Beiträge zum thermischen Verhalten wasserfreier Phosphate. IX. Darstellung und Kristallstruktur von Cr6(P2O7)4. Ein gemischtvalentes Pyrophosphat mit zwei- und dreiwertigem Chrom

Contributions on the Thermal Behaviour of Anhydrous Phosphates. IX. Synthesis and Crystal Structure of Cr₆(P₂O₇)₄. A Pyrophosphate Containing Di- and Trivalent Chromium Cr₆(P₂O₇)₄ (Cr₂²⁺Cr₄³⁺(P₂O₇)₄) can be obtained reducing CrPO₄ by phosphorus (950°C, 48 h, 100 mg iodine as mineralizer). By means of chemical transport reactions (transport agent iodine; 1050 → 950°C) the compound has been separated from its neighbour phases (Cr₂P₂O₇, CrP₃O₉) and crystallized (greenish, transparent crystals; edge length up to 0.3 mm). The crystal structure of Cr₆(P₂O₇)₄ (Spcgrp.: P-1; z = 1; a = 4.7128(8) Å, b = 12.667(3) Å, c = 7.843(2) Å, α = 89.65(2)°, β = 92.02(2)°, γ = 90.37(2) has been solved and refined from single crystal data (2713 unique reflections, 194 parameter, R = 0.035). Cr²⁺ is surrounded by six oxygen atoms which occupy the corners of an elongated octahedron (4 × d^{Cr? O} ≈? 2.04 Å; 2 × d^{Cr? O} ≈? 2.62 Å). The Cr³⁺ ions are also coordinated octahedraly (1.930 Å ≤ d_{Cr? O} ≤ 2.061 Å). The crystallographically independent pyrophosphate groups show nearly eclipsed conformation. The bridging angles (P? O? P) are 136.5° and 138.9° respectively.     

Ein Beitrag zur Kristallstruktur von CuYW2O8, CuHoW2O8 und CuYbW2O8

A Contribution on the Crystal Structure of CuYW₂O₈, CuHoW₂O₈, and CuYW₂O₈ Single crystals of (I) CuY₂O₈, (II), CuHoW₂O₈, and (III) CuYbW₂O₈ were prepared and investigated by X-ray technique. (I) crystallizes with triclinic symmetry, space group C? P1 (a = 5.939 Å, b = 6.042 Å, c = 5.025 Å; α = 112.30°, β = 111.77°; Z = 1). (II) and (III) belong to monoclinic symmetry, space group C? P2/n (II) (a = 10.045 Å, b = 5.808 Å, c = 5.021 Å; β = 94.38°; z = 2 (III) a = 9.948 Å, b = 5.824 Å, c = 5.008 Å; β = 93.36°; Z = 2). The crystal structures will be discussed with respect to other to copper rare earth tungstates.     

Tribochemische und thermische Umwandlungen von LnTa3O9 (Ln = Pr,Nd) – röntgenographische und elektronenmikroskopische Untersuchungen

Tribochemical and Thermal Transitions of LnTa₃O₉ (Ln = Pr, Nd) — X-ray and Electron Microscopic Investigations Upon grinding crystals of M1? LnTa₃O₉ (Ln = Pr, Nd) [3] undergo a tribochemical phase transition. This leads to a new modifikation M2? LnTa₃O₉ with a significant higher density. We tried to find out more about the structure with high resolution electron microscopic investigations. According to electron diffraction and powder patterns the lattice parameters are (CuKα₁, λ = 1,54051 Å): M2? PrTa₃O₉: a = 6.2545(7) Å, b = 7.6736(7) Å, c = 6.5316(8) Å, β = 93.93(9)°; M2? NdTa₃O₉: a = 6.2552(5) Å, b = 7.6598(7) Å, c = 6.5103(4) Å, β = 94.096(7)°; (Z = 2). Using the intensities of powder patterns two structure models were calculated (space group P2₁/m, P2/m; R < 20%, heavy metal positions only). A through focus series of high resolution images was in better agreement with the first model (space group P2₁/m). Both models show a remarkable similarity to the structure of M? CeTa₃O₉ [4]. A thermal phase transition leads to M? PrTa₃O₉ and M? NdTa₃O₉ which are both isostructural to M? CeTa₃O₉.     

