Umsetzung von C(NMe2)4 mit Ni(CO)4 – Synthesen und Strukturen von [C(NMe2)3][(CO)3NiC(O)NMe2], [C(NMe2)3]2[Ni5(CO)12] und [C(NMe2)3]3[Ni6(CO)12][O2CNMe2]

Reaction of C(NMe₂)₄ with Ni(CO)₄ – Syntheses and Structures of [C(NMe₂)₃][(CO)₃NiC(O)NMe₂], [C(NMe₂)₃]₂[Ni₅(CO)₁₂], and [C(NMe₂)₃]₃[Ni₆(CO)₁₂][O₂CNMe₂] The reaction of C(NMe₂)₄ with Ni(CO)₄ in THF produces the carbamoyl complex [C(NMe₂)₃][(CO)₃NiC(O)NMe₂] ( 1 ); side products are the purple cluster compound [C(NMe₂)₃]₂[Ni₅(CO)₁₂] · THF ( 2 · THF) and the red cocristallization product [C(NMe₂)₃]₃[Ni₆(CO)₁₂][O₂CNMe₂] ( 3 ). All compounds were studied by X‐ray diffraction analyses. The cations of 3 are all disordered but not those of 1 and 2 . The unit cell of 1 contains two crystallographically independent anions (I and II) which differ in the dihedral angle between the plane of the carbamoyl ligand and the plane defined by the atoms C_Carbamoyl–Ni–CO amounting 0° in the anion I and 18° in the anion II.     

Salze von Halogenophosphorsäuren. XIX. Über die Darstellung von Kupfer(II)-monofluorophosphat-Solvaten und die Kristallstruktur von Aquamonofluorophosphatokupfer(II)-1,4-Dioxan 2/1, 2[Cu(H2O)PO3F] · C4H8O2

Salts of Halogenophosphoric Acids. XIX. Preparation of Copper(II) Monofluorophosphate Solvates and the Crystal Structure of Aquamonofluorophosphatocopper(II)-1,4-Dioxane 2/1, 2[Cu(H₂O)PO₃F] · C₄H₈O₂ The mixed solvate Aquamonofluorophosphatocopper(II)-1,4-Dioxane 2/1 1 was obtained by the reaction of aqueous solutions of NH₄HPO₃F and acidified (NH₄)₂PO₃F, respectively, using 1,4-dioxane as precipitating agent. 1 crystallizes in the monoclinic space group C2/m with a = 2130.9(2), b = 655.45(6), c = 447.30(4) pm, b? = 96.207(7)° and Z = 2. Copper(II) monofluorophosphate-methanol 1/1, CuPO₃F · CH₃OH 2 was obtained by the reaction of copper(II) salts with alkaline or ammoniummonofluorophosphates in methanol. 1 and 2 react in the presence of water vapor to copper(II) monofluoro phosphate dihydrate, CuPO₃F · 2H₂O 3 , which reacts reversibly with dioxan or CH₃OH under formation of 1 and 2 , respectively.     

Über die Reaktionen von CH2=P(NMe2)3 mit Fe(CO)5, Cr(CO)6 und CS2; Molekülstrukturen von [MeP(NMe2)3][(CO)5CrC(O)CH=P(NMe2)3] und (CO)4Fe=C(OMe)CH=P(NMe2)3

