NiH3IO6 · 6H2O — Kristallstruktur und Schwingungsspektren

NiH₃IO₆ · 6 H₂O — Crystal Structures and Vibrational Spectra The crystal structure of NiH₃IO₆ · 6 H₂O has been determined by X-ray single-crystal diffraction (Pc, Z = 2, a = 516.74(9), b = 981.5(2), c = 1052.5(2) pm, β = 116.496(8)°) on the basis of 4169 unique reflections (R = 1.96%). The structure is built up of distorted Ni(H₂O)₆²⁺ and H₃IO₆^2? octahedra linked by hydrogen bonding. IR and Raman spectra of both the title compound and isostructural MgH₃IO₆ · 6 H₂O as well as of deuterated specimens are given. There are up to 14 different OH(OD) modes in the spectra of isotopically dilute samples due to the 15 different hydrogen positions of the structure. The internal modes of the meridional H₃IO₆^2? ions (pseudo C_2v symmetry) are discussed with respect to that double T-shaped entity, which gives rise to only two instead of 3I? O, I? O(H), and OH stretches in the IR and Raman spectra, i.e. the same as for facial (C_3v) structured ions.     

Gitterschwingungsspektren. LXXI. Wasserstoffbrückenbindungen und synergetischer Effekt in kristallinen Amiden am Beispiel von NaAl(NH2)4

Lattice Vibration Spectra. LXXI Hydrogen Bonding and Synergetic Effect in Solid Amides: a Case Study for NaAl(NH₂)₄ IR and Raman spectra (4000 - 200 cm^?1, 90 K and 300 K) of NaAl(NH₂)₄ and of deuterated samples are recorded and discussed with respect to the bonding of NH₂^? ions in condensed phases compared to that of H₂O molecules and OH^?-ions. The bands observed are assigned to the internal vibrations and librations of the NH₂^? ions and skeleton vibrations of the distorted tetrahedral Al(NH₂)₄^? units (breathing vibration v₁, 572 cm^?1). Owing to the high charge density of the Al³⁺ ions the NH-stretching modes are shifted to higher wavenumbers by as many as 200 cm^?1 compared to those of free amide ions. Furthermore the H-bond donor strenght of the NH₂^? ions is so much enlarged (synergetic effect) that weak, unusally long (d( …? N) > 360 pm) NH₂ …? NH₂ hydrogen bonds are formed. These H-bonds share layers of vertex connected Al(NH₂)₄ and Na(NH₂)₄ tetrahedra within the structure.     

Gitterschwingungsspektren. LXXVI. Zur Kenntnis basischer Kupfersalze — Kristallstruktur und schwingungsspektroskopische Untersuchungen an Cu2(OH)3NO2

Lattice Vibration Spectra. LXXVI. On Basic Copper Salts — Crystal Structure, IR and Raman Spectra of Cu₂(OH)₃NO₂ Single-crystal X-ray as well as IR and Raman data of Cu₂(OH)₃NO₂ are presented and discussed with respect to an order-disorder (OD) phase transition and the strength of hydrogen bonds. Cu₂(OH)₃NO₂ crystallizes pseudosymmetrically in the monoclinic space group P2₁/m (Z = 2, a = 562.22(4), b = 605.94(5), c = 663.55(4) pm and β = 95.415(5)°) forming a layered structure of edge-connected, elongated CuO₆ octahedra (final R value 2.5% for 1047 symmetry averaged reflections with I ≥ 2.5 μ₁). The NO₂^? ions are on a split position with dynamic disordering at ambient temperature. On temperature lowering the disorder is frozen out with a symmetry decrease to space group P2₁. The disorder of the NO₂^? ions causes four different arrangements of OH₍₂₎^? with different strengths of the H…O hydrogen bonds present OD stretching modes in the spectra of isotopically dilute samples 2628, 2535, 2435, and 2343 cm^?1 at 90 K. The OH₍₁₎^? ions form weak H…N H-bonds to the lone-pair of the nitrogen atoms of the NO₂^? ions (v_OD 2563 cm^?1).     

