Synthese,Kristallstruktur und Magnetismus von [(CH3)2NH2][PrCl4(H2O)2]

Preparation, Crystal Structure, and Magnetism of [(CH₃)₂NH₂][PrCl₄(H₂O)₂] The complex water containing chloride [(CH₃)₂NH₂][PrCl₄(H₂O)₂] has been prepared for the first time and the crystal structure has been determined from single crystal X‐ray diffraction data. The compound crystallizes orthorhombically in the space group Cmca (Z = 8) with a = 1796.6(2) pm, b = 940.7(1) pm, and c = 1238.4(2) pm. The anionic part of the structure is built up by chains of edge‐connected trigondodecahedra [PrCl₆(H₂O)₂]^3– according to [PrCl_4/2Cl₂(H₂O)₂]^–, which are held together by dimethylammonium cations ([(CH₃)₂NH₂]⁺). In order to study the interactions between the praseodymium cation (Pr³⁺) and the ligands magnetic measurements were carried out. The magnetic data were interpreted by ligand field calculations applying the angular overlap model.     

Synthese,Kristallstruktur und magnetisches Verhalten von (2,4,6‐Trimethylpyridinium)10[ErCl6][ErCl5(H2O)]2Cl3

Preparation, Crystal Structure, and Magnetic Behaviour of (2,4,6‐Trimethylpyridinium)₁₀[ErCl₆][ErCl₅(H₂O)]₂Cl₃ Crystals of the complex chloride (2,4,6‐Trimethylpyridinium)₁₀[ErCl₆][ErCl₅(H₂O)]₂Cl₃ have been prepared by reaction of ErCl₃·6H₂O with 2,4,6‐Trimethylpyridiniumchloride in ethanol solution for the first time. The crystal structure has been determined from single crystal X‐ray diffraction data. The compound crystallizes monoclinically in the space group P2₁/a (Z = 2) with a = 1704.5(3) pm, b = 1696.7(2) pm, c = 1798.5(4) pm and β = 90.76(3)°. The structure contains octahedral building units [ErCl₆]^3— and [ErCl₅(H₂O)]^2—. The octahedra, the organic cations and isolated chloride anions are interconnected via hydrogen bonds forming layers parallel to the ac‐plane (0 1 0). The magnetic behaviour of (2,4,6‐Trimethylpyridinium)₁₀[ErCl₆][ErCl₅(H₂O)]₂Cl₃ has been studied. The magnetic data are interpreted by ligand field calculations applying the angular overlap model.     

Synthese und Kristallstruktur von Praseodympropionat-trihydrat,Pr(CH3CH2COO)3(H2O)3

Synthesis and Crystal Structure of Praseodymium Propionate Trihydrate, Pr(CH₃CH₂COO)₃(H₂O)₃ Single crystals of Pr(CH₃CH₂COO)₃(H₂O)₃ were obtained by dissolving freshly prepared praseodymium hydroxide in diluted propionic acid. The crystal structure (monoclinic, P2₁/c, Z = 4, a = 1034.2(2) pm, b = 1521.2(3) pm, c = 2086.3(7) pm, β = 102.87(2)°, R1 = 0.0864, wR2 = 0.1196) consists of one-dimensional infinite chains parallel [010]. Pr1 and Pr2 are coordinated by four tridentate-bridging propionate groups. Additionally, Pr1 is coordinated by three “coordination water” molecules, Pr2 by two bidentate propionate groups. There are, in addition, three “crystal water” molecules so that praseodymium propionate trihydrate should be formulated as [(H₂O)₃Pr1(CH₃CH₂COO)₄Pr2(CH₃CH₂COO)₂] (H₂O)₃.     

Darstellung und Kristallstruktur von (CH3NH3)8[NdCl6][NdCl4(H2O)2]2Cl3

Preparation and Crystal Structure of (CH₃NH₃)₈[NdCl₆][NdCl₄(H₂0)₂]₂Cl₃ (CH₃NH₃)₈[NdCl₆][NdCl₄ (H₂O)₂]₂Cl₃ is for the first time prepared and investigated by X-ray, single crystal work. It crystallizes in the monoclinic system (space group C2/m, Z = 2) with a = 9.358(5), b = 17.424(9), c = 15.360(8) Å, β = 108.30(4)°. The structure contains besides isolated Cl^? ions distorted [NdCl₆]^3? octahedra and [NdCl₄(H₂O)₂]^? chains.     

