X-ray structure determination. Space group P1 , Z = 1. Lattice dimensions at ?90°C: a = 855.5, b = 1 069.9, C = 1 143.5 pm, α = 105.71°, β = 95.29°, γ = 102.25° (4 096 independent observed reflexions, R = 0.039). Short Na…?F contacts of 234 pm with the four axial fluoro ligands of the dimeric anion [MoNF₄]₂^2? allow formulation of a triple ion. The centrosymmetric anion is dimerized by bent fluoro bridges with Mo? F distances of 198 and 245 pm. The long Mo? F distances of the MoF₂Mo ring are in transposition to the nitrido ligands, the bond lengths of which (165 pm) correspond to triple bonds.     

Zur Reaktion von Diphenylfluorphosphan mit Aldehyden Kristallstruktur von Diphenylphosphinigsäure-[α-(difluorodiphenyl-λ5-phosphanyl)]piperonylester

Reaction of Diphenylfluorophosphane with Aldehydes. Crystal Structure of [α-(Difluorodiphenyl-λ⁵-phosphanyl)] Piperonyl Diphenylphosphinite Diphenylfluorophosphane, Ph₂PF, reacts with aldehydes forming phosphinito phosphoranes, Ph₂F₂P? CHR? O? PPh₂. [α-(Difluorodiphenyl-λ⁵-phosphanyl)] piperonyl diphenyl-phosphinite, obtained by the reaction of Ph₂PF with piperonal, crystallizes in the triclinic space group P1 with a = 969.3 pm, b = 2360 pm, c = 607,3 pm, α = 88.33°, β = 102.79°, γ = 92.40° and Z = 2.     

Element-Element-Bindungen. VI. Kristallines 2-Chlor-1,3,2-benzoxathiastibol – ein mehrfach verknüpftes Koordinationspolymeres

Element-Element-Bonds. VI. Crystalline 2-Chloro-1,3,2-benzoxathiastibole – a Multiply Linked Coordination Polymer Yellow 2-chloro-1,3,2-benzoxathiastibole 4a first prepared by Anchisi and coworkers [3] from o-hydroxythiophenol and antimony trichloride, crystallizes in the monoclinic space group P2₁/n {a = 1109.9(3); b = 610.5(2); c = 1201.5(2) pm; β = 100.35(2)° at ?120 ± 3°C; Z = 4}. An X-ray structure determination (R = 0.029) shows the molecules to form coordination polymeric layers via Sb…?Cl, Sb…?O and Sb…?η²-arene interactions in the solid. Characteristic structural features are Sb? Cl…?Sb? Cl helices (Sb? Cl…?Sb 119°; Cl? Sb…?Cl 95°) and centrosymmetric, four membered Sb₂O₂-rings (O? Sb…?O 64°; Sb? O…?Sb 116°). The ligands set up a strongly distorted octahedron around the antimony atom: Sb? S 242; Sb? Cl 243; Sb…?Cl 328; Sb? O 201; Sb…?O 287; Sb…?C 338 and 341 pm; S? Sb? O 85°; S? Sb? Cl 94°; O? Sb? Cl 92°.     

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.     

The Monohydrate of Basic Mercuric Nitrate, [Hg(OH)](NO3)(H2O)

Colourless single crystals of [Hg(OH)](NO₃)(H₂O) were obtained by slow evaporation of an aqueous solution of Hg(NO₃)₂ and Bi(NO₃)₃. The crystal structure (orthorhombic, Pbca, Z = 8, a = 943.2(2), b = 697.6(1), c = 1349.0(2) pm, R₁(all) = 0.0780) contains [Hg(OH)] = …OH–Hg–OH–Hg… zig zag chains (O–Hg–O angle: 168°, Hg–O–Hg angle: 112°, Hg–OH distance: 212 pm) to which one water molecule is attached loosely. The [Hg(OH)](H₂O) chains are connected via bis‐monodentate‐bridging nitrate ions to corrugated layers that are stacked in the [001] direction. Hg²⁺ has an effective 2+2+2(+1) coordination.     

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.     