Polyol-Metall-Komplexe. XIII [1]. Na2[Be(C4H6O3)2] · 5H2O und Na2[Pb(C4H6O3)2] · 3H2O – zwei homoleptische Bis-polyolato-metallate mit Beryllium und mit Blei

Polyol Metal Complexes. XIII. Na₂[Be(C₄H₆O₃)₂] · 5H₂O and Na₂[Pb(C₄H₆O₃)₂] · 3H₂O – Two Homoleptic Bis Polyolato Metallates with Beryllium and with Lead Na₂[Be(C₄H₆O₃)₂] · 5H₂O ( 1 ) and Na₂[Pb(C₄H₆O₃)₂] · 3H₂O ( 2 ) crystallize from concentrated, alkaline aqueous solutions. The polyol anhydroerythritol is deprotonated twice in the mononuclear, homoleptic complex anions. The preference of beryllium for the binding of cis-furanoid diols is shown. In 2 , a stereochemically active lone pair at the central atom is the reason for the construction of low dimensional aggregates from three plumbate and three sodium ions.     

Über die Darstellung der N-Chlor-N-Methylammoniumsalze (CH3)nNCl4–n+MF6− (n = 1–3; M = As,Sb) und (CH3)2NCIX+MF6− (X = F,Br)

About the Preparation of N-Chloro-N-Methylammonium Salts (CH₃)_nNCl_4–n⁺MF₆^? (n = 1–3; M = As, Sb) and (CH₃)₂NClX⁺MF₆^? (X = F, Br) Simple one-step methods for the preparation of the methylated chloroammonium salts (CH₃)_nNCl_4–n⁺MF₆^? (n = 1–3; M = As, Sb) and for (CH₃)₂NClX⁺MF₆^? (X = F, Br) are reported. Their vibrational and NMR-spectroscopical data are discussed in comparison.     

Alternativ-Liganden. XXI. Neue Donor/Akzeptor-Liganden Me2PCH2CH2SiFnMe3-n,Me2PCH2CH2SiR(C6H4F)2 und (2-Me2PC6H4)SiXMe2

Alternative Ligands. XXI. Novel Donor/Acceptor Ligands Me₂PCH₂CH₂SiF_nMe_3-n, Me₂PCH₂CH₂SiR(C₆H₄F)₂, and (2-Me₂PC₆H₄)SiXMe₂ Donor/acceptor ligands of the type Me₂PCH₂CH₂SiX₃ [X = Cl ( 1 ), F ( 2 ), Me ( 3 ), OMe ( 4 )], (Me₂PCH₂CH₂)₂SiX₂ [X = Cl ( 6 ), F ( 7 )], Me₂PCH₂CH₂SiX(C₆H₄F)₂ [X = F ( 5 ), Me ( 8 )], and Me₂PCH₂CH₂SiX_nMe_3-n[n = 1; X = Cl ( 10 ), F ( 11 ); n = 2; X = F ( 9 )] are prepared in yields between 42 and 95% by photochemical addition of Me₂PH to the corresponding vinylsilane precursors. In case of the halogen containing representatives formation of solid polyadducts, due to Lewis acid/base interaction between P-donor and Si-acceptor function, reduces the yields. Ligands of the type (2-Me₂PC₆H₄)SiXMe₂ [X = NMe₂ ( 12 ), Cl ( 13 ), F ( 14 )] are obtained by two different routes (Abb. 3), using 2-chlorobromobenzene as the starting material. New compounds have been characterized by analytical (C, H) and spectroscopic (NMR, MS) investigations. In order to elucidate the associative properties compounds 2 and 9 were used for the following experiments:

• – Study of the influence of dissolution on the proton and fluorine resonances of 2 and 9 ,
• – investigation of the adduct equilibrium (–H₂CF₃Si←PMe₂CH₂–)n + nBF₃ → n[F₃B←PMe₂CH₂CH₂SiF₃],
• – cleavage of the polyadduct of 2 using [NH₄]F and [Me₄N]F, respectively, for the formation of hexacoordinate complex anions [Me₂PCH₂CH₂SiF₅]^2?.

The results obtained confirm the assumption that oligo- and polymerisation are due to P→Si interaction.     