The Reactions of CH₂=P(NMe₂)₃ with Fe(CO)₅, Cr(CO)₆, and CS₂; Molecular Structures of [MeP(NMe₂)₃][(CO)₅CrC(O)CH=P(NMe₂)₃], and (CO)₄Fe=C(OMe)CH=P(NMe₂)₃ The ylide CH₂=P(NMe₂)₃ ( 1 ) reacts with several binary transition metal carbonyls M(CO)_x to produce the corresponding salt like compounds [MeP(NMe₂)₃][(CO)_x–1MC(O)CH=P(NMe₂)₃] (M = Fe ( 3 ), Cr ( 4 )). The related reaction with CS₂ leads to the salt [MeP(NMe₂)₃][SC(S)CH=P(NMe₂)₃] ( 2 ). While 4 is thermally stable, 3 rapidly decomposes at room temperature with formation of [MeP(NMe₂)₃]₂[Fe₂(CO)₈] ( 8 ). Alkylation of 3 (at –50 °C) and 4 with MeSO₃CF₃ produces the related carbene complexes (CO)_x–1M=C(OMe)CH=P(NMe₂)₃ ( 5 ) and ( 6 ); the reaction of 3 with Me₃SiCl results in the formation of the carbene complex (CO)₄Fe=C(OSiMe₃)CH=P(NMe₂)₃ ( 7 ). 4 crystallizes in the space group P2₁2₁2₁ (No. 19) with a = 1111.1(2), b = 1476.1(3), c = 1823.1(4) pm and Z = 4. 5 crystallizes in the space group P2₁/n (No. 14) with a = 1303.6(3), b = 910.5(4), c = 1627.0(4) pm, β = 96.06(2)° and Z = 4. The compounds have been characterized by elemental analyses, NMR (¹H, ¹³C, ³¹P) and IR spectroscopy.     

Über die Kristallstruktur von Barium-Acetylendicarboxylat Monohydrat – Ba[C2(COO)2] · H2O

On the Crystal Structure of Barium Acetylene Dicarboxylate Monohydrate – Ba[C₂(COO)₂] · H₂O Ba[C₂(COO)₂] · H₂O crystallizes in the monoclinic space group P2₁/a. The lattice constants are a = 753.4(2), b = 921.8(2), c = 881.8(2) pm and β = 102.00(2)°. The crystal structure is characterized by an intricate three-dimensional framework made up by Ba²⁺ and [C₂(COO)₂]^2? ions. Ba²⁺ has coordination number 9 and is bound to two water molecules and seven oxygen atoms belonging to carboxylate groups of the dianion. The [C₂(COO)₂]^2? ion does not merely act like a multiple monodentate ligand, but coordinates Ba²⁺ in a chelate-like manner as well. The carboxylate groups of the dianion are inclined to each other by 65°.     

Synthese und Kristallstruktur von [C(NMe2)3]2[(CO)4Fe(μ‐InCl2)2Fe(CO)4]

Synthesis and Crystal Structure of [C(NMe₂)₃]₂[(CO)₄Fe(μ‐InCl₂)₂Fe(CO)₄] Treatment of [C(NMe₂)₃]₂[(CO)₄FeInCl₃] ( 1 ) with hot water produces the dinuclear complex [C(NMe₂)₃]₂[(CO)₄Fe(μ‐InCl₂)₂Fe(CO)₄] ( 2 ) which could be crystallized from dichloromethane/pentane. 2 crystallizes in the monoclinic space group P2₁/n with a = 835.7(1), b = 1187.8(1), c = 1902.7(1) pm, β = 91.877(5)° and Z = 2. The anion contains a four‐membered Fe—In—Fe—In ring with octahedral environment at the iron atom and tetrahedral coordination at the In atom.     

Darstellung und spektroskopische Charakterisierung von Kupfer(II)- und Nickel(II)-tricyanmethanid-Komplexen mit Imidazol-Derivaten – Kristallstruktur von [Cu{C(CN)3}2(2-meiz)2]

Synthesis and Spectroscopic Characterization of Copper(II) and Nickel(II) Tricyanomethanide Complexes with Imidazoles – Crystal Structure of [Cu{C(CN)₃}₂(2-meiz)₂] The copper(II) and nickel(II) tricyanomethanide complexes with imidazoles of the type [Cu{C(CN)₃}₂L₄], [L = 2- or 4-methylimidazole (meiz)] and [M{C(CN)₃}₂L₂] [M = Cu, L = imidazole (iz), 2- or 4-meiz; M = Ni, L = iz, 2- or 4-meiz] were prepared and characterized by electronic, infrared, and – some of them – by ESR spectroscopy. The structure [Cu{C(CN)₃}₂(2-meiz)₂], solved by X-ray crystallographic analysis, shows a two-dimensional network with unsymmetric C(CN)₃-bridges between the Cu^II atoms. Polymeric structures with bridging C(CN)₃-groups were identified by means of spectroscopic methods also for the other [M{C(CN)₃}₂L₂] complexes. On the other hand, for the complexes [M{C(CN)₃}₂L₄] follow molecular structures, in which monodentate C(CN)₃ ligands are present. All compounds under investigation show a tetragonal-bipyramidal geometry with various degree of tetragonal distortion.     