Zur Darstellung und Struktur neuer Modifikationen von CeTa3O9

Preparation and Structure of New CeTa₃O₉ Modifications The modifications M? , O? and P? CeTa₃O₉ could be prepared by chemical transport reactions (T₂ → T₁; T₂ = 1100°C; T₁ = 1000°C) with chlorine as transport agent. M? CeTa₃O₉ crystallizes in the monoclinic space group C 2/m with a = 12.415(1) Å, b = 7.6317(8) Å, c = 6.5976(8) Å, β = 93.31(1)°; Z = 4; R = 4.88%, R_w = 3.67%. The structure consists of two types of Ta? O-polyhedra. Especially remarkable are chains of edge sharing pentagonal TaO₇-bipyramids which are connected by TaO₆-octahedra at opposite sides. Tunnels running along [010] are created by the framework of Ta? O-polyhedra and are filled with Ce in levels of y = 1/2 and y = 0. O? CeTa₃O₉ crystallizes orthorhombically with a = 6.5429(7) Å, b = 7.6491(7) Å, c = 12.583(1) Å and is isostructural to O? LaTa₃O₉ (space group: Pnma). O? CeTa₃O₉ contains the same characteristic structural units namely pentagonal TaO₇-bipyramides and TaO₆-octahedra. The difference between O? and M? CeTa₃O₉ is based on the orientation of the tunnels: in the orthorhombic modification they are arranged zigzag-like, in the latter parallel. Both modifications of CeTa₃O₉ can be irreversibly converted into the well-known perovskite-related P? CeTa₃O₉ structure with a lower density by heating in air to 1200°C.     

Beiträge zur Kristallchemie und zum thermischen Verhalten von wasserfreien Phosphaten. XXXIII [1] In2P2O7, ein Indium(I)‐diphosphato‐indat(III) und In4(P2O7)3 — Darstellung,Kristallisation und Kristallstrukturen

Contributions on Crystal Chemistry and Thermal Behaviour of Anhydrous Phosphates. XXXIII [1] In₂P₂O₇ an Indium(I)‐diphosphatoindate(III), and In₄(P₂O₇)₃ — Synthesis, Crystallization, and Crystal Structure Solid state reactions via the gas phase lead to the new mixed‐valence indium(I, III)‐diphosphate In₂P₂O₇. Colourless single crystals of In₂P₂O₇ have been grown by isothermal heating of stoichiometric amounts of InPO₄ and InP (800 °C; 7d) using iodine as mineralizer. The structure of In₂P₂O₇ [P2₁/c, a = 7.550(1) Å, b = 10.412(1) Å, c = 8.461(2) Å, b = 105.82(1)°, 2813 independent reflections, 101 parameter, R1 = 0.031, wR2 = 0.078] is the first example for an In⁺ cation in pure oxygen coordination. Observed distances d(In^I‐O) are exceptionally long (d_min(In^I‐O) = 2.82 Å) and support assumption of mainly s‐character for the lone‐pair at the In⁺ ion. Single crystals of In₄(P₂O₇)₃ were grown by chemical vapour transport experiments in a temperature gradient (1000 → 900 °C) using P/I mixtures as transport agent. In contrast to the isostructural diphosphates M₄(P₂O₇)₃ (M = V, Cr, Fe) monoclinic instead of orthorhombic symmetry has been found for In₄(P₂O₇)₃ [P2₁/a, a = 13.248(3) Å, b = 9.758(1) Å, c = 13.442(2) Å, b = 108.94(1)°, 7221 independent reflexes, 281 parameter, R1 = 0.027, wR2 = 0.067].     