[Be3(μ3‐O)3(MeCN)6{Be(MeCN)3}3](I)6 – ein Berylliumkomplex mit Cyclo‐(Be3O3)‐Kern und sein Hydrolyseprodukt [Be(H2O)4](I)2·2MeCN

Single crystals of [Be₃(μ₃‐O)₃(MeCN)₆{Be(MeCN)₃}₃](I)₆·4CH₃CN ( 1 ·4CH₃CN) were obtained in low yield by the reaction of beryllium powder with iodine in acetonitrile suspension, which probably result from traces of beryllium oxide containing the applied beryllium metal. The compound 1 ·4CH₃CN forms moisture sensitive, colourless crystal needles, which were characterized by IR spectroscopy and X‐ray diffraction (Space group Pnma, Z = 4, lattice dimensions at 100(2) K: a = 2317.4(1), b = 2491.4(1), c = 1190.6(1) pm, R₁ = 0.0315). The hexaiodide complex cation 1 ⁶⁺consists of a cyclo‐Be₃O₃ core with slightly distorted chair conformation, stabilized by coordination of two acetonitrile ligands at each of the beryllium atoms and by a {Be(CH₃CN)₃}²⁺ cation at each of the oxygen atoms. This unique coordination behaviour results in coplanar OBe₃ units with short Be–O distances of 155.0 pm and 153.6 pm on average of bond lengths within the cyclo‐Be₃O₃ unit and of the peripheric BeO bonds, respectively. Exposure of compound 1 ·4CH₃CN to moist air leads to small orange crystal plates of [Be(H₂O)₄]I₂·2CH₃CN ( 3 ·2CH₃CN). According to the crystal structure determination (Space group C2/c, Z = 4, lattice dimensions at 100(2) K: a = 1220.7(1), b = 735.0(1), c = 1608.5(1) pm, β = 97.97(1)°, R₁ = 0.0394), all hydrogen atoms of the dication [Be(H₂O)₄]²⁺ are involved to form O–H ··· N and O–H ··· I hydrogen bonds with the acetonitrile molecules and the iodide ions, respectively. Quantum chemical calculations (B3LYP/6‐311+G**) at the model [Be₃(μ₃‐O)₃(HCN)₆{Be(HCN)₃}₃]⁶⁺ show that chair and boat conformation are stable and that the distorted chair conformation is stabilized by packing effects.     

Darstellung der Iminiumsalze CF3?NXCF2+MF6− (X = CH3, F und M = As,Sb) und CF3?NCl = CF2+ AsF6−

Preparation of the Iminium Salts CF₃? NX?CF₂⁺MF₆^? (X = CH₃, F and M = As, Sb) and CF₃? NCl?CF₂⁺ AsF₆^? The preparation of the iminiumsalts CF₃? NX?CF₂⁺ MF₆^? (X = CH₃, F and M = As, Sb) and CF₃? NCl?CF₂⁺ AsF₆^? is reported. The salts were characterized by NMR and infrared spectroscopy. CF₃? NCH₃?CF₂⁺MF₆^? decompose into MF₅ and (CF₃)₂NCH₃.     

AlCl3 · 2NH3 – eine Verbindung mit der Kristallstruktur eines Tetraammindichloroaluminium-tetrachloroaluminats – [AlCl2(NH3)4]+[AlCl4]−

ACl₃ · 2NH₃ – a Compound with the Crystal Structure of a Tetraammine Dichloroaluminiumtetrachloroaluminate – [AlCl₂(NH₃)₄]⁺[AlCl₄]^? Ammoniates of aluminiumchloride AlCl₃ · xNH₃ are in discussion as starting materials for the synthesis of aluminiumnitride. Therefore the reactions of melts of monoamminealuminiumchloride with ammonia were investigated. They react at 150°C within 10 min with one mole of ammonia to the diammoniate, [AlCl₂(NH₃)₄]⁺[AlCl₄]^?. The pure compound can be obtained by sublimation at 200°C in vacuumline apparatus. X-ray structure determination on [AlCl₂(NH₃)₄]⁺[AlCl₄]^? was carried out: see “Inhaltsübersicht”.     