Synthese und Kristallstruktur von [Cr(NH3)6][Cr(NH3)2F4][BF4]2

Synthesis and Crystal Structure of [Cr(NH₃)₆][Cr(NH₃)₂F₄][BF₄]₂ The action of ammonium fluoride on a mixture of boron and chromium in a sealed Monel ampoule at 300 °C yields single crystals of [Cr(NH₃)₆][Cr(NH₃)₂F₄][BF₄]₂. The crystal structure (tetragonal, P4/mbm, Z = 2, a = 1056.0(1), c = 781.7(1) pm; R₁ = 0.0414; wR₂ = 0.1087 for 411 reflections with I₀ > 2σ(I)) contains [Cr(NH₃)₆]³⁺ and [Cr(NH₃)₂F₄]^– octahedra and twice as many [BF₄]^– tetrahedra that are arranged in a quadrupled super‐structure of the CsCl‐type of structure.     

Synthese,Kristallstruktur und Magnetismus von Natriumtetrachlorotitanat(II), Na2TiCl4

Synthesis, Crystal Structure and Magnetism of Sodium Tetrachlorotitanate(II), Na₂TiCl₄ Na₂TiCl₄ is obtained as single crystals by metallothermic reduction of TiCl₃ with sodium (525°C, 90 d, Ta container). Pure powder samples may be prepared by synproportionation of TiCl₃ with Ti in the presence of NaCl (950–520°C, 21 d). The structure refinement from four-circle diffractometer data confirms that Na₂TiCl₄ is isotypic with Sr₂PbO₄ (orthorhombic, space group Pbam (No. 55), Z = 2 a = 694.2(1), b = 1 198.9(2), c = 385.6(1) pm, R = 0.055, R_w = 0,038). Ti²⁺ is surrounded by a distorted octahedron of Cl^?. The octahedra are connected via common edges to chains, [TiCl_2/1Cl_4/2]^2?, that run in the [001] direction. Magnetic susceptibility data were recorded in the 2 to 300 K temperature range at various field strengths. The interpretation of the data was carried out with the aid of crystal-field calculations taking magnetic interactions into account. The non-Curie behaviour of the reciprocal magnetic susceptibility of Ti²⁺ in Na₂TiCl₄ is due to the influence of spin-obit coupling.     

Metallampullen als Mini‐Autoklaven: Synthese und Kristallstrukturen der Ammoniakate [Al(NH3)4Cl2][Al(NH3)2Cl4] und (NH4)2[Al(NH3)4Cl2][Al(NH3)2Cl4]Cl2

Metal Ampoules as Mini‐Autoclaves: Syntheses and Crystal Structures of [Al(NH₃)₄Cl₂][Al(NH₃)₂Cl₄] and (NH₄)₂[Al(NH₃)₄Cl₂][Al(NH₃)₂Cl₄]Cl₂ The salts [Al(NH₃)₄Cl₂]⁺[Al(NH₃)₂Cl₄]^–≡AlCl₃ · 3 NH₃ ( 1 ) and (NH₄⁺)²[Al(NH₃)₄Cl₂]⁺[Al(NH₃)₂Cl₄]^–(Cl^–)₂≡ AlCl₃ · 3 NH₃ · (NH₄)Cl ( 2 ) have been obtained as single crystals during the reactions of aluminum and aluminum trichloride, respectively, with ammonium chloride in sealed Monel metal containers. The crystal structure of 1 was determined again [triclinic, P‐1; a = 574.16(10); b = 655.67(12); c = 954.80(16) pm; α = 86.41(2); β = 87.16(2); γ = 84.89(2)°], that of 2 for the first time [monoclinic, I2/m; a = 657.74(12); b = 1103.01(14); c = 1358.1(3) pm; β = 103.24(2)°].     

Synthese,Kristallstruktur und magnetisches Verhalten von Gd(CF3CF2COO)3(H2O)3

Synthesis, Crystal Structure and Magnetic Behaviour of Gd(CF₃CF₂COO)₃(H₂O)₃ Single crystals of Gd(CF₃CF₂COO)₃(H₂O)₃ have been obtained by reaction of Gd₂O₃ with an aqueous solution of CF₃CF₂COOH. The compound crystallizes triclinically in the space group (No. 2; Z = 2; a = 928.5(1) pm, b = 1037.1(1) pm, c = 1147.3(2) pm, α = 90.44(2)°, β = 108.56(1)°, γ = 106.49(1)°). In the crystal structure the gadolinium ions are bridged by carboxylate groups to dimers and are coordinated eightfold by oxygen atoms. The magnetic behaviour was investigated in the temperature range of 1.77 to 300 K. The magnetic data indicate weak antiferromagnetic interactions within the dimeric unit (J_ex = ?0.0057 cm^?1).     