Darstellung,Kristallstruktur und quantenchemische Berechnung von [C(NMe2)3]2[(CO)4FeInCl3]

Preparation, Structure, and Quantum Chemical Calculation of [C(NMe₂)₃]₂[(CO)₄FeInCl₃] The title compound ( 1 ) has been obtained as colorless crystals by reacting InCl₃ with [C(NMe₂)₃][(CO)₄FeC(O)NMe₂] in THF solution. The crystal structure determination (monoclinic, C2/c) shows the presence of separate ions with one disordered and one non disordered cation. In the dianion the CO groups of the trigonal bipyramidal coordinated iron atom and the Cl atoms of the tetrahedral coordinated indium atom form a staggered conformation with a relatively short In–Fe bond distance of 252 pm. Quantum Chemical DFT calculations of [CO)₄FeInCl₃]^2– show that the Fe–In bond has a strong ionic character and that it should be considered as an adduct of [Fe(CO)₄]^2– and InCl₃.     

Über die Reaktion von W3O mit lod. Darstellung,Kristallstruktur und Eigenschaften von WOI3

On the Reaction of W₃O with Iodine: Preparation, Crystal Structure, and Properties of WOI₃ The novel tungsten oxide iodide WOI₃ is obtained from the reaction of the metalrich tungsten oxide W₃O (also known as ‘β-tungsten’) with iodine in a sealed glass tube placed in a temperature gradient (440–400°C). In the low-temperature region WOI₃ is formed as mouse-grey intergrown needle-like crystals. WOI₃ crystallizes in the tetragonal NbOCl₃ structure type, space group P4₂/mnm, with a = 12.346(2), c = 3.765(1) Å (20°C). The crystal structure at – 130°C was determined from single-crystal diffractometer data (R = 0.023). Results of magnetic susceptibility and vibrational spectroscopic measurements are given together with the mass spectrum of WOI₃ obtained on heating.     

Synthesis of a new salt containing polyoxometallate anion and M?Cu?S cluster cation [MS4Cu4(γ-MePy)8][M6O19] (M = Mo,W). Crystal structure of [WS4Cu4(γ-MePy)8] [W6O19]

Reactions of (NH₄)₂MS₄, AgBr and CuBr in γ-methylpyridine produced one new compound, [MS₄Cu₄(γ-MePy)8][M₆O₁₉] (1, M = W; 2 , M = Mo), of which 1 was characterized by single crystal X-ray analysis. The crystal data: orthorhombic, Pbcn, a = 15.434(4), b = 16.732(2), c = 28.657(7) Å, V = 7400.8(8) ų, Z = 4 , R = 0.072 for 3121 independent data. The compound is the first example which contains both polyoxotungstate anion and heteropolynuclear cluster cation. In the structure of the cation four edges of the tetrahedral WS^2?₄ core are coordinated by four copper atoms, giving a WS₄Cu₄ aggregate of approximate D_2h symmetry. The differences between the reaction of Cu⁺ with MS^2?₄ and that of Ag+ with MS^2?₄ in pyridine and its derivatives are discussed.     

Reaktion von cyclopentadienyl-substituierten Molybdän(V)-tetrachloriden mit LiPH(2,4,6-BuC6H2) und KPPh2(Dioxan)2. Molekülstrukturen von [Cp0Mo(μ-Cl)2]2 und [CpMo2(μ-Cl)3(μ-PPh2)] (Cp0 = C5Me4Et)