Cobalt- und Rhodiumphthalocyanine mit O-, S- und Se-Donorliganden

Phthalocyanines of Cobalt and Rhodium with O, S, and Se Donor Ligands Di(phenolato)-, -(benzenethiolato)- and -(benzeneselenonato)phthalocyaninatocobaltate(III) and -rhodate(III) are prepared by the reaction of di(hydroxo)phthalocyaninatometalate with phenol resp. benzenethiol or benzeneselenol and isolated as poorly soluble tetra(n-butyl)ammonium salts of the formula (ⁿBu₄N)[M(EPh)₂Pc^2?] (M = Co, Rh; E = O, S, Se). In the Uv-vis spectra π–π* transitions in the Pc^2?-typical B, Q, N and L regions are observed. For the Rh-complexes with E = S, Se there is a further band at 18.0 kK due to excitonic π(Ph)–π(Pc) interactions. The (E→Rh-charge-transfer(CT)) transition is observed for E = Se at 26.0 kK, being obscured by the Q, N region for E = O, S. The strong, broad (E → Co? CT) transition (E = O, S, Se) absorbs at ～20.5 kK. A second CT-transition is detected within the Q, N region for E = S, Se. Molecular vibrations (in cm^?1) are examined by m.i.r., f.i.r, FT-Raman and dispersive resonance-Raman(RR) spectra. The C? E stretching mode (v_7a) of the axial EPh ligands is observed for E = O at 1256/1262, 1269 (Co, m.i.r./RR), 1246/1265 (Rh), for E = S at 1085 (Co, Rh; RR) and for E = Se at 1069 (Co, Rh; RR). The C? C? E deformation mode (v_6a) is assigned for E = O at 554/557 (Co, RR), 568 (Rh, RR) and for E = S at 420 (Co, Rh; RR). The following vibrational modes of the trans-ME₂N₄ skeleton are assigned: v_s(ME) for Co: 381 (O)/271 (S)/139 (Se); for Rh: 408/297/156; v_as(ME) for Co: 352/277/235; for Rh: 391/278/225; v_as(MN) absorbs nearly independent of M and E at ～325 (f.i.r.) M? E? C deformation modes are observed between 246 and 200 (f.i.r.) resp. 217 and 186 (RR).     

Darstellung,Eigenschaften und elektronische Raman-Spektren von Bis(chloro)phthalocyaninatoferrat(III), -ruthenat(III) und -osmat(III)

Preparation, Properties and Electronic Raman Spectra of Bis(chloro)-phthalocyaninatoferrate(III), -ruthenate(III) and -osmate(III) Bis(chloro)phthalocyaninatometalates of Fe^III, Ru^III and Os^III [MCl₂Pc(2-)]^?, with an electronic low spin ground state are formed by the reaction of [FeClPc(2-)] resp. H[MX₂Pc(2?)] (M = Ru, Os; X = Cl, I) with excess chloride in weakly coordinating solvents (DMF, THF) and are isolated as (n-Bu₄N) salts. The asym. M? Cl stretch (ν_as(MCl)) is observed in the f.i.r. at 288 cm^?1 (Fe), 295 cm^?1 (Ru), 298 cm^?1 (Os), ν_as(MN) at 330 cm^?1 (Fe), 327 cm^?1 (Ru), and 317 cm^?1 (Os); only ν_s(OsCl) at 311 cm^?1 is resonance Raman (r.r.) enhanced with blue excitation. The m.i.r. and FT-Raman spectra are typical for hexacoordinated phthalocyanines of tervalent metal ions. The UV-vis spectra show besides the characteristic π-π* transitions (B, Q, N, L band) of the Pc ligand a number of extra bands at 12–15 kK and 18–24 kK due to trip-doublet and (Pc→M)CT transitions. The effect of metal substitution is discussed. The r.r. spectra obtained by excitation between the B and Q band (λ₀ = 476.5 nm) are dominated by the intraconfigurational transition Γ₇ Γ ₈ arrising from the spin-orbit splitting of the electronic ground state for Fe^III at 536 cm^?1, for Ru^III at 961 cm^?1 and Os^III at 3 028 cm^?1. Thus the spin-orbit coupling constant increases very greatly down the iron group: Fe^III (357 cm^?1)< Ru^III (641 cm^?1)< Os^III (2 019 cm^?1). The Γ₇ Γ ₈-transition is followed by a very pronounced vibrational finestructure being composed in the r.r. spectra by the coupling with ν_s(MCl), δ(MClN) and the most intense fundamental vibrations of the Pc ligand. In absorption only vibronically induced transitions are observed for the Ru and Os complex at 1 700-2800 rsp. 3100-5800 em^?1 instead of the 0-0 phonon transitions. The most intense lines are attributed to combinations of the intense odd vibrational mo-des at ≈ 740 and 1120 cm^?1 with ν₅(MCI), δ(MClN).     