Die Kristallstrukturen und Phasentransformationen des tetramorphen RbGel3

Crystal Structures and Phase Transitions of the Tetramorphic RbGeI₃ The thermal behaviour of RbGeI₃ has been studied by X-ray diffraction, Raman spectroscopy, and DTA/DSC. The compound is tetramorphic. Yellow crystals of the LT-form have been obtained by crystallization from aqueous HI solutions. The orthorhombic crystal structure of LT? RbGeI₃ (space group P2₁2₁2₁; a = 10.1441(8) Å; b = 4.5460(5) Å; c = 16.8438(9) Å) shows a distorted NH₄CdCl₃ type structure with pyramidal GeI₃ anions. Three reversible phase transformations were found by heating. In a first step at 181°C LT? RbGeI₃ is transferred into the orthorhombic perovskite MT1—RbGeI₃ (red, space group Pn2₁a; a = 8.566(3) Å; b = 11.868(6) Å; c = 8.018(4) Å; RbGeBr₃ type structure) by a reconstructive phase transition. Subsequently at 221°C the phase MT2—RbGeBr₃ with a rhombohedrically deformed perovskite type structure (black, space group R3m; a = 5.990(2) Å; α = 88,89(3)°; CsGeCl₃ type structure) is formed. The high temperature modification HT? RbGeI₃ shows the cubic perovskite type structure (space group Pm3m; a = 5.994(3) (Å) and is stable above 244°C until decomposition occurs at 334°C.     

Beiträge zur Strukturchemie phosphorhaltiger Ketten und Ringe. 7. Die Kristall- und Molekülstruktur des Diphosphagermetans (t-BuP)2(GePh2)2

Structural Chemistry of Phosphorus Containing Chains and Rings. 7. Molecular and Crystal Structure of the Diphosphagermetane (t-BuP)₂(GePh₂)₂ The compound 1,2-di-tert-butyl-3,3,4,4-tetraphenyl-diphospha-3,4-digerma-cyclobutan, (t-BuP)₂(GePh₂)₂, crystallizes monoclinically in the space group P2₁/c with a = 996.8 pm, b = 1337.3 pm, c = 2403.4 pm, β = 92.66° and Z = 4 formula units. The main structural feature is a non-planar four-membered ring. The (average) bond lengths are d(Ge? Ge) = 242.1 pm, d(Ge? P) = 234.0 pm, d(P? P) = 221.6 pm, d(Ge? C) = 194.9 pm, d(P? C) = 188.tyl4 pm, d(C? C)_Ph = 136.l5 pm, d(C? C)_t-Bu = 151.8 pm, d(C? H)_Ph = 91 pm, d(C? H)_t-Bu ? 95 pm. The geometry of the substituents phenyl and tert-butyl is quite normal.     

Über Chalkogenolate. 118. Kristall- und Molekülstruktur von Oxovanadin(V)-ethylxanthat

On Chalcogenolates. 118. Crystal and Molecular Structure of Oxovanadium(V) Ethylxanthate VO[S₂C? OC₂H₅]₃ crystallizes with Z = 8 in the monoclinic space group P2₁/n with cell dimensions a = 15.065(7) Å, b = 18.540(48) Å, c = 12.824(7) Å, = 99.31(7)°. The crystal and molecular structure has been determined from single crystal X-ray data at 20°C and refined to a conventional R of 0.045.     

Über Rubidiumozonid. Reindarstellung und Kristallstruktur

On Rubidium Ozonide. Synthesis and Crystal Structure An improved route for the synthesis of rubidium ozonide is reported. Via repeated ozonization of the hyperoxide at room temperature and extraction with liquid ammonia, pure rubidium ozonide is for the first time available in preparative amounts (1–5 g) and moreover as single crystals. The crystal structure determination (P2₁/c; a = 645.2(3), b = 602.2(3), c = 876.3(3) pm, ß 122.34(2)°; ?20°C; MoKα 2640 diffractometer data; R_w = 2.6%) proves the expected constitution of the anion O₃^?, which within the range of error belongs to the point group C_2v with d (O? O) = 133.6(9) pm and a bonding angle of 113.7(7)°. With respect to the packing of cations and anions there is a close relationship to the CsCl-type of structure.     

Synthese und Kristallstruktur von Cu9Ti2[B2O5]2[BO3]2O6 — ein Kupfertitanboratpyroboratoxid?

