Phosphaniminato-Komplexe des Schwefels. Synthese und Kristallstrukturen von [SO(Cl)(NPPh3)], [SO2(Cl)(NPPh3)] und [SCl(NPPh3)2]Cl

Phosphorane Iminato Complexes of Sulfur. Synthesis and Crystal Structures of [SO(Cl)(NPPh₃)], [SO₂(Cl)(NPPh₃)], and [SCl(NPPh₃)₂]Cl The title compounds have been prepared by the reaction of Me₃SiNPPh₃ with SOCl₂, SO₂Cl₂, and SCl₂, respectively. They form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy and by crystal structure determinations. [SO(Cl)(NPPh₃)]: Space group P2₁/n, Z = 4, structure determination with 2 434 observed unique reflections, R = 0.047. Lattice dimensions at 19°C: a = 1 304.8, b = 996.5, c = 1 339.5 pm, β = 93.75°. The compound forms monomeric molecules with a remarkably long S? Cl bond of 234.2 pm and distances SN and PN of 154.6 and 161.6 pm, respectively, which agree with double bonds. [SO₂(Cl)(NPPh₃)]: Space group P2₁/n, Z = 4, structure solution with 2 872 observed, unique reflections, R = 0.047. Lattice dimensions at 20°C: a = 956.9, b = 1 909, c = 1 002.0 pm, β = 106.06°. The compound forms monomeric molecules with distances S? Cl of 207.1 pm, SN of 154.5 pm, and PN of 161.6 pm. [SCl(NPPh₃)₂]Cl: Space group P2₁/c, Z = 4, structure solution with 5 224 observed, unique reflections, R = 0.042. Lattice dimensions at 20°C: a = 1 108.6, b = 1 603.8, c = 1 840.5 pm, β = 99.98°. The compound forms ions [SCl(NPPh₃)₂]⁺ and Cl^?. In the cation the sulfur atom is φ-tetrahedrally coordinated with a long S? Cl distance of 248.5 pm and SN bond lengths of 154.5 and 156.0 pm.     

Chelatkomplexe von Rheniumtetrachlorid. Die Kristallstrukturen von ReCl4(DME) und ReCl4(DPPE) · Tolan

Chelate Complexes of Rhenium Tetrachloride. The Crystal Structures of ReCl₄(DME) and ReCl₄(DPPE) · Tolan Bright green crystals of ReCl₄(DME) have been prepared by the reaction of rhenium pentachloride with dimethoxyethane (DME) in dichloromethane. ReCl₄(DPPE) · tolan was obtained in form of red crystals by the reaction of the alkyne complex [ReCl₄(Ph? C?C? Ph)(POCl₃)] with bis(diphenylphosphino)ethane (DPPE) in dichloromethane. The complexes were characterized by X-ray structure determinations. ReCl₄(DME): Space group I4 2d, Z = 8, 829 observed unique reflexions, R = 0.022. Lattice dimensions at 19.5°C: a = b = 960.60(6), c = 2337.2(6) pm. The complex forms monomeric molecules with DME as chelating ligand; the Re? O bond lengths are 213.1 pm. The chlorine atoms, arranged in trans position to the chelating ligand, have slightly shorter Re? Cl bonds than the chlorine atoms in cis position (232,1 pm). ReCl₄(DPPE) · tolan: Space group P2₁/n, Z = 4,4313 observed unique reflexions, R = 0.040. Lattice dimensions at ?80°C: a = 1095.7(1), b = 1764.2(2), c = 1898.0(2) pm, β = 99.229(8)°. The compound consists in form of monomeric molecules [ReCl₄(DPPE)] and diphenylacetylene molecules, which are incorporated in the lattice. The two phenyl rings of the tolan molecules are twisted towards each other along the C? C axis with a dihedral angle of 21°. The DPPE molecules are bonded to the rhenium atom in a chelating fashion with medium Re? P lengths of 250.4 pm. The chlorine atoms, arranged in trans position to this ligand, with Re? Cl bond lengths of 234.5 pm are slightly longer than the Re? Cl bonds in cis position with 232.3 pm.     