Reaction of Cyclopentadienyl Substituted Molybdenum(V) Tetrachlorides with LiPH(2,4,6-Bu C₆H₂) and KPPh₂(Dioxane)₂. Crystal Structures of [Cp⁰Mo(μ? Cl)₂]₂ and [Cp Mo₂(μ? Cl)₃(μ? PPh₂)] (Cp⁰ = C₅Me₄Et) The reaction of [Cp⁰Mo(CO)₃]₂ (Cp⁰ = C₅Me₄Et) and [Cp′Mo(CO)₃]₂ (Cp′ = C₅H₄Me) with PCl₅ in CH₃CN furnishes the Mo(V) complexes Cp⁰MoCl₄(CH₃CN) 1 and Cp′MoCl₄(CH₃CN) 2 in good yields. While 1 and 2 are reduced by LiPH(2,4,6-BuC₆H₂) to the Mo(III) complexes [Cp⁰Mo(μ? Cl)₂]₂ 3 and [Cp′Mo(μ? Cl)₂]₂ 4 , the reaction of 1 with KPPh₂(dioxane)₂ yields the reduction/substitution product [CpMo₂(μ? Cl)₃(μ? PPh)] 5 in low yield. 1 – 4 were characterized spectroscopically (i.r., mass, 3 and 4 also n.m.r.). An X-ray crystal structure determination was carried out on 3 and 5. 3 crystallizes in the triclinic space group P1 (No. 2) with a = 8.278(4), b = 12.508(7), c = 12.826(7) Å, α = 86.78(5), β = 81.55(2), γ = 75.65(4)°, V = 1 272.4 ų and two formula units in the unit cell (data collection at ? 67°C, 4 255 independent observed reflections, R = 2.9%); 5 crystallizes in the triclinic space group P1 (No. 2) with a = 11.536(8), b = 12.307(9), c = 13.157(9) Å, α = 91.41(6), β = 100.42(5), γ = 112.26(6)°, V = 1 688.7 ų and two formula units in the unit cell (data collection at ? 60°C, 6 147 independent observed reflections, R = 4.9%). The crystal structure of 3 shows the presence of centrosymmetric dimeric molecules with four bridging chloro ligands. In 5, two Mo atoms are bridged by three chloro ligands and one PPh₂ ligand. The Mo? Mo bond length in 3 and 5 (2.600(2), 2.596(2) Å and 2.6388(8) Å) is in agreement with a Mo? Mo bond.     

Lithiumtriamidostannat(II), Li[Sn(NH2)3] – Synthese und Kristallstruktur

Lithium Triamidostannate(II), Li[Sn(NH₂)₃] – Synthesis and Crystal Structure Rusty-red glistening, transparent crystals of Li[Sn(NH₂)₃] were obtained by reaction of metallic lithium with tetraphenyl tin in liquid ammonia at 110 °C. The structure was determined from X-ray single-crystal diffractometer data: Space group P 2₁/n, Z = 4, a = 8.0419(9) Å, b = 7.1718(8) Å, c = 8.5085(7) Å, β = 90.763(8)°, R₁ (F _o ≥ 4σ(F _o)) = 2.8%, wR₂ (F ≥ 2σ(F )) = 5.3%, N(F ≥ 2σ(F )) = 1932, N(Var.) = 65. The crystal structure contains trigonal pyramidal complex anions [Sn(NH₂)₃]^– with tin at the apex, which are connected to layers of sequence A B A B … by lithium in tetrahedra-double units [Li(NH₂)_2/2(NH₂)₂]₂.     

Kaliumtriamidostannat(II), K[Sn(NH2)3] – Synthese und Kristallstruktur

Potassium Triamidostannate(II), K[Sn(NH₂)₃] – Synthesis and Crystal Structure Rusty‐red crystals of K[Sn(NH₂)₃] were obtained by the reaction of SnBr₂ and KNH₂ in a 1 : 3 molar ratio in liquid ammonia at 233 K in the form of platelets. The structure was determined from single crystal X‐ray diffractometer data: Space group P3; Z = 2; a = 6.560(1) Å, c = 7.413(2) Å. The structure contains trigonal pyramidal complex anions [Sn(NH₂)₃]^– and potassium cations. These ions are arranged to one another following the motif of a strongly distorted hexagonal close packing of sequence A(Sn) B(Sn) A′(K) B′(K) …     

Darstellung und Kristallstruktur von Kupfer(II)-monofluorophosphat-Dihydrat CuPO3F · 2H2O

Salts of Halogenophosphoric Acids. XVII. Preparation and Crystal Structure of Copper(II) Monofluorophosphate Dihydrate CuPO₃F · 2H₂O Copper(II) monofluorophosphate dihydrate, CuPO₃F · 2H₂O 1 was obtained by the reaction of aqueous NH₄HPO₃F and acid (NH₄)₂PO₃F solutions, respectively, using acetone or ethanol as precipitating agents. The thermal dehydration of 1 gives the water-free copper monofluorophosphate CuPO₃F ( 2 ). 1 crystallizes in the monoclinic space group P2₁/c with a = 761,44, b = 780,97, c = 921,02 pm, β = 112,94° and Z = 4.     