High-spin Mangan(II)-Phthalocyanine: Darstellung und spektroskopische Eigenschaften von Acidophthalocyaninatomanganat(II)

High Spin Manganese(II) Phthalocyanines: Preparation and Spectroscopical Properties of Acidophthalocyaninatomanganate(II) Acidophthalocyaninatomanaganese(III) is reduced by boranate, thioacetate or hydrogensulfide to yield acidophthalo-cyaninatomanganate(II) ([Mn(X)Pc^2?]^?; X = Cl, Br, NCO, NCS) being isolated as tetra(n-butyl)ammonium salt. In the cyclovoltammogram of [Mn(NCO)Pc^2?]^? the halv-wave potential for the redoxcouple Mn^II/Mn^III is at ?0.13 V, that of the first ring reduction at ?0.99 V. The magnetic moments are indicative of high-spin ⁶A₁ ground states: μ_Mn = 5.84 (NCO), 5.78(Cl), 5.65 (Br), 5.68 μ_B (NCS). A Curie-like temperature dependence of μ_Mn is observed in the region 300–30 K. Below 30 K an increase in μ_Mn occurs due to weak intermolecular ferromagnetic coupling. The ESR spectra confirm the S = 5/2 ground state with a strong g = 6 resonance observed (A_Mn = 80 G) as expected for an axially distorted ligand-field. Besides the typical π-π* transitions of the Pc^2?-ligand several weak bands are observed in the Uv-vis-n.i.r. spectra at ca. 7.5, 9.1, 14.0 and 19.0 kK that are assigned to trip-multiplet transitions. In resonance with the band at 19.0 kK the Mn? X stretching vibration (v(MnX)) is resonance Raman enhanced: X = NCO: 319, Cl: 286, SCN: 238, Br: 202 cm^?1. These vibrational frequencies are confirmed by the f.i.r. spectra. In the case of the thiocyanato-complex probably both forms of bonding of the ambident NCS-ligand are present (v(Mn? NCS): 274 cm^?1). The frequencies of the vibrations of the inner (CN)₈ ring are reduced by up to 20 cm^?1 as compared with those of low spin Mn^II phthalocyanines.     

Crystal Structures and Raman Spectra of cis‐[SnCl4(H2O)2]·2H2O,cis‐[SnCl4(H2O)2]·3H2O, [Sn2Cl6(OH)2(H2O)2]·4H2O,and [HL][SnCl5(H2O)]·2.5H2O (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime,C18H18N4O2)

The complexes cis‐[SnCl₄(H₂O)₂]·2H₂O ( 1 ), [Sn₂Cl₆(OH)₂(H₂O)₂]·4H₂O ( 3 ), and [HL][SnCl₅(H₂O)]·2.5H₂O ( 4 ) were isolated from a CH₂Cl₂ solution of equimolar amounts of SnCl₄ and the ligand L (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime, C₁₈H₁₈N₄O₂) in the presence of moisture. 1 crystallizes in the monoclinic space group Cc with a = 2402.5(1) pm, b = 672.80(4) pm, c = 1162.93(6) pm, β = 93.787(6)° and Z = 8. 4 was found to crystallize monoclinic in the space group P2₁, with lattice parameters a = 967.38(5) pm, b = 1101.03(6) pm, c = 1258.11(6) pm, β = 98.826(6)° and Z = 2. The cell data for the reinvestigated structures are: [SnCl₄(H₂O)₂]·3H₂O ( 2 ): a = 1227.0(2) pm, b = 994.8(1) pm, c = 864.0(1) pm, β = 103.86(1)°, with space group C2/c and Z = 4; 3 : a = 961.54(16) pm, b = 646.29(7) pm, c = 1248.25(20) pm, β = 92.75(1)°, space group P2₁/c and Z = 4.     