Silylierte Phosphanimin-Komplexe von Chrom(II), Palladium(II) und Kupfer(II). Die Kristallstrukturen von [CrCl2(Me3SiNPMe3)2], [PdCl2(Me3SiNPEt3)2] und [CuCl2(Me3SiNPMe3)]2

Silylated Phosphaneimine Complexes of Chromium(II), Palladium(II), and Copper(II). The Crystal Structures of [CrCl₂(Me₃SiNPMe₃)₂], [PdCl₂(Me₃SiNPEt₃)₂], and [CuCl₂(Me₃SiNPMe₃)]₂ The title compounds have been prepared by the reaction of the silylated phosphaneimines Me₃SiNPR₃ (R = CH₃, C₂H₅) with CrCl₂(THF)₂, PdCl₂ and CuCl₂, respectively, in dichloromethane suspensions. All donor-acceptor complexes were characterized by IR spectroscopy and by crystal structure determinations. [ CrCl₂(Me₃SiNPMe₃ )₂]: Space group Pccn, Z = 4, structure determination with 2104 observed unique reflections, R = 0.045. Lattice dimensions at ?70°C: a = 1326.3, b = 1562.5, c = 1171.5 pm. Within the monomeric molecular structure the chromium atom is planarly coordinated within the trans-configuration of the Cl atoms and the N atoms with distances of Cr? Cl = 235.94 pm and Cr? N = 211.7 pm. [ PdCl₂(Me₃SiNPEt₃)₂ ]: Space group P2₁/n, Z = 2, structure determination with 2412 observed unique reflections, R = 0.031. Lattice dimensions at 20°C: a = 917.3, b = 1390.2, c = 1161.7 pm, β = 95.80°. Within the monomeric molecular structure the palladium atom is planarly coordinated within the trans-configuration of the Cl atoms and the N atoms with distances of Pd? Cl = 222.9 pm and Pd? N = 209.5 pm. [ CuCl₂(Me₃SiNPMe₃)₂ ]: Space group Pbca, Z = 4, structure determination with 1861 observed unique reflections, R = 0.067. Lattice dimensions at ?70°C: a = 1440.2, b = 1205.1, c = 1536.5 pm. The compound forms centrosymmetric dimeric molecules, in which the Cu atoms are linked via almost symmetrical chloro-bridges with Cu? Cl distances of 231.4 pm. The distance Cu? N is 196.7 pm.     

Zur Element-Stickstoff-Doppelbindung in Kationen cyclischer Bis(amino)-phospha-, -arsa-, -stiba- und -bismutane

The Element-Nitrogen Double Bond in Cations of Cyclic Bis(amino)phospha-, -arsa-, -stiba-, and bismuthines Bis(amino)sila-phospha, -arsa-, -stiba-, and bismaetidines which bear a positive charge and incorporate a formally two valent element of group V are obtained from the corresponding bis(amino)elementchlorides by transfer of the chloride anion to the Lewis acids AlCl₃, GaCl₃, and InCl₃. X-ray structure analyses on the compounds Me₂Si(N^tBu)₂P⁺AlCl₄- ( 2a ), Me₂Si(N^tBu)₂Sb⁺AlCl₄- ( 2c ), and Me₂Si(N^tBu)₂Bi⁺AlCl₄ -( 2d ) reveal that the electron lack at the element(V) can be compensated by two different bonding mechanisms. In the case of the phosphorus derivative 2a the electronic balance is accomplished by intramolecular backbonding from the neighbouring nitrogen atoms (mean N-P⁺ = 163.3 pm). In the antimony and bismuth derivatives ( 2c and 2d ) the chlorine atoms of the AlCl₄ anions coordinate to the unsaturated element(V) in an intermolecular manner (mean: Sb·Cl = 305, Bi ?Cl = 309 pm). The N? Si? N group which is identical in all molecules, may be used as a probe for the electronic balance within the ring systems. The bond lengths and angles vary dramatically with respect to the electron acceptor properties of the element to which the group is bonded. 2a forms orthorhombic crystals, space group Pnma, Z = 8 (a = 3023.7(9), b = 1001.0(3), c = 1414.6(5) pm), and 2c and 2d are isotypic, again orthorhombic, space group Pbca with Z = 8 ( 2c a = 2030.8(8), b = 1193.1(4), c = 1777.1(6) pm; 2d : a = 2025.9(8), b = 1198.0(4), c = 1761.3(6) pm).     