Über den Einfluß von Substitution auf die Kristallstruktur von SrNi2P2

About the Effect of Substitution on the Crystal Structure of SrNi₂P₂ With several series of mixed crystals the effect of substitution on the crystal structure of SrNi₂P₂ (polymorphic, the structures are variants of the ThCr₂Si₂ type) is investigated by X-ray methods. In the compound Ni completely can be substituted by Co and Cu respectively and also P by As; in Sr_1–xCa_xNi₂P₂ there is a gap of the miscibility between 0.3 ≤ x ≤ 0.6. A low substitution of the several elements more than proportionally changes the structure parameters. In this range the mixed crystals with Ca, Cu, and As, respectively, undergo first order phase transitions with significant changes of the bond distances, which will be interpreted by the results of band structure calculations.     

AlCl3 · 3NH3 — eine Verbindung mit der Kristallstruktur eines Tetraammindichloroaluminium-diammintetrachloroaluminats: [AlCl2(NH3)4]+[AlCl4(NH3)2]−

AlCl₃ · 3NH₃ — a Compound with the Crystal Structure of a Tetraammine Dichloro Aluminium-Diammine Tetrachloro Aluminate: [AlCl₂(NH₃)₄]⁺[AlCl₄(NH₃)₂]^? . AlCl₃ · 3 NH₃ ? [AlCl₂(NH₃)₄]⁺ [AlCl₄(NH₃)₂]^? forms during the reaction of two mole NH₃ with AlCl₃(NH₃) at T ≥ 200°C. Repeated heating and cooling within 48 h between 200°C and 250°C gives a homogeneous product with total uptake of the necessary amount of NH₃. Slow sublimation in a vacuum line apparatus at 200°C gives crystals of the triammoniate sufficient for a X-ray structure determination: The compound contains elongated [AlCl₂(NH₃)₄]⁺ octahedra and compressed [AlCl₄(NH₃)₂]^? octahedra. Besides ionic bonding hydrogen bridge bonds with 3.369 Å ? d(N—H … Cl) ? 3.589 Å stabilize the atomic arrangement.     

Synthese und Kristallstruktur von Cu4[PhN3C6H4N3(H)Ph]4(μ2-O)2, einem vierkernigen Kupfer(II)-Komplex mit 1-Phenyltriazenido-2-phenyltriazenobenzol als Ligand

Synthesis and Crystal Structure of Cu₄[PhN₃C₆H₄N₃(H)Ph]₄(μ₂-O)₂, a Tetranuclear Copper(II) Complex with 1-Phenyltriazenido-2-phenyltriazeno-benzene as Ligand Cu₄[PhN₃C₆H₄N₃(H)Ph]₄(μ-O)₂ ( 1 ) results from the reaction of an aqueous solution of [Cu(NH₃)₄]²⁺ with 1,2-bis(phenyltriazeno)benzene in ether. 1 crystallizes in the orthorhombic space group Pba2 with the lattice parameters a = 1661.5(5), b = 1914.7(7), c = 1269.2(5) pm; Z = 2. In the tetrameric complex with the symmetry C₂ the Cu²⁺ cations form a tetrahedron (Cu? Cu: 298.3(1)?337.1(1) pm). The μ₂-oxo ligands occupy the twofold axis and bridge two opposite edges of the Cu₄ tetrahedron (Cu? O: 190.0(3) and 192.5(4) pm). The 1-phenyltriazenido-2-phenyltriazeno benzene anions bridge two Cu²⁺ ions chelating one metal ion and coordinating monodentate the neighbouring one (Cu? N: 191.0(5)–204.1(4) pm).     