Poly(hydrogen Fluorides) with the Tetramethylammonium Cation: Preparation,Stability Ranges,Crystal Structures, [HnFn+1]− Anion Homology,Hydrogen Bonding F-H…︁F [2]

The melting diagram of the system (CH₃)₄NF? HF was studied between 50 and 100 mole-% HF and from ?185°C to the respective liquidus temperatures (at most 162°C) by difference thermal analysis aided by temperature-dependent X-ray powder diffraction. The system was found to be quasi-binary with the HF-rich intermediary stable compounds (CH₃)₄NF · 2 HF (melting point 110°C), (CH₃)₄NF · 3 HF (20°C, decomposition), (CH₃)₄NF · 5 HF (?76°C, decomposition), and (CH₃)₄NF · 7 HF (?110°C, decomposition), most of which undergo solid-solid phase transitions. Crystal structures were determined of the low-temperature form of (CH₃)₄NF · 2 HF (stable below 83°C, orthorhombic, space group Pbca, Z = 8 formula units per unit cell), the high-temperature form of (CH₃)₄NF · 3 HF (stable above ?87°C, monoclinic, P2/c, Z = 4), and of (CH₃)₄NF · 5 HF (tetragonal, I4 , Z = 2). The structures are those of poly(hydrogen fluorides) (CH₃)₄N[H_nF_n+1] with homologous anions [H₂F₃]^?, [H₃F₄]^?, and [H₅F₆]^?, respectively, formed by strong hydrogen bonding F? H…?F. The anion [H₅F₆]^? is the first one of this composition established by crystal structure analysis. Its structure can be written as [(FH)₂FHF(HF)₂]^? with four equivalent terminal hydrogen bonds of 248.4 pm and a very short central one of 226.6 pm (F…?F distances) through a 4 point of the space group.     

Protonation and Hydrogen Atom Abstraction Reactions in the Synthesis of the [HP7M(CO)3]2– Ions (M = Cr,W)

Ethylenediamine (en) solutions of [P₇M(CO)₃]^3– (M = Cr, W) react with weak acids to give [HP₇M(CO)₃]^2– ions where M = Cr ( 4 a ) and W ( 4 b ) in high yields. Competition studies with known acids revealed a pK_a range for 4 b in DMSO of 17.9 to 22.6. The [P₇M(CO)₃]^3– complexes also react with one-half equivalent of I₂ to give 4 through an oxidation/hydrogen atom abstraction process. Labeling studies show that the abstracted hydrogen originates from the [K(2,2,2-crypt)]⁺ ions or from the solvent (DMSO-d₆) in the absence of [K(2,2,2-crypt)]⁺ or other good hydrogen atom donors. In the solid state, the ions have no crystallographic symmetry but in solution they show virtual C_s symmetry (³¹P NMR spectroscopy) due to an intramolecular wagging process. Crystallographic data for [K(2,2,2-crypt)]₂[HP₇W(CO)₃]: triclinic, P 1, a = 10.9709(8) Å, b = 13.9116(10) Å, c = 19.6400(14) Å, α = 92.435(6)°, β = 93.856(6)°, γ = 108.413(6)°, V = 2831.2(4) ų, Z = 2, R(F) = 7.65%, R(wF²) = 14.17% for all 7400 reflections. For [K(2,2,2-crypt)]₂[HP₇Cr(CO)₃]: triclinic, P 1, a = 12.000(3) Å, b = 14.795(3) Å, c = 17.421(4) Å, α = 93.01(2)°, β = 93.79(2)°, γ = 110.72(2)°, V = 2877(2) ų, Z = 2.     

Synthese,Struktur und magnetische Eigenschaften von [CrCl(μ-Cl)(TMEDA)]2

Synthesis, Structure, and Magnetic Properties of [CrCl(-μCl)(TMEDA)]₂ The title complex [CrCl(μ-Cl)(TMEDA)]₂ ( 1 ) is obtained in an equimolar reaction of CrCl₂(THF) with TMEDA in high yield. 1 crystallises in the monoclinic space group P2₁/c with a = 843.2(2), b = 1 109.(2), c = 1 147.4(3) pm, β = 102.99(2)° and Z = 2. The molecular structure of 1 contains two, slightly distorted quadratic pyramidal CrL₅-subunits, which are linked via two unsymmetrical Cl-bridges. The μ-Cl-functions take the apical position of one and a basal position of the second CrL₅-unit, wherein the apical Cr–Cl bond (277.6(1) pm) is destinctly longer than the basal Cr–Cl bond (240.6(1) pm). The terminal Cr–Cl bond is still shorter (237.5(1) pm). The Cr…Cr distance is far beyond any bonding interaction. This is confirmed by means of magnetic susceptibility measurements, which show four unpaired electrons per Cr centre; however, a small antiferromagnetic coupling of J/k = ?7.3 K can be calculated. This coupling is suggested to be originated by a 90°-σ-superexchange via the asymmetric μ-Cl functions.     