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)°.     

Aufbau von Trimethylsilyl-substituierten Polyedern aus Calcium,Zinn(II) und Phosphor

Synthesis of Trimethylsilyl Substituted Polyhedra of Calcium, Tin(II), and Phosphorus The reaction of calcium-bis[bis(trimethylsilyl)amide] with bis(trimethylsilyl)phosphane in thf yields the heteroleptic, dimeric (tetrahydrofuran-O)calcium-bis(trimethylsilyl)amidebis(trimethylsilyl)phosphanide 1 (triclinic, P 1 , a = 1066,6(2), b = 1141,3(2), c = 1226,6(2)pm, α = 97,78(3)°, β = 107,47(3)°, γ = 101,12(3)°, Z = 1 dimer). The bridging phosphanide-substituent displays with Ca? P bond lengths of 292,6 and 300,5 pm a distortion of the four-membered Ca₂P₂-cycle. The reaction with another equivalent of HP(SiMe₃)₂ in thf leads to the formation of tetrakis(tetrahydrofuran-O)calcium-bis[bis(trimethylsilyl)phosphanide] 2 mit Ca? P distances of 292 pm (monoclinic, P2₁/c, a = 1626,0(3), b = 1295,3(4), c = 2039,5(5) pm, β = 102,60(2)°, Z = 4). The performance of the reaction in the presence of bis[bis(trimethylsilyl)amino]stannylene yields heterobimetallic compounds with a central polyhedron of Ca-, Sn- and P-atoms. Dependent on the Sn/Ca ratio the isolation of tris(trimethylsilyl)phosphane as well as bis[tris(tetrahydrofuran-O)calcium]-ditin(II)-tetrakis(μ₃-trimethylsilylphosphandiide) 3 with a central dicalcia-distanna-tetraphosphacubane-fragment or (thf)₂CaSn₂[μ-P(SiMe₃)₂]₂[μ₃-PSiMe₃]₂ 4 (orthorhombic, Pnma, a = 2247,7(2), b = 1868,9(1), c = 1168,0(1) pm, Z = 4), respectively, succeeds. The Ca? P distances lie at 291 pm.     

Die Kristallstrukturen von [ReCl4(PhCCPh)]2 · 2 CH2Cl2 und von PPh4[ReOCl4]

Crystal Structures of [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂ and PPh₄[ReOCl₄] Single crystals of [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂ were obtained by chilling dilute solutions of the solvate [ReCl₄(PhC?CPh)POCl₃] in CH₂Cl₂. PPh₄[ReOCl₄] was formed by the reaction of the diphenyl acetylene complex [ReCl₅(PhC?CPh)] with PPh₄Cl · H₂O in CH₂Cl₂ solution. [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂: space group P2₁/c, Z = 2, 2244 observed independent reflexions, R = 0.038. Lattice parameters (19°C): a = 987.2 pm; b = 1533.9 pm; c = 1193.8 pm; β = 90.17° The compound forms centrosymmetrical dimeric molecules with ReCl₂Re bridges with Re? Cl distances of 241.2 and 267.6 pm. The longer Re? Cl bond is situated in trans-position to the equatorial, side-on coordinated diphenyl acetylene ligand with mean Re? C distances of 200 pm. PPh₄[ReOCl₄]: space group P4/n, Z = 2, 1487 observed, independent reflexions, R = 0.047. Lattice parameters (19°C): a = b = 1272.0 pm; c = 771.3 pm. The compound crystallizes in the AsPh₄[RuNCl₄] type; it consists of [ReOCl₄]^? anions and PPh₄⁺ cations. The anions are tetragonal with C_4v symmetry and bond lengths Re? O = 165.4 pm and Re? Cl = 232.6 pm; the bond angle OReCl is 106.7°.     