Synthesis and Crystal Structure of Cu₉Ti₂[B₂O₅]₂[BO₃]₂O₆ — a Copper Titanium Borate Pyroborate Oxide? The new compound Cu₉Ti₂[B₂O₅]₂[BO₃]₂O₆ was prepared by a B₂O₃ flux-technique and crystallizes in a triclinic and completely novel structure type. X-ray investigations on single crystals led to the space group C–P1 (Nr. 2); a = 7.246(4) Å; b = 10.637(5) Å; c = 11.436(6) Å; α = 104.53(5)°; β = 96.25(4)°; γ = 90.36(3)°; Z = 2. The metal distribution is ordered. Ti^IV-sites are distorted octahedraly coordinated by oxygen-ions. The copper oxygen polyhedra are distorted square planar or pyramidal respectively. The structure contains isolated planar BO₃-units, nearly planar pyroborate groups and oxygen which is not coordinated to boron.     

Lithiumphthalocyanine: Synthese,Eigenschaften und Kristallstruktur von Bis(triphenylphosphin)iminiumphthalocyaninatolithaten mit verschiedenen Konformationen des Kations

Lithiumphthalocyanines: Synthesis, Properties, and Crystal Structure of Bis(triphenylphosphine)iminiumphthalocyaninatolithates with Different Conformations of the Cation Reaction of tri(n-dodecyl)n-butylammoniumphthalocyaninatolithate, (TDBA)[LiPc^2?] with bis(triphenylphosphin)iminiumbromide, (PNP)Br in dichloromethane yields (PNP)[LiPc^2?]. It crystallizes in the triclinic space group P1 as dichloromethane solvate ( 1 ) and in the monoclinic space group P2₁/n as hydrate ( 2 ). The crystal structures of ( 1 ) and ( 2 ) are reported. Each salt contains two crystallographically slightly different discrete [LiPc^2?]^? anions, in which the square-planar coordinated Li⁺ cation is centered within the planar Pc^2? ligand (D_av.(Li? N_iso) = 1.945 Å). There are three different conformations for the (PNP) cation: ( 1 ) only contains the bent conformer (d_av.(P? N) = 1.575 Å; φ(P? N? P) = 140.8°), while in ( 2 ) an hybrid (d_av.(P? N) = 1.562 Å; φ(P? N? P) = 158.1°) and the linear conformer (d_av.(P? N) = 1.547 Å; φ(P? N? P) = 176.8°) are present. The very soluble, blue-green salts melt at 265°C without decomposition. In accordance with cyclovoltammetric data thin films of (PNP)[LiPc^2?] are oxidized by NO₂ or Br₂ to yield brown violet [LiPc^?]. The electronic absorption spectra and the vibrational spectra are discussed.     

Er3Pd7P4 — Kristallstrukturbestimmung und Extended Hückel Rechnungen

Er₃Pd₇P₄ — Crystal Structure Determination and Extended Hückel Calculations Er₃Pd₇P₄ was prepared by heating the elements (1050°C) and investigated by means of single-crystal X-ray methods. The compound crystallizes in a new structure (C2/m; a = 15.180(3) Å, b = 3.955(1) Å, c = 9.320(1) Å, β = 125,65(1)°; Z = 2) with a three-dimensional framework of Pd and P atoms and with Er atoms in the holes. The Pd atoms are surrounded tetrahedrally, trigonally or linearly by P atoms, which are coordinated by nine metal atoms in the form of a tricapped trigonal prism. Therefore the atomic arrangement of Er₃Pd₇P₄ is related to the structures of ternary transition metal phosphides with a metal: phosphorus ratio of 2:1. Band calculations using the Extended Hückel method show strong covalent Pd? P bonds and weak bonding interactions between Pd atoms with Pd? Pd distances shorter than 2.9 Å.     

Polyanionic Frameworks in the Lithium Phosphidogermanates Li2GeP2 and LiGe3P3 – Synthesis,Structure, and Lithium Ion Mobility

Recently fast lithium ion conductors were discovered in compounds containing tetrahedral SiP₄^8– and GeP₄^8– units. In the context of material development for all solid state batteries the ternary Li/Ge/P phase system has been further investigated and two new lithium phosphidogermanates were discovered on the lithium poor side of the ternary composition diagram. Li₂GeP₂ crystallizes in space group I4₁/acd with unit cell parameters of a = 12.3069(1) Å and c = 19.0306(4) Å, consists of a framework of Ge₄P₁₀ supratetrahedra, and exhibits an ionic conductivity of 1.5(3)×10^–7 S · cm^–1 at 27 °C. LiGe₃P₃ crystallizes in Pbam with a = 9.8459(5) Å, b = 15.7489(7) Å, and c = 3.5995(2) Å. In LiGe₃P₃ Ge and P atoms form a two dimensional polyanion. The slabs consist of five- and six-membered heteroatomic rings comprising GeP₄ and Ge(P₃Ge) tetrahedra including homoatomic Ge–Ge bonds. A semiconducting behavior with an electronic conductivity of ∼10^–4 S · cm^–1 and a remarkable stability vs. air and moisture is observed.     

