Synthese und Kristallstruktur von 2‐Azido‐4,6‐dichloro‐s‐triazin

Synthesis and Crystal Structure of 2‐Azido‐4,6‐dichloro‐s‐triazine Single crystals of 2‐azido‐4,6‐dichloro‐s‐triazine were obtained from a reaction between cyanuric chloride and sodium azide. The structure of this compound was determined by single crystal X‐ray diffraction. 2‐Azido‐4,6‐dichloro‐s‐triazine crystallizes in the orthorhombic space group Pbca (no. 61), Z = 8, a = 746.48(8) pm, b = 952.6(1) pm, c = 2001.6(2) pm. The crystal structure contains (C₃N₃)(N₃)Cl₂ molecules being arranged in a tape‐like fashion, with tapes running along a‐axis direction. The tapes are combined with each other by interlocking azide‐ligands including an angle of approximately 90°. This arrangement leads to the formation of corrugated layers in the crystal structure.     

1, 3, 4, 4'‐Tetra(triphenylphosphanimin)‐2‐iodo‐2‐butenal‐4‐carboniumiodid, [O=C(NPPh3)C(I)=C(NPPh3)‐C(NPPh3)2]+I‐

Pale yellow single crystals of [O=C(NPPh₃)C(I)=C(NPPh₃)‐C(NPPh₃)₂]⁺I^‐·1.5 thf ( 1 ·1.5 thf) have been obtained by the reaction of INPPh₃ with thallium in thf suspension. They are characterized by IR spectroscopy and by a crystal structure determination. 1 ·1.5 thf crystallizes in the monoclinic space group P2₁/n, Z = 4, lattice dimensions at ‐83?C: a = 1101.7(1), b = 3449.0(2), c = 2000.4(1) pm, β = 104.88(1)?, R₁ = 0.0382. 1 can be understood as a cationic variation of (Z)‐2‐butenale in which all H atoms are substituted by triphenylphosphoraneimine residues and by a iodine atom, respectively.     

Hydrogen Bonds in Rubidium Amide‐Ammonia(3/2), RbNH2·2/3NH3

Rubidium amide‐ammonia(3/2), RbNH₂·2/3NH₃, was synthesized from Rubidiumhydride, RbH, in liquid ammonia at ?78 °C. The compound crystallizes in the cubic space group I2₁3 with Z = 4, a = 10.0490(12) Å, and V = 1014.77(20) Å as isometric colorless crystals. The crystal structure was solved from single‐crystal X‐ray data. The structure contains a three‐dimensional network of amide anions and ammonia molecules, which are interconnected via hydrogen bonds.     

[Mn4Br(CH=CMe2)3(μ3‐NPEt3)4] — ein 2‐Methyl‐prop‐1‐enyl‐Phosphaniminato‐Komplex von Mangan(II) mit Heterokubanstruktur

[Mn₄Br(CH=CMe₂)₃(μ₃‐NPEt₃)₄] — a 2‐Methyl‐prop‐1‐enyl‐Phosphoraneiminato Complex of Manganese(II) with Heterocubane Structure [Mn₄Br(CH=CMe₂)₃(μ₃‐NPEt₃)₄] ( 1 ) has been prepared from [MnBr(μ₃‐NPEt₃)]₄ and BrMg(CH=CMe₂) in thf solution and subsequent extraction of the solvent‐free residue with n‐hexane. 1 forms red single crystals from diethylether solution, which are characterized by a crystal structure determination. Space group P1¯, Z = 2, lattice dimensions at —80 °C: a = 1144.7(1), b = 1411.3(2), c = 1521.8(2) pm, α = 91.581(14), β = 90.163(14), γ = 91.947(14)°, R₁ = 0.0448. 1 exhibits a Mn₄N₄ heterocubane core, a terminally coordinated bromine ligand and three Mn—CH=CMe₂ groups with M—C bond lengths of 213.8 pm on average.     