Reaktion von Chlornitrat mit CF3I: Isolierung von Trifluormethylchloriodnitrat CF3I(Cl)ONO2 und Kristallstruktur von Trifluormethylioddinitrat CF3I(ONO2)2

Reaction of Chlorine Nitrate with CF₃I: Isolation of Trifluormethylchloroiodinenitrate CF₃I(Cl)ONO₂ and the Crystal Structure of Trifluormethyliodinedinitrate CF₃I(ONO₂)₂ CF₃I reacts with ClONO₂ to Iodine(III)-compounds. After an addition CF₃I(Cl)ONO₂ is isolated and characterized by vibrational spectra. With surplus ClONO₂ it is formed CF₃I(ONO₂)₂. CF₃I(ONO₂)₂ crystallizes monoclinic in the space group P2₁/c with the cell parameters a = 1 024.3(6) pm, b = 873.5(6) pm, c = 873.4(6) pm and Z = 4. We measered following bonding distances: I? O: 207.3(3) and 220.8(2) pm, I? C: 221.1(4) pm and N? O: from 119.1(4) to 141.5(3) pm. Through an intermolecular I ··· O-contact the central iodine becomes a distorted plane geometry.     

Chlorthionitrenkomplexe des Wolframs Die Kristallstruktur von [WCl4(NSCl)]2

Chlorothionitrene Complexes of Tungsten. Crystal Structure of [WCl₄(NSCl)]₂ Tungsten hexachloride reacts with trithiazyl chloride, (NSCl)₃, yielding the chlorothionitrene complex [WCl₄(NSCl)]₂, from which AsPh₄[WCl₅(NSCl)] can be obtained by reaction with AsPh₄Cl. Both complexes are characterized by their i.r. spectra. The crystal structure of [WCl₄(NSCl)]₂ was determined and refined with X-ray diffraction data (1059 reflexes, R = 0.055). It crystallizes in the monoclinic space group P2₁/n with the lattice constants a = 1523, b = 904, c = 583 pm and β = 91.35°. In the unit cell there are two centrosymmetric [WCl₄(NSCl)]₂ molecules in which the W atoms are linked via two chloro bridges; short and long W? Cl distances (244 and 265 pm) alternate in the W₂Cl₂ ring, the NSCl groups are found in the trans positions to the longer W? Cl bonds. The WNS bond angle (175°) and short bond distances correspond to a formulation .     

Darstellung,Eigenschaften und Kristallstruktur von Cl3(bpy)Ta  NOCH3, einem Methoxynitrenkomplex des Tantals

Synthesis, Properties, and Crystal Structure of Cl₃(bpy)Ta≡NOCH₃, a Methoxynitrene Complex of Tantalum TaCl₅ reacts in the presence of 2,2′-bipyridine with O-methyl-hydroxylamine or bis(trimethylsilyl)-O-methyl-hydroxylamine to yield the methoxynitrene complex Cl₃(bpy)Ta≡NOCH₃. The red complex decomposes only slowly at moist air. It crystallizes in the monoclinic space group C2/c with the lattice constants a = 1588.5, b = 1515.9, c = 1414.2 pm, β = 122.78°, Z = 8. The monomeric complex exhibits a distorted octahedral coordination for the tantalum atom. The methoxynitrene ligand is coordinated by a Ta? N triple bond resulting in a linear Ta≡N? O arrangement with Ta? N? O = 174.0° and distances Ta? N = 174.4 pm and N? O = 134.8 pm. v(Ta? N) is observed in the i.r. spectrum at 950 cm^?1.     