Synthesis and Crystal Structure of an Ion- pair Compound: [HL]_2[Ni(CN)_4]·4H_2O (L = 4-(2- Hydroxyphenyl)-1,5, 9-triazacyclododecan-2-one)

1INTRODUCTIONCyclicpolyamineshaveoriginatedagreatdealofinterestowingtotheirbiologicalactivity[1～3]andalotofmetalcomplexeswithmacrocyclicpoly-amineligandssuchastriamine[12]aneN4,tetra-aminecyclen,cyclam,pentaamine[16]aneN5,theirderivativesandsoonhavebeens…     

Über die Reaktion von 2,2-Dimethylpropylidinphosphan mit Molybdänpentachlorid; die Kristallstruktur von [Mo2Cl6(α,α′-Dipyridyl)3]

Reaction of 2,2-Dimethylpropylidynephosphine with Molybdenum Pentachloride; Crystal Structure of [Mo₂Cl₆(α,α′-dipyridyl)₃] 2,2-Dimethylpropylidynephosphine and molybdenum pentachloride dissolved in POCl₃ react with oxydation of the phosphorus and reduction of the molybdenum atom to give the alkyne complex [Mo₂Cl₄(μ-Cl)₂(μ-H₉C₄? C?C? C₄H₉)(OPCl₃)₂]. Addition of α,α′-dipyridyl or of methyltriphenylphosphonium chloride in dichloromethane results in a displacement of the ligands POCl₃ and H₉C₄? C?C? C₄H₉ from this complex and in the formation of [Mo₂Cl₆(dipy)₃] or [(H₅C₆? )₃P? CH₃]₃[Mo₂Cl₉]. Besides the latter compound small amounts of [(H₅C₆? )₃P? CH₃]₂[MoCl₆] can be isolated from the reaction mixture. [Mo₂Cl₆(dipy)₃] which has already been prepared by other methods crystallizes in the monoclinic space group P2₁/c with {a = 1612; b = 148; c = 1296 pm; γ 109.3°; Z = 4} at 20°C. As shown by a crystal structure determination the complex is built up from [MoCl₂(dipy)₂]⁺ cations and [MoCl₄(dipy)]^? anions. The molybdenum atoms are both octahedrally surrounded. With average values of 238 and 243 pm the Mo? Cl bond distances in the cation, where a cis-arrangement of the chlorine atoms is observed, and in the anion differ significantly from each other. [Mo₂Cl₆(dipy)₃] which has already been prepared by other methods crystallizes in the monoclinic space group P2₁/c with {a = 1612; b = 148; c = 1296 pm; γ = 109.3°; Z = 4} at 20°C. As shown by a crystal structure determination the complex is built up from [MoCl₂(dipy)₂]⁺ cations and [MoCl₄(dipy)]^? anions. The molybdenum atoms are both octahedrally surrounded. With average values of 238 and 243 pm the Mo? Cl bond distances in the cation, where a cis-arrangement of the chlorine atoms is observed, and in the anion differ significantly from each other.     

Bis(N‐acetyltriethylphosphaniminium)‐tetraacetato‐dichloro‐dicuprat(II), [MeC(O)N(H)PEt3]2[Cu2(O2C–Me)4Cl2]

Bis(N‐acetyltriethylphosphaneiminium)‐tetraacetato‐dichloro‐dicuprate(II), [MeC(O)N(H)PEt₃]₂[Cu₂(O₂C–Me)₄Cl₂] The title compound has been prepared by the reaction of Me₃SiNPEt₃ with [Cu₂(O₂C–Me)₄] and MeC(O)Cl in dichloromethane solution to give colourless crystals which include four molecules CH₂Cl₂ per formula unit. The complex is characterized by IR spectroscopy and by a crystal structure determination. [MeC(O)N(H)PEt₃]₂[Cu₂(O₂C–Me)₄Cl₂] · 4 CH₂Cl₂: Space group P2₁/n, Z = 2, lattice dimensions at –70 °C: a = 794.1(1), b = 2356.9(6), c = 1327.3(2) pm; β = 91.00(1)°; R₁ = 0.0597. The structure consists of N‐acetyltriethylphosphaneiminium cations and dianions [Cu₂(O₂C–Me)₄Cl₂]^2– which form an iontriple with N–H…Cl hydrogen bridges.