Die Kristallstruktur des 1 : 1-Adduktes zwischen Antimontrichlorid und Diphenylammoniumchlorid,SbCl3 · (C6H5)2NH2+Cl−

The Crystal Structure of the 1:1 Addition Compound between Antimony Trichloride and Diphenylammonium Chloride, SbCl₃ · (C₆H₅)₂NH₂⁺Cl^? The 1:1 addition compound between antimony trichloride and diphenylammoniumchloride SbCl₃ · (C₆H₅)₂NH₂⁺Cl^? crystallizes in the monoclinic space group P2₁/n with a = 5.668(8), b = 20.480(12), c = 14.448(17) Å, β = 110.4(1)° and Z = 4 formula units. Chains of SbCl₃ molecules and anion cation chains are bridged by Cl ions and form square tubes. The coordination of the Sb atoms by Cl atoms by Cl atoms and Cl ions is distorted octahedral. Mean distances are Sb? Cl = 2.37 Å for Sb? Cl (3×), 3.09 Å for Sb…Cl^? (2×) and 3.42 Å for Sb…Cl (1×). The Sb…Cl^? contacts and hydrogen bonds NH…Cl^? at 3.15 Å generate tetrahedral coordination of the Cl ions.     

Polysulfonylamine. XL Darstellung von Silber(I)-disulfonylamid-Acetonitril-Komplexen. Röntgenstrukturanalytische und thermochemische Charakterisierung von Tetraacetonitrilsilber(I)-bis(dimesylamido)argentat(I) und von (1,1,3,3-Tetraoxo-1,3,2-benzodithiazolido)acetonitrilsilber(I)

Polysulfonyl Amines. XL. Preparation of Silver(I) Disulfonylamide Acetonitrile Complexes. Characterization of Tetraacetonitrilesilver(I) bis(dimesylamido)argentate(I) and (1,1,3,3-Tetraoxo-1,3,2-benzodithiazolido)acetonitrilesilver(I) by X-Ray Diffractometry and Thermal Analysis The following silver(I) disulfonylamides were prepared for the first time or by improved procedures: AgN(SO₂CH₃)₂ ( 2a ); AgN(SO₂C₆H₄-4-X)₂ with X = F ( 2b ), Cl ( 2c ), Br ( 2d ), CH₃ ( 2e ); silver(I) 1,2-benzenedisulfonimide AgN(SO₂)₂C₆H₄ ( 2f ). With acetonitrile, the salts 2a to 2e form (1/2) complexes AgN(SO₂R)· 2 CH₃CN ( 4a to 4e ), whereas 2f gives the (1/1) complex AgN(SO₂)₂C₆H · CH₃CN ( 4f ). The crystallographic data (at - 95°C) for the title compounds 4a and 4f are: 4a , space group C2/c, a = 1 967.6(4), b = 562.2(1), c = 2 353.0(5) pm, β = 102.21(2)°, V = 2.5440 nm³, Z = 4, D_x = 1.891 Mg m^?3; 4f , space group P2₁/m, a = 741.5(3), b = 980.4(4), c = 756.6(3) pm, β = 99.28(2)°, V = 0.5428 nm³, Z = 2, D_x = 2.246 Mg m^?3. 4a forms an ionic crystal [Ag(NCCH₃)₄]^⊕[Ag{N(SO₂CH₃)₂}₂]^? with a tetrahedrally coordinated silver atom (lying on a twofold axis) in the cation (225.3/225.7 pm for the two independent Ag? N distances, N? Ag? N 106.2—114.5°) and a linear-dicoordinated silver atom in the centrosymmetric anion (Ag? N 213.9 pm, two intraionic secondary Ag…O contacts 303.4 pm). 4f consists of uncharged molecules [C₆H₄(SO₂)₂N¹AgN²CCH₃] with crystallographic mirror symmetry (Ag? N¹ 218.8, Ag? N² 216.1 pm, N¹? Ag? N² 174.3°), associated into strands by intermolecular secondary silver-oxygen contacts (Ag…O 273.8 pm, O…Ag…O 175.6, N? Ag…O 91.9/88.2°). The thermochemical behaviour of 4f was investigated using thermogravimetry, differential scanning calorimetry (DSC), time- and temperature-resolved X-ray diffractometry (TXRD), and solution calorimetry. The desolvation process occurs in the temperature range from 60 to 200°C and appears to be complex, although no crystalline intermediate could be detected. The desolvation enthalpy at 298 K was found to be + 26.8(4) kJ mol^?1. 4a is desolvated in two steps at - 15 to 60°C and 60 to 95°C (DSC), suggesting the formation of AgN(SO₂CH₃) · CH₃CN as an intermediate.     