Kristall- und Molekülstruktur von fac-Trichloro-tris(dimethylsulfoxid)bismut(III) BiCl3(DMSO)3

Crystal and Molecular Structure of fac-Trichloro-tris(dimethyl sulfoxide)bismuth(III) BiCl₃(DMSO)₃ Crystals of the known, although structurally not characterized title compound were fortuitously obtained from a reaction mixture containing (CH₃)₃SiN(SO₂CH₃)₂, BiCl₃, DMSO, CH₂Cl₂ and CH₃NO₂. Crystallographic data (at ?130°C): triclinic, space group P1 1, a = 816.1(5), b = 885.1(6), c = 1 360.6(8) pm, α = 77.58(3), β = 77.39(3), γ = 64.42(3)°, U = 0.8569 nm³, Z = 2. The DMSO ligands are bound through oxygen to the Bi atom. Important bond distances and angles in the resulting fac-octahedral complex are as follows: Bi? Cl 258.9, 261.0, 263.0, Bi? O 242.6, 245.7, 246.1 pm; Cl? Bi? O (trans) 170.3, 170.6, 176.9, Cl? Bi? Cl 94.6, 94.7, 96.0, O? Bi? O 81.7, 85.4, 87.9, Cl? Bi? O (cis) in the range 87.2–92.6, Bi? O? S 123.4, 126.1, 129.6°.     

Zur Kenntnis von CsLiCl2

On CsLiCl₂ CsLiCl₂ crystallizes with a = 492.35(9), c = 950.0(3) pm (Guinier data), tetragonal, P4/nmm, Z = 2. The crystal structure was determined and refined from single crystal data (R = 5.2, R_w = 4.0%). It is essentially that proposed earlier for KCoO₂ which is isotypic with CsLuO₂. In CsLiCl₂ Cs⁺ has C.N. = 9 (d? = 363 pm), Li⁺ C.N. = 5 (tetragonal pyramid) with d(Li? Cl) = 231 and 4 × 260 pm, respectively.     

Darstellung und Kristallstruktur von SnTl4Se3 mit einer Anmerkung zu TlSe

Preparation and Crystal Structure of SnTl₄Se₃ with a Note on TlSe We describe the preparation and crystal structure of SnTl₄Se₃. It crystallizes as a low symmetric distorted derivative with the In₅Bi₃ type of structure, which itself should be considered as a subfamily of the Cr₅B₃ type of structure: a = 852.2(2) pm, c = 1 272.2(6) pm, c/a = 1.49, Z = 4. Short Sn? Se distances of 311 pm, and 326 pm, respectively, are obtained in [SnSe_2/2] chains running along [001]. Furthermore, short Tl? Se distances are found in quasimolecular bent moieties Tl₂Se: 300 pm, 313 pm, and 347 pm, respectively. SnTl₄Se₃ is a semiconductor. The conductivity of some closely related phases are also reported. Finally, the structure of the well known compound TlSe has been refined for the first time, in order to get some more information about Tl¹⁺? Se distances for square-antiprismatic coordinated Tl¹⁺ ions.     

Phosphaniminato-Komplexe des Schwefels. Synthese und Kristallstrukturen von [O3SS(NPPh3)2] · CH3CN, [SO(NPPh3)2] und [SCl(NPMe3)2]Cl

Phosphorane Iminato Complexes of Sulfur. Syntheses and Crystal Structures of [O₃SS(NPPh₃)₂] · CH₃CN, [SO(NPPh₃)₂], and [SCl(NPMe₃)₂]Cl The title compounds have been prepared by the reaction of Me₃SiNPPh₃ with SO₂ and SOCl₂, respectively, and by the reaction of Me₃SiNPMe₃ with S₂Cl₂. They form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy and by crystal structure determinations. [O₃SS((NPPh₃)₂)] · CH₃CN : Space group Pca2₁, Z = 4, structure solution with 4016 observed unique reflections, R = 0.050. Lattice dimensions at ?60°C: a = 1865.1, b = 1168.4, c = 1569.0 pm. The compound has a zwitterionic structure with a S? S bond length of 218.2 pm and bond lengths S? N of 161.2 and P? N of 160.1 pm. [SO(NPPh₃)₂] : Space group P2₁/c, Z = 4, structure solution with 2854 observed unique reflections, R = 0.113. Lattice dimensions at ?50°C: a = 1173.1, b = 1585.6, c = 1619.2 pm, b? = 98.13°. The compound forms monomeric molecules, in which the positions of S and N atoms are disordered in two positions. The bond lengths are S? N 166 pm and P? N 163 pm in average. [SCl(NPMe₃)₂]Cl : Space group P1 , Z = 2, structure solution with 2416 observed unique reflections, R = 0.038. Lattice dimensions at 20°C: a = 613.2, b = 1030.3, c = 1111.4 pm, α = 88.48°, b? = 88.01°, γ = 83.10°. The compound forms ions [SCl(NPMe₃)₂]⁺ and Cl^?. In the cation the sulfur atom is ?-tetrahedrally coordinated with a long S? Cl distance of 246.9 pm and bond lengths S? N of 155.3 pm and P? N of 164.3 pm in average.     