Die Tieftemperaturmodifikationen von Ag6Si2O7 und Ag6Ge2O7 – Darstellung,Kristallstruktur und Vergleich der Ag?Ag-Abstände

On the Low Temperature Modifications of Ag₆Si₂O₇ and Ag₆Ge₂O₇ – Synthesis, Crystal Structure, and Comparison of Ag? Ag Distances For the first time, single crystals of Ag₆Si₂O₇ and Ag₆Ge₂O₇ have been obtained by solid state reactions of the binary oxides at temperatures of 350°C while applying oxygen pressures of 700 bar. According to the results of X-ray crystal structure determinations both compounds crystallize isostructural in P2₁ (Ag₆Si₂O₇: a = 5.3043(5) Å, b = 9.7533(7) Å, c = 15.9283(13) Å, β = 91.165(8)°, 3881 independent reflections, R1 = 3.3%, wR2 = 7.2%; Ag₆Ge₂O₇: a = 5.3713(4) Å, b = 9.9835(8) Å, c = 16.2249(14) Å, β = 90.904(8)°, 2111 independent reflections, R1 = 4.3%, wR2 = 6.0%, Z = 4). The crystal structures contain two independent M₂O₇^6? anions, one in a staggered, and the other in an ecliptic conformation. The cationic partial structure may be described as a distorted bcc arrangement of Ag⁺ and M⁴⁺. Comparison of the structures with respect to the Ag? Ag separations reveals the latter to be probably due to intrinsic d¹⁰–d¹⁰ bonding interactions as far as the range of 2.89 Å to 3.25 Å is considered.     

Verbesserte Darstellung,Kristallzüchtung und Strukturanalyse von P4O6S2 und P4O6S3

Improved Syntheses, Crystal Growth, and Crystal Structure Determination of P₄O₆S₂ and P₄O₆S₃ Syntheses and single crystal growths of the title compounds are described. Both compounds crystallize in the space group P2₁/c (P₄O₆S₂: a = 11.293(4); b = 6.457(3); c = 11.588(4) Å; β = 90.29(2)°, 2 450 diffractometer data, R_w = 0.035/P₄O₆S₃: a = 15.611(5); b = 8,303(3); c = 9.697(4) Å; β = 127.12(2)°, 2 481 diffractometer data, R_w = 0.034). The structural data for the series P₄O₆S_n (n = 1 – 4) thus completed are compared to their oxide analogues P₄O₆O_n (n = 1 – 4). The changes in the geometry of the P₄O₆-cage in course of its successive oxidation are discussed.     

Untersuchungen über S?H …︁ S-Wasserstoffbrücken Die Kristallstruktur der Diphenyldithiophosphinsäure bei 140 und 293 K