Phosphanimin‐ und Phosphaniminato‐Komplexe von Beryllium. Kristallstrukturen von [BeCl2(HNPPh3)2], [BeCl(HNPPh3)2(Py)]Cl und [Be3Cl2(NPPh3)4]

Phosphanimine and Phosphoraneiminato Complexes of Beryllium. Crystal Structures of [BeCl₂(HNPPh₃)₂], [BeCl(HNPPh₃)₂(Py)]Cl, and [Be₃Cl₂(NPPh₃)₄] Tetraphenylphosphonium hexachlorodiberyllate, (Ph₄P)₂[Be₂Cl₆], reacts with lithium phosphoraneiminate, [LiNPPh₃]₆, in dichloromethane to give the three‐nuclear beryllium phosphoraneiminate [Be₃Cl₂(NPPh₃)₄] ( 3 ). As a by‐product the phosphaneimine complex [BeCl₂(HNPPh₃)₂] ( 1 ) can be isolated, which reacts with pyridine to give the ionic complex [BeCl(HNPPh₃)₂(Py)]Cl ( 2 ). On the other hand, the silylated phosphanimine Me₃SiNP(p‐tolyl)₃ ( 5 ) does not react with BeCl₂ or (Ph₄P)₂[Be₂Cl₆] forming the expected phosphoraneiminates. From CH₂Cl₂ solutions only the amino‐phosphonium salt [(C₇H₇)₃PNH₂]Cl ( 4 ) can be obtained. The compounds 1 ‐ 5 are characterized by single X‐ray analyses and by IR spectroscopy. 1 ·C₇H₈: Space group C2/c, Z = 4, lattice dimensions at 193 K: a = 1408.9(2), b = 1750.9(2), c = 1633.2(2) pm, β = 106.50(1)°; R₁ = 0.0385. 1 forms a molecular structure with short Be—N distances of 169.8(3) pm. 2 ·Py: Space group P1¯, Z = 4, lattice dimensions at 193 K: a = 969.5(1), b = 2077.1(2), c = 2266.4(2) pm, α = 72.24(1)°, β = 87.16(1)°, γ = 77.42(2)°, R₁ = 0.0776. 2 forms ion pairs in which the NH atoms of the phosphaneimine ligands act as hydrogen bridges with the chloride ion. The HNPPh₃ ligand realizes short Be—N bonds of 169.0(6) pm, the Be—N distance of the pyridine molecule is 182.5(6) pm. 3 ·3CH₂Cl₂: Space group P1¯, Z = 2, lattice dimensions at 193 K: a = 1333.2(2), b = 1370.2(2), c = 2151.8(3) pm, α = 107.14(1)°, β = 91.39(1)°, γ = 105.15(1)°, R₁ = 0.0917. The structure of the three‐nuclear molecule 3 corresponds with a Be²⁺ ion which is tetrahedrally coordinated by the nitrogen atoms of two {ClBe(NPPh₃)₂}^— chelates. 4 ·CH₂Cl₂: Space group P2₁/c, Z = 4, lattice dimensions at 193 K: a = 1206.6(2), b = 1798.0(2), c = 1096.2(1) pm, β = 97.65(1)°, R₁ = 0.0535. 4 forms dimeric units in which the NH₂ groups of the [(C₇H₇)₃PNH₂]⁺ cations act as hydrogen bridges with the chloride ions to give centrosymmetric eight‐membered rings. 5 : Space group P2₁/n, Z = 4, lattice dimensions at 193 K: a = 1074.3(2), b = 2132.2(3), c = 1075.5(2) pm, β = 110.68(1)°, R₁ = 0.0664. 5 forms molecules with distances PN of 154.6(3), SiN of 168.8(3) pm, and bond angle SiNP of 134.4(2)°.     