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.     

Synthese und Kristallstruktur von Tetraphenylphosphonium-Aquabis(tetrasulfido)thionitrosyl-Osmat,PPh4[Os(NS)(S4)2(H2O)]

Synthesis and Crystal Structure of Tetraphenylphosphonium Aqua-bis(tetrasulfido)thionitrosyl Osmate, PPh₄[Os(NS)(S₄)₂(H₂O)] PPh₄[Os(NS)(S₄)₂(H₂O)] has been prepared as redbrown crystals by reacting PPh₄[OsNCl₄] with a solution of excess disodium tetrasulfide in dimethylformamide/H₂O and characterized by IR spectroscopy and by a crystal structure determination. Space group P2₁/n, Z = 4, structure solution with 4162 independent reflections, R = 0.059 for reflections with I > 2σ(I). Lattice dimensions at ?40°C: a = 1138.9(5), b = 1301.4(4), c = 2092.7(7) pm, β = 104.74(3)º. Os? N, Os? O, and Os? S distances are 175.2(12), 219.8(12), and 237.5(4)?239.1(4) pm, respectively. The Os?N?S moiety is approximately linear, with an OsNS angle of 171.2(7)º.     

Darstellung sowie Kristall- und Molekülstruktur von Triphenylphosphinoxidhydrogenfluorid, (C6H5)3PO · HF

Preparation, Crystal and Molecular Structure of Triphenylphosphineoxide Hydrogen - fluoride (C₆H₅)₃PO · HF (C₆H₅)₃PO · HF was prepared from hydrofluoric acid (40%) and (C₆H₅)₃PO in benzene. It crystallizes in the monoclinic space group P2₁/c with a = 1 032.8(3), b = 1 051.0(7), c = 1695.5(2) pm, β = 121.95(2)° and Z = 4; d (calc./obs.) 1.27/1.26 g ° cm^?3. The structure was determined by direct methods from 2 709 independent reflections and has been refined by full matrix least squares methods to R = 0.049. In the compound HF and (C₆H₅)₃PO are linked by a short H-bond. Some distances: O? F 238.4(5), O? H 142.3, H? F 99.8, P? O 149.5(4) pm. Angle O? H? F 159.8°.     

Die Reaktion von SeCl4 mit Übergangsmetalltetrachloriden. Synthese und Kristallstrukturen von (SeCl3)2MCl6 mit M = Zr,Hf, Mo,Re

The Reaction of SeCl₄ with Transition Metal Tetrachlorides. Synthesis and Crystal Structures of (SeCl₃)₂MCl₆ with M = Zr, Hf, Mo, Re The transition metal tetrachlorides ZrCl₄, HfCl₄ and MoCl₄ react with SeCl₄ in closed ampoules at temperatures of 140°C to (SeCl₃)₂MCl₆ (M = Zr, Hf, Mo) which are all isotypic and crystallize in the (SeCl₃)₂ReCl₆ structure type (orthorhombic, Fdd2, Z = 8, lattice constants for M = Zr: a = 1165.7(1)pm, b = 1287.2(2)pm, c = 2180.2(2)pm; for M = Hf: a = 1162.9(2)pm, b = 1285.0(2)pm, c = 2178.2(3)pm; for M = Mo: a = 1153.8(1)pm, b = 1267.7(1)pm, c = 2147.4(2)pm). The Cl^? ions form a hexagonal closest packing with one fourth of the octahedral holes filled by Se⁴⁺ and M⁴⁺ in an ordered way. The MCl₆ octahedra are regular, the SeCl₆ octahedra are distorted with 3 short and 3 long Se? Cl bonds (mean 215 pm and 287 pm). The structures can thus be regarded as built of SeCl₃⁺ and MCl₆^2? ions. Magnetic susceptibility measurements show for M = Zr the expected diamagnetic behavior, for M = Mo and Re paramagnetic behavior according to the Curie-Weiss law with magnetic moments of 2.5 B. M. for M = Mo and 3.7 B. M. for M = Re corresponding to 2 and 3 unpaired electrons respectivly.     