Die Kristallstruktur der Diphenyldithiophosphinsäure (C₆H₅)₂P(S)SH wurde röntgenographisch bei tiefer Temperatur und Normaltemperatur aus Einkristalldiffraktometerdaten bestimmt und bis zu R-Werten von 0,037 (140 K, (sin Θ)/λ < 0,81 Å^?1) und 0,035 (293 K, (sin Θ)/λ < 0,64 Å^?1) verfeinert. Die Verbindung kristallisiert in der monoklinen Raumgruppe P2₁/c mit den bei 140 K (in Klammern: 293 K) gemessenen Gitterkonstanten a = 9,824(3) (9,887), b = 10,061(3) (10,175), c = 14,342(4) (14,433) Å, β = 122,08(3) (121,73)° und V = 1201,1 (1234,9) ų, Z - 4. Im Kristall sind individuelle Moleküle über fast lineare S? H…?S-Wasserstoffbrückenbindungen zu schraubenförmig gewundenen Ketten verknüpft. Bei 140 K beträgt der S…?S-Abstand innerhalb der Brücke 3,790(1) Å; die weiteren geometrischen Daten der Wasserstoffbrücke sind: d(S? H): 1,25(2), d(S…?H): 2,56(2), d(P? S): 2,077(1), d(P?S): 1,954(1) Å, ? (S? H…?S): 169,5(14), ? (P? S…?S): 98,87(2), ? (P?S…?S): 96,65(2)°. Investigations on Compounds Containing S? H…?S Hydrogen Bonds. Crystal Structure of Diphenyldithiophosphinic Acid at 140 and 293 K The crystal structure of diphenyldithiophosphinic acid (C₆H₅)₂P(S)SH was determined from X-ray diffraction data collected at 140 and 293 K and was refined to R factors of 0.037 (140 K, (sin Θ)/λ < 0.81 Å^?1) and 0.035 (293 K, (sin Θ)/λ < 0.64 Å^?1) respectively. The compound crystallizes in the monoclinic space group P2₁/c with unit cell parameters at 140 K (in parentheses: at 293 K): a = 9.824(3) (9.887), b = 10.061(3) (10.175), c = 14.342(4) (14.433) Å, β = 122.08(3) (121.73)° and V = 1201.1 (1234.9) ų, Z = 4. In the crystalline state individual molecules are linked together by nearly linear S? H…?S hydrogen bonds so that endless helical chains are formed. At 140 K the S…?S distance within the hydrogen bond is 3.790(1) Å; the other distances and angles associated with the bridge are: d(S? H): 1,25(2), d(S…?H): 2,56(2), d(P? S): 2,077(1), d(P?S): 1.954(1) Å, ? (S? H…?S): 169.5(14), ? (P? S…?S): 98.87(2), ? (P? S…?S): 96.65(2)°.     

Darstellung und Kristallstruktur von Na2Mn3O7

Synthesis and Crystal-Structure of Na₂Mn₃O₇ Single crystals of Na₂Mn₃O₇ have been grown hydrothermally applying high oxygen pressure (p = 2 kbar). The new compound cystallizes triclinic; space group P1 ; a = 6.636(6) Å, b = 6.854(6) Å, c = 7.548(6) Å, α = 105.76(6)°, β = 106.86(6)°, γ = 111.60(6)°; Z = 2. The crystal structure has been solved and refined to R = 7.9% and R_w = 6.2% (diffractometer data, 1044 independent reflexions). The crystal structure consists of Mn₃O₇^2? anions with manganese coordinated octahedrally by oxygen. These layered anions are hold together by Na⁺ ions (coordination numbers 5 and 6).     

Zur Darstellung und Struktur von LaNb5O14

Preparation and Structure of LaNb₅O₁₄ Single crystals of LaNb₅O₁₄ could be prepared by chemical transport reactions (T₂ → T₁; T₂ = 1050°C; T₁ = 950°C) using chlorine as transport agent. LaNb₅O₁₄ crystallizes in the orthorhombic space group Pbem with cell dimensions a = 3.8749(2) Å; b = 12.4407(6) Å and c = 20.2051(9) Å; Z = 4; R = 6.28%, R_w = 3.74%. The structure consists of two types of Nb? O-polyhedra. Especially remarkable are chains of edge-sharing pentagonal NbO₇-bipyramids, which are interconnected by corner-sharing NbO₆-octahedra. Tunnels running in a-direction are created by this framework of NbO₆- and NbO₇-polyhedra. Lanthanum atoms are located in these tunnels at levels inbetween the niobium atoms. The relationship to O? LaTa₃O₉ and M? CeTa₃O₉ type structures will be discussed.     