IR- und Raman-Spektren der isotypen Iodathydrate M(IO3)2 · 4 H2O (M = Mg,Ni, Co); Kristallstruktur von Co(IO3)2 · 4 H2O

Infrared and Raman Spectroscopy of the Isostructural Iodate Hydrates M(IO₃)₂ · 4 H₂O (M = Mg, Ni, Co)-Crystal Structure of Cobalt Iodate Tetrahydrate The iodate tetrahydrates Mg(IO₃)₂ · 4 H₂O, β-Ni(IO₃)₂ · 4 H₂O, Co(IO₃)₂ · 4 H₂O and their deuterated specimens were studied by X-ray, infrared and Raman spectroscopic methods. The title compounds are isostructural crystallising in the monoclinic space group P2₁/c (Z = 2). The crystal structure of Co(IO₃)₂ · 4 H₂O (a = 836.8(5), b = 656.2(3), c = 850.2(5) pm and β = 100.12(5)°) has been refined by single-crystal X-ray methods (R_obs = 3.08%, 693 unique reflections I₀ > 2σ(I)). Isolated Co(IO₃)₂(H₂O)₄ octahedra form layers parallel (100). Within these layers, the two crystallographically different hydrate water molecules form nearly linear hydrogen bonds to adjacent IO₃^– ions (ν_OD of matrix isolated HDO of Co(IO₃)₂ · 4 H₂O (isotopically diluted samples) 2443 (H3), 2430 (H2), and 2379 cm^–1 (H1 and H4), –180 °C). Intramolecular O–H and intermolecular H…O distances were derived from the novel ν_OD vs. r_OH and the traditional ν_OD vs. r_H…O correlation curves, respectively. The internal modes of the iodate ions of the title compounds are discussed with respect to their coupling with the librations of the hydrate H₂O molecules, the distortion of the IO₃^– ions, and the influence of the lattice potential.     

Darstellung und spektroskopische Charakterisierung von Di(acido)phthalocyaninatorhodaten(III)

Preparation and Spectroscopical Characterization of Di(acido)phthalocyaninatorhodates(III) Triethylendiaminorhodiumiodide reacts quickly and completely with boiling phthalodinitrile precipitating ?rhodiumphthalocyanine”?, which is purified and dissolved in alkaline media as di(hydroxo)phthalocyaninatorhodate(III). Acidification in the presence of halides or pseudohalides yields less soluble acidophthalocyaninatorhodium reacting with tetra-n-butyl-ammonium(pseudo)halide to give (blue)green tetra-n-butyl-ammoniumdi(acido)phthalocyaninatorhodate(III), (ⁿBu₄N)[Rh(X)₂Pc^2?] (X = Cl, Br, I, N₃, CN, NCO, SCN, SeCN). The asym. Rh? X-stretching vibration (v_as(RhX)) is observed in the f.i.r. at 290 (X = Cl), 233 (Br), 205 (I), 366 (N₃), 347 (CN), 351 (NCO), 257 (SCN) and 214 cm^?1 (SeCN). v_s(RhI) is the only sym. Rh? X-stretching vibration excited at 131 cm^?1 in the Raman spectrum. The m.i.r. and resonance Raman spectra are typical for hexacoordinated phthalocyaninatometalates(III). The influence of the axial ligands is very small. The frequency of the stretching vibrations of the pseudohalo-ligands are as expected (in the case of the ambident ligands the bonding atom is named first): v_as(NN) at 2006 and v_s(NN) at 1270 cm^?1 (N₃); v_as(CN) at 2126 (CN), 2153 (NCO), 2110 (SCN) and 2116 cm^?1 (SeCN). The characteristic π–π*-transitions of the Pc^2?-ligand dominate the UV-vis spectra. The splitting of the Q and N region is discussed and the weak absorbance at ca. 22 kK is assigned to a n–π*-transition.     

Metallorganische Lewis-Säuren. XLII. Carbonyl- und Nitrosyl-Komplexe von Mangan und Rhenium mit schwach koordinierten Anionen (Ph3P)2(ON)2MnX, (Ph3P)n(OC)5–nMX (M = Mn,Re; n = 1, 2; X = FBF3, OSO2CF3, OSO2F,OCORf)