Synthese und Kristallstrukturen der Phosphaniminato-Komplexe [AlCl2(NPEt3)]2, [GaI2(NPEt3)]2 und [GaI2(NPPh3)]2

Synthesis and Crystal Structures of the Phosphoraneiminato Complexes [AlCl₂(NPEt₃)]₂, [GaI₂(NPEt₃)]₂, and [GaI₂(NPPh₃)]₂ [AlCl₂(NPEt₃)]₂ ( 1 ) is made according to the known method by reaction of aluminium trichloride with the silylated phosphaneimine Me₃SiNPEt₃ in acetonitrile; it is isolated as colourless, moisture sensitive crystals. The phosphoraneiminato complexes [GaI₂(NPEt₃)]₂ ( 2 ) and [GaI₂(NPPh₃)]₂ ( 3 ), on the other hand, are obtained by redox reactions as pale yellow crystals; ( 2 ) of “gallium(I) iodide” with Me₃SiNPEt₃ in toluene and ( 3 ) of gallium with N-iodine triphenylphosphaneimine, INPPh₃, in tetrahydrofuran. 1 and 3 are characterized spectroscopically and by crystal structure determinations; 2 is characterized only crystallographically. 1 : Space group Pbca, Z = 4; lattice dimensions at –70 °C: a = 1232.6(2), b = 1341.1(2), c = 1393.4(3) pm, R₁ = 0.0315. 1 forms centrosymmetric molecules in which the Al atoms are linked via Al–N bonds of the two (NPEt₃^–) groups; with 185.0 and 184.4 pm these bonds are of almost the same lengths. 2 : Space group Pbca, Z = 4; lattice dimensions at –80 °C: a = 1380.0(1), b = 1311.0(1), c = 1429.1(1) pm, R₁ = 0.0273. 2 crystallizes isotypically with 1 . The gallium atoms of the centrosymmetric Ga₂N₂ four-membered ring are connected with Ga–N distances of equal length (190.9 pm). 3 · THF: Space group P2₁2₁2₁, Z = 2; lattice dimensions at –140 °C: a = 1494.6(1), b = 1536.3(1), c = 974.6(1) pm, R₁ = 0.0382. 3 forms dimeric molecules in which the gallium atoms are linked via the N atoms of the (NPPh₃^–) groups to form a non-planar Ga₂N₂ four-membered ring of C₂ symmetry with Ga–N bonds of equal lengths – within standard deviations – of 194.7 pm. The phosphoraneiminato groups are arranged in a synperiplanar way.     

Die Kristallstrukturen von ErSeI und NaErSe2

The Crystal Structures of ErSeI and NaErSe₂ It is reported about attempts to synthesize lanthanoide selenidehalides of the formula LnSeX (X ? Cl, Br, I) exemplary for Ln ? Er. The relative stabilities of these compounds are discussed. X-ray crystal structure analysis revealed for the compounds ErSeBr and ErSeI the FeOCl-structure type (space group Pmmn, Z = 2, a = 406.3(5) pm, b = 559.2(6) pm, and c = 795(1) pm, and a = 418.26(6) pm, b = 558.4(1) pm, and c = 889.0(2) pm, respectively). A corresponding chloride was not found within the scope of this investigation. From the educts Er₂Se₃ and ErCl₃ in the presence of NaCl as flux in Nb-ampoules the compound NaErSe₂ was formed instead which crystallizes in an α-NaFeO₂-type structure (space group R3 m, Z = 3, a = 408.41(2) pm and c = 2067.4(2) pm).