Darstellung, 11B-NMR-, Schwingungsspektren und Kristallstruktur von [(C5H5N)2CH2][1-(O2N)B10H9]

Preparation, ¹¹B NMR, Vibrational Spectra, and Crystal Structure of [(C₅H₅N)₂CH₂][1-(O₂N)B₁₀H₉] By reaction of [B₁₀H₁₀]^2? in aqueous acetonitrile with a saturated solution of NO₂ in dichloromethane [1-(O₂N) · B₁₀H₉]^2? and [B₁₀H₉(NO)B₁₀H₉]^3? are formed which can be separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound. The X-ray structure determination of [(C₅H₅N)₂CH₂][1-(O₂N)B₁₀H₉] (triclinic, space group P1 , a = 7.1530(9), b = 8.3753(8), c = 15.198(2) Å, α = 96.00(1), β = 95.48(1), γ = 95.60(1)°, Z = 2) reveals the coordination of the NO₂ group via N with a B1? N distance of 1.535(5) Å and an O2? N? O1 angle of 119.3(3)°. The ¹¹B NMR spectrum exhibits the characteristic feature (1 : 1 : 4 : 4) of an apical monosubstituted B₁₀ cluster with a strong downfield shift of the ipso-B atom at +13.4 ppm. The IR and Raman spectra show strong NO stretching vibrations at 1381 und 1420 cm^?1.     

Synthese und Kristallstruktur von (C5H5)Mo(CO)3(AuPPh3) und [(C5H5)Mo(CO)2(AuPPh3)4]PF6

Synthesis and Crystal Structure of (C₅H₅)Mo(CO)₃(AuPPh₃) and [(C₅H₅)Mo(CO)₂(AuPPh₃)₄]PF₆ CpMo(CO)₃(AuPPh₃) is obtained by the reaction of Li[CpMo(CO)₃] with Ph₃PAuCl at ?95°C in CH₂Cl₂. It crystallizes in the monoclinic space group C2/c with a = 2625.1(7), b = 883.2(1), c = 2328.4(7) pm, β = 116.39(1)° und Z = 8. In the complex the AuPPh₃ group is coordinated to the CpMo(CO)₃ fragment with a Au? Mo bond of 271,0 pm. The Mo atom thus achieves a square pyramidal coordination with the center of the Cp ring in apical position. CpMo(CO)₃(AuPPh₃) reacts under uv irradiation with an excess of Ph₃PAuN₃ to afford the cluster cation [CpMo(CO)₂(AuPPh₃)₄]⁺. It crystallizes as [CpMo(CO)₂(AuPPh₃)₄]PF₆ · 2 CH₂Cl₂ in the orthorhombic space group P2₁2₁2₁ with a = 1553.9(1), b = 1793.8(2), c = 2809.8(7) pm und Z = 4. The five metal atoms form a trigonal bipyramidal cluster skeleton with the Mo atom in equatorial position. The Mo? Au distances range from 275.5 to 280.8 pm, and the Au? Au distances are between 281.2 and 285.6 pm.     

Synthese und Kristallstruktur von [N(Hex)4][Cu2(CN)3]

Synthesis and Crystal Structure of [N(Hex)₄] [Cu₂(CN)₃] [N(Hex)₄][Cu₂(CN)₃] has been prepared by solvothermal reaction of CuCN with Tetra‐n‐hexylammoniumiodide in acetone. The crystal structure is built up by condensed (CuCN)₆ and (CuCN)₇ rings, forming a zeolith type cyanocuprate(I) framework [Cu₂(CN)₃^—]. Space group R3; α = 44.482(6), c = 21.283(4) Å, V = 36471(9) ų; Z = 9.     

Hydrogendiazid Synthese und Kristallstruktur von PPh4[N3HN3]

Hydrogen Diazide – Synthesis and Crystal Structure of PPh₄[N₃HN₃] PPh₄[N₃HN₃] has been prepared from PPh₄N₃ and Me₃SiN₃ by the reaction with water or ethanol forming colourless nonexplosive crystal needles, which were characterized by IR spectroscopy and by a crystal structure determination. Space group C2/c, Z = 12, lattice dimensions at –70 °C: a = 3782.4(3), b = 727.8(2), c = 2512.4(2) pm, β = 110.13(1)°, R = 0.0841. The [N₃HN₃]^– ion is characterized by an asymmetric N–H…N hydrogen bridge with a NN distance of 272(1) pm.     