Synthese,Struktur und Reaktionen von Vanadiumsäureestern VO(OR)3: Umesterung und Reaktion mit Oxalsäure

Synthesis, Structure, and Reactions of Vanadium Acid Esters VO(OR)₃: Transesterification and Reaction with Oxalic Acid The reaction of tert.‐Butyl Vanadate VO(O‐tert.Bu)₃ ( 1 ) with H₂C₂O₄ in the primary alcohols ethanol and propanol results in the formation of (ROH)(RO)₂OV^V(C₂O₄)V^VO(OR)₂(HOR) (with R = C₂H₅ 2 and R = C₃H₇ 3 ). Compounds 2 and 3 are the first structurally characterized neutral, binuclear oxo‐oxalato‐complexes with pentavalent vanadium. The two vanadium atoms are connected by a bisbidentate oxalate group. The {VO₆} coordination at each vanadium site is completed by a terminal oxo group, an alcohol ligand and two alcoxide groups. The binuclear molecules are connected to chains by hydrogen bonding. In the case of 2 a reversible isomorphic phase transition in the temperature range of –90 °C to –130 °C is observed. From methanolic solution the polymeric Methyl Vanadate [VO(OMe)₃] ( 4 ) was obtained by transesterification. A report on the crystal structures of 1 , 2 and 3 as well as a redetermination of the structure of 4 is given. Crystal data: 1, orthorhombic, Cmc2₁, a = 16.61(2) Å, b = 9.274(6) Å, c = 10.784(7) Å, V = 1662(2) ų, Z = 4, d_c = 1.144 gcm^–1; 2 (–90 ° C) , monoclinic, I2/a, a = 33.502(4) Å, b = 7.193(1) Å, c = 15.903(2) Å und β = 143.060(3)°, V = 2303(1) ų, Z = 4, d_c = 1.425 gcm^–1; 2 (–130 ° C) , monoclinic, I2/a, a = 33.274(4) Å, b = 7.161(1) Å, c = 47.554(5) Å, β = 142.798(2)°, V = 6851(1) ų, Z = 12, d_c = 1.438 gcm^–1; 3 , triklinic, P1, a = 9.017(5) Å, b = 9.754(5) Å, c = 16.359(9) Å, α = 94.87(2)°, β = 93.34(2)°, γ = 90.42(2)°, V = 1431(1) ų, Z = 2, d_c = 1.340 gcm^–1; 4 , triklinic, P1, a = 8.443(2) Å, b = 8.545(2) Å, c = 9.665(2) Å, α = 103.202(5)°, β = 96.476(5)°, γ = 112.730(4)°, V = 610.2(2)ų, Z = 4, d_c = 1.742 gcm^–1.     

Magnesiumphthalocyanine: Darstellung und Eigenschaften von Halogenophthalocyaninatomagnesat, [Mg(X)Pc2−]− (X = F,Cl, Br); Kristallstruktur von Bis(triphenylphosphin)iminiumchloro(phthalocyaninato)magnesat-Aceton-Solvat

Magnesium Phthalocyanines: Synthesis and Properties of Halophthalocyaninatomagnesate, [Mg(X)Pc^2?]^? (X = F, Cl, Br); Crystal Structure of Bis(triphenylphosphine)iminiumchloro-(phthalocyaninato)magnesate Acetone Solvate Magnesium phthalocyanine reacts with excess tetra(n-butyl)ammonium- or bis(triphenylphosphine)iminiumhalide ((ⁿBu₄N)X or (PNP)X; X = F, Cl, Br) yielding halophthalocyaninatomagnesate ([Mg(X)Pc^2?]^?; X = F, Cl, Br), which crystallizes in part as a scarcely soluble (ⁿBu₄N) or (PNP) complex-salt. Single-crystal X-ray diffraction analysis of ^b(PNP)[Mg(Cl)Pc^2?] · CH₃COCH₃ reveals that the Mg atom has a tetragonal pyramidal coordination geometry with the Mg atom displaced out of the center (Ct) of the inner nitrogen atoms (N_iso) of the nonplanar Pc ligand toward the Cl atom (d(Mg? Ct) = 0.572(3) Å; d(Mg? Cl) = 2.367(2) Å). The average Mg? N_iso distance is 2.058 Å. Pairs of partially overlapping anions are present. The cation adopts a bent conformation (^b(PNP)⁺: d(P1? N(K)) = 1.568(3) Å; d(P2? N(K)) = 1.587(3) Å; ?(P1? N(K)? P2) = 141.3(2)°). Electrochemical and spectroscopic properties are discussed.