Hirshfeld Surface Analysis,Crystal Structure and Spectroscopic Studies of a New Cu(II) Halocuprate Salt with Protonated N-Amino-Ethyl-Piperazine

(C₆H₁₈N₃)₄[CuCl₅]₂[CuCl₄]₃·1.42H₂O is prepared and characterized by various physicochemical techniques. The single crystal X-ray diffraction structural analysis reveals that the title compound belongs to the orthorhombic system with the space group Cmca. Its unit cell dimensions are: a = 24.286(2) Å, b = 14.3082(14) Å, c = 16.6160(16) Å, Z = 4, V = 5773.8(10) ų. Its crystal structure is determined and refined down to R = 0.024 and wR(F²) = 0.059. The structure contains three crystallographically independent Cu²⁺ ions coordinated to chlorine anions in various fashions. Cu1 is five-coordinated in a distorted square pyramidal fashion, while Cu2 and Cu3 are four-coordinated in square planar and distorted tetrahedral fashions, respectively. The entities are interconnected by means of the hydrogen bonding [O(W)–H…Cl, N–H…Cl, C–H…Cl and C–H…O(W)], forming a three-dimensional network. Intermolecular interactions are investigated by Hirshfeld surfaces and the contacts of the eight different chloride atoms are notably compared. The vibrational absorption bands are identified by infrared spectroscopy. The optical study is performed by UV-vis absorption.     

Die Kristallstrukturen von SeCl3 +SbCl6−, SeBr3+GaBr4−, PCl4+SeCl5− und (PPh4+)2SeCl42− · 2 CH3CN

Crystal Structures of SeCl₃⁺SbCl₆^?, SeBr₃⁺GaBr₄^?, PCl₄⁺SeCl₅^?, and (PPh₄⁺)₂SeCl₄^2? · 2 CH₃CN The crystal structures of the title compounds were determined by X-ray diffraction. SeCl₃⁺SbCl₆^?: Space group P2₁/m, Z = 4, structure determination with 1795 observed unique reflections, R = 0.022. Lattice dimensions at ?80°C: a = 940.9, b = 1066.3, c = 1234.9 pm, β = 102.79°. The compound forms ion pairs with the structure of a double octahedron with linked surfaces. SeBr₃⁺GaBr₄^?: Space group Pc, Z = 2, structure determination with 1461 observed unique reflections, R = 0.058. Lattice dimensions at ?60°C: a = 660.1, b = 655.3, c = 1431.3 pm, β = 101.177°. The compound crystallizes in the SCl₃[AlCl₄] lattice type. Between the ions there are two relatively short Se … Br? Ga contacts. PCl₄⁺SeCl₅^?: Space group Ima2, Z = 8, structure determination with 1757 observed unique reflections, R = 0.029. Lattice dimensions at ?50°C: a = 1651.6, b = 1201.2, c = 1166.4 pm. The SeCl₅^? ions are associated to chains via interionic Se? Cl … Se contacts along the crystallographic c-axis. (PPh₄⁺)₂SeCl₄^2? · 2CH₃CN: Space group P2₁/n, Z = 2, structure determination with 2578 observed unique reflections, R = 0.050. Lattice dimensions at ?80°C: a = 1288.5, b = 726.0, c = 2585.8 pm, β = 101.65°. The compound includes planar-tetragonal SeCl₄^2? ions, which almost meet D_4h symmetry.     

[Na(15-Krone-5)][ReFCl3(NO)(CH3CN)] Synthese,IR-Spektrum und Kristallstruktur

[Na(15-crown-5)][ReFCl₃(NO)(CH₃CN)] Synthesis, IR Spectrum, and Crystal Structure The title compound has been prepared by the reaction of [ReCl₃(NO)₂(CH₃CN)] with the equivalent amount of sodium fluoride in the presence of 15-crown-5 in boiling acetonitrile, forming blue crystals. They were characterized by IR spectroscopy and by an X-ray structure determination. Space group P2₁/n, Z = 4,2117 observed independent reflections, R = 0.037, wR = 0.029. Lattice dimensions at 20°C: a = 834.0(2), b = 1600.0(3), c = 1670.0(3) pm; β = 104.19(3)°. The compound forms an ion pair via one Na F contact of 234.4 pm and one Na Cl contact of 293.4 pm; the nitrosyl ligand ist in trans-position to the F atom of the anion [ReFCl₃(NO)(CH₃CN)]⁻.     