A combined crystallographic,thermal, Raman and computational study on polymorphism and phase transition in 1‐(4‐hexyloxy‐3‐hydroxyphenyl)ethanone

The crystal structure of the triclinic polymorph of 1‐(4‐hexyloxy‐3‐hydroxyphenyl)ethanone, C₁₄H₂₀O₃, differs markedly from that of the orthorhombic polymorph [Manzano et al. (2015). Acta Cryst. C 71 , 1022–1027]. The two molecular structures are alike with respect to their bond lengths and angles, but differ in their spatial arrangement. This gives rise to quite different packing schemes, even if built up by similar chains having the hydroxy–ethanone O—H…O hydrogen‐bond synthon in common. Both phases were found to be related by a first‐order thermally driven phase transformation at 338–340 K, which is discussed in detail. The relative stabilities of both polymorphs are explained on the basis of both the noncovalent interactions operating in each structure and quantum chemical calculations. The polymorphic phase transition has also been studied experimentally by means of differential scanning calorimetry (DSC) experiments, conducted on individual single crystals, Raman spectroscopy and controlled heating under a microscope of individual single crystals, which were further characterized by powder and single‐crystal X‐ray diffraction.     

Structural Characterization of Mn2+—ß″—Al2O3(Mn0.77Al10.46Mg0.54O17)

The structure of completely exchanged Mn²⁺—ß″—Al₂O₃(Mn_0.77Al_10.46Mg_0.54O₁₇) crystals has been investigated by single—crystal X—ray diffraction methods at room temperature (trigonal, R3¯, Z = 3, a = 560.65(7), c = 3329.3(9) pm). The manganese ions (Mn²⁺) are found to occupy Beevers‐Ross (56 %) and mid—oxygen positions (44 %) in nearly the same amounts. The crystal composition was confirmed by electron probe microanalyses on various crystals.     

Gd3(SeO3)4F: Ein Fluoridselenit mit μ3‐SeO32–und μ3‐F–‐überkappten Gd3‐Ringen

Gd₃(SeO₃)₄F: A Fluoride Selenite with μ₃‐SeO₃^2– and μ₃‐F^– Capped Gd₃ Rings The decomposition of Gd₂(SeO₄)₃ in the presence of LiF in sealed gold ampoules yields single crystals of Gd₃(SeO₃)₄F (hexagonal, P6₃mc, Z = 2, a = 1044.3(1), b = 694.32(7) pm, R_all = 0.0286). In the crystal structure one SeO₃^2– group and one F^– ion cap a ring of three Gd atoms. Furthermore, the crystal structure is strongly influenced by the lone pairs of the SeO₃^2– ions.     

The high‐temperature modification of zinc catena‐polyphosphate, β‐Zn(PO3)2

Single crystals of the high‐temperature modification of zinc catena‐polyphosphate, β‐Zn(PO₃)₂, were grown from a melt and quenched from 1093 K to room temperature. The structure was solved from single‐crystal X‐ray diffraction data and is built of corrugated (PO₃)_∞ polyphosphate chains, which extend along the c direction with an eight‐tetrahedra repeat. Slightly distorted [ZnO₄] tetrahedra link the polyphos­phate chains into a three‐dimensional network.     

Synthesis and Structural Analysis of ϵ‐Fe2O3

Powder material of ?‐Fe₂O₃ was obtained by thermal decomposition of the clay mineral nontronite and subsequent isolation of the ferric oxide by leaching the silicate phases. Additionally, crystals of ?‐Fe₂O₃ were grown as precipitates by internal oxidation of a Pd₉₆Fe₄ alloy. Analysis of the precipitate crystals by electron diffraction yields an orthorhombic crystal system and space group Pna2₁ ab initio. X‐ray diffraction data of the powder containing small amounts of Al substituting Fe were refined by the Rietveld method. The refinement yields lattice parameters a = 507.15 pm, b = 873.59 pm and c = 941.78 pm, and atom positions. ?‐Fe₂O₃ is isostructural with κ‐Al₂O₃, AlFeO₃, and GaFeO₃ having an anion stacking sequence /ABAC/, and 1/4 of the cations in tetrahedral co‐ordination. Some strongly distorted FeO₆ octahedrons with one large Fe‐O distance, which may be considered as a 5+1 co‐ordination, appear to be characteristic for ?‐Fe₂O₃. The structure shows elements known from silicates and oxyhydroxides of iron, respectively.     