Darstellung und Kristallstrukturen von [P(C6H5)4][1-(NH3)B10H9] und Cs[(NH3)B12H11] · 2CH3OH

Synthesis and Crystal Structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH The reduction of [1-(NO₂)B₁₀H₉]^2? with aluminum in alkaline solution yields [1-(NH₃)B₁₀H₉]^? and by treatment of [B₁₂H₁₂]^2? with hydroxylamine-O-sulfonic acid [(NH₃)B₁₂H₁₁]^? is formed. The crystal structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] (triclinic, space group P1 , a = 7.491(2), b = 13.341(2), c = 14.235(1) Å, α = 68.127(9), β = 81.85(2), γ = 86.860(3)°, Z = 2) and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH (monoclinic, space group P2₁/n, a = 14.570(2), b = 7.796(1), c = 15.076(2) Å, β = 111.801(8)°, Z = 4) reveal for both compounds the bonding of an ammine substituent to the cluster anion.     

Synthese und Kristallstruktur von Mangan(II)‐ und Zinkamid,Mn(NH2)2 und Zn(NH2)2

Synthesis and Crystal Structure of Manganese(II) and Zinc Amides, Mn(NH₂)₂ and Zn(NH₂)₂ Metal powders of manganese resp. zinc react with supercritical ammonia in autoclaves in the presence of a mineralizer Na₂Mn(NH₂)₄ resp. Na₂Zn(NH₂)₄_.0.5NH₃ to well crystallized ruby‐red Mn(NH₂)₂ (p(NH₃) = 100 bar, T = 130°C, 10 d) resp. colourless Zn(NH₂)₂ (p(NH₃) = 3.8 kbar, T = 250°C, 60 d). The structures including all H‐positions were solved by x‐ray single crystal data: Mn(NH₂)₂: I4₁/acd, Z = 32, a = 10.185(6) Å, c = 20.349(7) Å, N(F_o) with F > 3σ (F) = 313, N(parameter) = 45, R/R_w = 0.038/0.043. Zn(NH₂)₂: I4₁/acd, Z = 32, a = 9.973(3) Å, c = 19.644(5) Å, N(F_o) with F > 3σ (F) = 489, N(parameter) = 45, R/R_w = 0.038/0.043. Both compounds crystallize isotypic with Mg(NH₂)₂ [1] resp. Be(NH₂)₂ [2]. Nitrogen of the amide ions is distorted cubic close packed. One quarter of tetrahedral voids is occupied by Mn²⁺‐ resp. Zn²⁺‐ions in such an ordered way that units M₄(NH₂)₆(NH₂)_4/2 occur. The H‐atoms of the anions have such an orientation that the distance to neighboured cations is optimum.     

Synthese und Kristallstruktur von Calcium-Kupfer-Diarsenat CaCuAs2O7

Synthesis and Crystal Structure of the Calcium Copper Diarsenate CaCuAs₂O₇ Solid state reactions led to single crystals of CaCuAs₂O₇. X-ray investigations revealed monoclinic symmetry, space group C⁵_2h-P2₁/c, lattice constants a = 7.272(1); b = 8.946(2); c = 9.307(2) Å; β = 109.48(2)°; Z = 4. CaCuAs₂O₇ is characterized by ¹_∞[CaO₆] chains, connected by As₂O₇ double tetrahedra and elongated square CuO₅ pyramids. The hitherto unknown crystal structure shows relationships to CaCuP₂O₇ but not to CaCuV₂O₇.     

Synthese und Kristallstruktur von [(n‐Bu)4N][W6Cl18]

Synthesis and Crystal Structure of [(n‐Bu)₄N][W₆Cl₁₈] Single‐crystals of [(n‐Bu)₄N][W₆Cl₁₈] were obtained as thin needles by adding methanol to a solution of W₆Cl₁₈ and [(n‐Bu)₄N]Cl in tetrahydrofuran. The structure was determined by single‐crystal X‐ray diffraction at 210 K. [(n‐Bu)₄N][W₆Cl₁₈] crystallizes in the monoclinic space group C 2/c with Z = 8 and the lattice parameters a = 2175.6(1) pm, b = 1738.0(1) pm, c = 2160.36(9) pm, and β = 91.680(5) °. The crystal structure contains isolated [(W₆Cl₁₂ⁱ)Cl₆^a]^— clusters and [(n‐Bu)₄N]⁺ ions.     

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.     

Synthese,Kristallstruktur und magnetische Eigenschaften von TbAl3Cl12

Synthesis, Crystal Structure, and Magnetic Properties of TbAl₃Cl₁₂ TbAl₃Cl₁₂ was synthesized and the crystal structure was determined from single crystal X‐ray diffraction data for the first time. The compound crystallizes trigonally in space group P3₁12 with a = 1049.8(1) and c = 1567.3(2) pm. Terbium cations are located in quadratic antiprisms of chloride anions. Magnetic measurements were performed to study the interactions between Tb³⁺ and Cl^–. Magnetic data were interpreted by ligand field calculations applying the angular overlap model.     