Synthese und Kristallstrukturen der Wolfram(VI)-Alkin-Komplexe [W2(O)(OMe)6(Et?Se?CC?Se?Et)2] und Li[W(OMe)5(Et?Te?CC?Te?Et)]

Synthesis and Crystal Structures of the Tungsten(VI)-alkyne Complexes [W₂(O)(OMe)₆(Et? Se? C?C? Se? Et)₂] and Li[W(OMe)₅(Et? Te? C?C? Te? Et)] The title compounds have been prepared by reactions of lithium methanolate with [WCl₄(Et? Se? C?C? Se? Et)(THF)] and [WCl₄(Et? Te? C?C? Te? Et)(THF)], respectively, in diethylether suspensions. Both complexes were characterized by crystal structure determinations. [W₂(O)(OMe)₆(Et? Se? C?C? Se? Et)₂]: Space group P1 , Z = 2, structure determination with 4 320 observed unique reflections, R = 0.041. Lattice dimensions at ?70°C: a = 949.3, b = 1 225.3, c = 1 285.0 pm, α = 82.48°; γ = 82.44°; β = 81.44°. The tungsten atoms are bridged by three μ₂-O-atoms of the OMe groups; the alkyne ligands are coordinated side-on in a metallacyclopropene-like fashion. Li[W(OMe)₅(Et? Te? C?C? Te? Et)]: Space group P1 , Z = 2, structure determination with 9 381 observed unique reflections, R = 0.038. Lattice dimensions at ?70°C: a = 983.4, b = 1606.9, c = 1971.5 pm, α = 66.09°, β = 84.29°, γ = 79.83°. The lithium ions link the [W(OMe)₅(Et? Te? C?C? Te? Et)]^? anions to a trimeric ion ensemble via the O atoms of three OMe groups of each anion.     

Die Kristallstrukturen von (NH4)2[ReCl6], [ReCl2(CH3CN)4]2[ReCl6] · 2CH3CN und [ReCl4(18-Krone-6)]

The Crystal Structures of (NH₄)₂[ReCl₆], [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN and [ReCl₄(18)(Crown-6)] Brown single crystals of (NH₄)₂[ReCl₆] are formed by the reaction of NH₄Cl with ReCl₅ in a suspension of diethylether. [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN crystallizes as brown crystal plates from a solution of ReCl₅ in acetonitrile. Lustrous green single crystals of [ReCl₄(18-crown-6)] are obtained by the reaction of 18-crown-6 with ReCl₅ in a dichloromethane suspension. All rhenium compounds are characterized by IR spectroscopy and by crystal structure determinations. (NH₄)₂[ReCl₆]: Space group Fm3 m, Z = 4, 75 observed unique reflections, R = 0.01. Lattice constant at ?70°C: a = 989.0(1) pm. The compound crystallizes in the (NH₄)₂[PtCl₆] type, the Re? Cl distance is 235.5(1) pm. [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN: Space group P1, Z = 1, 2459 observed unique reflections, R = 0.12. Lattice dimensions at ?60°C: a = 859.0(1), b = 974.2(7), c = 1287.3(7) pm, α = 102.69(5)°, b? = 105.24(7)°, γ = 102.25(8)°. The structure consists of two symmetry-independent [ReCl₂(CH₃CN)₄]⁺ ions with trans chlorine atoms, [ReCl₆]^2? ions, and included acetonitrile molecules. In the cations the Re? Cl bond lengths are 233 pm in average, in the anion they are 235 pm in average. [ReCl₄(18-crown-6)]: Space group P2₁/n, Z = 4, 3 633 observed unique reflections, R = 0.06. Lattice dimensions at ?70°C: a = 1040.2(4), b = 1794.7(5), c = 1090.0(5) pm, b? = 108.91(4)°. The compound forms a molecular structure, in which the rhenium atom is octahedrally coordinated by the four chlorine atoms and by two oxygen atoms of the crown ether molecule.