Organometallic Lewis Acids. XLII. Carbonyl- and Nitrosyl Complexes of Manganese and Rhenium of Weakly Coordinated Anions (Ph₃P)₂(ON)₂MnX, (Ph₃P)_n(OC)_5–nMX (M = Mn, Re; n = 1, 2; X = FBF₃, OSO₂CF₃, OSO₂F, OCOR_f) The complexes (Ph₃P)₂(ON)₂MnX (X = FBF₃, OSO₂CF₃, OSO₂F, OCOCF₃, OCOC₃F₇) and (Ph₃P)_n(OC)_5–nMX (M = Mn, Re; n = 1, 2; X = FBF₃, OSO₂CF₃) have been obtained by reaction of (Ph₃P)₂(ON)₂MnH and (Ph₃P)_n(OC)_5–nMeMe with the corresponding acids HX or from (Ph₃P)_n(OC)_5–nReBr (n = 1, 2) with silver salts AgX, respectively. The compounds have been characterized by their IR and partially by ¹⁹F-NMR data. An efficient method for the preparation of the hydride (Ph₃P)₂(ON)₂MnH is reported.     

Darstellung,Eigenschaften und Kristallstruktur von Bis(phthalocyaninato)cer(IV)

Preparation, Properties and Crystal Structure of Bis(phthalocyaninato)cerium(IV) The anodic or chemical oxidation with dibenzoylperoxide of solutions of bis(phthalocyaninato)cerate(III) in dichloromethane yields selectively sparely soluble bis(phthalocyaninato)cerium(IV), [Ce(Pc(2-)) 2 ]. Green, monoclinic needles cristallize with a = 18.783(12) Å b = 18.739(16) Å c= 15.618(10) Å ß114.30(7)°; Z = 4; space group C2/c. [Ce(Pc(2–)) 2 ] is a sandwich complex in which the cerium Atom is eightfold coordinated by the isoindole nitrogens of the two staggered convex Pc-rings. The u.v.-vis., m.i.r., f.i.r. and resonance Raman spectra are consistent with the structure.     

Syntheses and Structures of Na2Mg3(OH)2(SO4)3·4H2O and K2Mg3(OH)2(SO4)3·2H2O

The crystal structures of Na₂Mg₃(OH)₂(SO₄)₃ · 4H₂O and K₂Mg₃(OH)₂(SO₄)₃ · 2H₂O, were determined from conventional laboratory X‐ray powder diffraction data. Synthesis and crystal growth were made by mixing alkali metal sulfate, magnesium sulfate hydrate, and magnesium oxide with small amounts of water followed by heating at 150 °C. The compounds crystallize in space group Cmc2₁ (No. 36) with lattice parameters of a = 19.7351(3), b = 7.2228(2), c = 10.0285(2) Å for the sodium and a = 17.9427(2), b = 7.5184(1), c = 9.7945(1) Å for the potassium sample. The crystal structure consists of a linked MgO₆–SO₄ layered network, where the space between the layers is filled with either potassium (K⁺) or Na⁺‐2H₂O units. The potassium‐bearing structure is isostructural to K₂Co₃(OH)₂(SO₄)₃ · 2(H₂O). The sodium compound has a similar crystal structure, where the bigger potassium ion is replaced by sodium ions and twice as many water molecules. Geometry optimization of the hydrogen positions were made with an empirical energy code.     

Darstellung,Kristallstruktur, thermischer Abbau und Schwingungsspektren von [Co(NH3)6]2[Be4O(CO3)6] · 10 H2O

Preparation, Crystal Structure, Thermal Decomposition, and Vibrational Spectra of [Co(NH₃)₆]₂[Be₄O(CO₃)₆] · 10 H₂O [Co(NH₃)₆]₂[Be₄O(CO₃)₆] · 10 H₂O is a suitable compound for the quantitative determination of beryllium. It can be obtained by reaction of aqueous solutions of carbonatoberyllate with [Co(NH₃)₆]Cl₃. The crystal structure (trigonal‐rhombohedral, R3c (Nr. 161), a = 1071,6(1) pm, c = 5549,4(9) pm, V_EZ = 5519(1) · 10⁶ pm³, Z = 6, R1(I ≥ 2σ(I)) = 0,037, wR2(I ≥ 2σ(I)) = 0,094) contains [Co(NH₃)₆]³⁺‐ and [Be₄O(CO₃)₆]^6–‐ions, which are directly hydrogen bonded as well as with water molecules. The complex cations and anions occupy the positions of a distorted anti‐CaF₂‐type. The thermal decomposition, IR and Raman spectra are presented and discussed.