Kristallstrukturen der Fluorochloroplatinate(IV) cis-[(C5H5N)2CH2][PtF4Cl2], trans-[(C5H5N)2CH2][PtF4Cl2] · H2O und [(C5H5N)2CH2][PtF5Cl]

Crystal Structures of the Fluorochloroplatinates(IV) cis-[(C₅H₅N)₂CH₂][PtF₄Cl₂], trans-[(C₅H₅N)₂CH₂][PtF₄Cl₂] · H₂O, and [(C₅H₅N)₂CH₂][PtF₅Cl] The complex ions cis-[PtF₄Cl₂]^2?, trans-[PtF₄Cl₂]^2? and [PtF₅Cl]^2? have been synthesized by stereoselective ligand exchange reactions utilizing the trans effect and are separated by ion exchange chromatography on diethylaminoethyl cellulose. These anions form stable AB-type salts with the doubly charged cation dipyridiniomethane, [(C₅H₅N)₂CH₂]²⁺. X-ray structure determinations on single crystals of cis-[(C₅H₅N)₂CH₂][PtF₄Cl₂] ( 1 ) (monoclinic, space group P2₁/n with a = 10.379(10), b = 9.635(2), c = 13.738(2) Å, β = 99.142(10)°, Z = 4), trans-[(C₅H₅N)₂CH₂][PtF₄Cl₂] · H₂O ( 2 ) (triclinic, space group P1 with a = 7.757(4), b = 10.059(7), c = 10.408(6) Å, α = 82.49(5), β = 68.92(4), γ = 75.46(4)°, Z = 2) and [(C₅H₅N)₂CH₂][PtF₅Cl] ( 3 ) (orthorhombic, space group Pnma with a = 10.394(3), b = 13.320(2), c = 9.2694(10) Å, Z = 4), reveal the perfect ordering of the anion sublattice. The stronger trans influence of Cl compared with F is observed in asymmetric axes $ {\rm F}^ \bullet $? Pt? Cl′. The bond lengths Pt? $ {\rm F}^ \bullet $ are 0.026 Å (1.4%) longer and the Pt? Cl′ distances are 0.078 Å (3,3%) shorter in comparison with those of symmetrically coordinated axes. The weakening of the Pt? $ {\rm F}^ \bullet $ bond and the strengthening of the Pt? Cl′ bond is better recognizable from shifts of the stretching vibrations by 8% to lower and by 13% to higher frequencies, respectively. Correspondingly, the valence force constants are found to be 15% lower and 22% higher. The trans influence is observed most distinctly in the ¹⁹F-nmr spectra exhibiting the coupling constant ¹J($ {\rm F}^ \bullet $Pt) to be 29% smaller than ¹J(FPt).     

[Cu4(NPMe3)3(O2C?CH3)5] – ein tetramerer Phosphaniminato-Komplex von Kupfer(II). Synthese,Kristallstruktur, magnetisches Verhalten und EPR-Spektrum

[Cu₄(NPMe₃)₃(O₂C? CH₃)₅] – a Tetrameric Phosphorane Iminato Complex of Copper(II). Synthesis, Crystal Structure, Magnetic Behaviour, and EPR Spectrum The title compound and the corresponding benzoate complex [Cu₄(NPMe₃)₃(O₂C? C₆H₅)₅] have been prepared by reactions of copper(II)acetate and copper(II)benzoate, respectively, with Me₃SiNPMe₃ in dichloromethane. Both complexes are characterized by IR spectroscopy. The acetate complex is additionally characterized by the measurement of the magnetic susceptibility, by its EPR spectrum, and by a crystal structure determination. [Cu₄(NPMe₃)₃(O₂C? CH₃)₅] · CH₂Cl₂: Space group I4₁/a, Z = 16, structure solution with 7 960 independent reflections, R = 0.044. Lattice dimensions at ?70°C: a = b = 3 670.6; c = 1 091.9 pm. The structure consists of four Cu atoms which are arranged at the corners of a distorted tetrahedron with Cu…?Cu distances between 290 and 318 pm. Three of the faces of the tetrahedron are linked by μ₃-N atoms of the phosphorane iminato groups. Three of the acetate ligands form chelates, the other two are monofunctionally coordinated. Three of the copper atoms have a planar surrounding, the forth Cu atom has a (4 + 1) coordination.