Polymorphism of Anhydrous Cadmium Iodate Structure of ε‐Cd(IO3)2

The investigation of CdCl₂‐HIO₃ system, in aqueous and HNO₃ solutions, revealed that anhydrous cadmium iodate presents a marked polymorphism. No less than four new Cd(IO₃)₂polymorphs have been isolated and characterized, two of which showing second harmonic generation activity. Single crystals of ε‐Cd(IO₃)₂ are obtained by slowly evaporating, at 60 °C, a saturated solution of γ‐Cd(IO₃)₂ in 30 % nitric acid. This compound crystallizes in the orthorhombic space group Pca2₁ [a = 17.581(2), b = 5.495(2), c = 11.163(2) Å]. The basic structural unit can be described as the connection of two cadmium polyhedrons with a short metal – metal distance of 3.88Å. These units are further linked through two other iodate bridges resulting in layers parallel to the (100) plane. The 3D linkage is ensured by short bonds of the fourth iodate group.     

Single crystals of the filled Ti2N‐type η‐phase Ti3Zn3Ox (x = 1.07 and 1.23) prepared using a Bi flux

Single crystals of the filled Ti₂Ni‐type Ti₃Zn₃O_x η‐phase (cubic, space group Fdm) having {111} facets were obtained by heating Ti, Zn and ZnO with a Bi flux. The lattice parameter of a single crystal prepared at 800°C was 11.4990 (2) Å, which is close to that of Ti₃Zn₃O_∼0.5 (a = 11.502 Å), as reported by Rogl & Nowotny [Monatsh. Chem. (1977), 108 , 1167–1180]. The occupancies of the O1 (16c) and O2 (8a) sites were 1 and 0.071 (12), respectively, and the composition of the crystal was determined to be Ti₃Zn₃O_1.04. A single crystal from the sample prepared at 650°C had the same structure type, with a lattice parameter of 11.5286 (2) Å. However, O atoms were situated at a new 32e site in addition to the original 16c and 8a sites, and the Zn‐atom positions were split in accordance with the new O‐atom site. The chemical formula Ti₃Zn₃O_1.27 determined by X‐ray diffraction occupancy refinement agreed with the chemical composition obtained for the cross section of the single crystal determined with an electron probe microanalyzer.     

The Crystal and Molecular Structure of γ‐P4S6

The crystal and molecular structure of γ‐P₄S₆ was determined from single‐crystal X‐ray diffraction. It crystallizes monoclinically in the space group P2₁/m (No. 11) with a = 6.627(3) Å, b = 10.504(7) Å, c = 6.878(3) Å, β = 90.18(4)°, V = 478.8(4) ų, and Z = 2. The structure consists of cage‐like P₄S₆ molecules with C_S symmetry arranged with the topology of a cubic close packing.     

Dimorphism of ethyl 1,4‐dihydro‐2,4,6‐triphenylpyridine‐3‐carboxylate

The title compound, C₂₆H₂₃NO₂, (Ia) and (Ib), shows polymorphism with crystals obtained from different solvents displaying different crystal structures. However, it is not the geometry of the single mol­ecules nor the hydrogen‐bond pattern that is different in (Ia) and (Ib), but the way in which the hydrogen‐bonded chains, running along the a‐axis direction, are arranged with respect to each other.     

Synthese und Kristallstruktur des ersten Oxonitridoborates — Sr3[B3O3N3]

Synthesis and Crystal Structure of the First Oxonitridoborate — Sr₃[B₃O₃N₃] The cyclotri(oxonitridoborate) Sr₃[B₃O₃N₃] was synthesized at 1450 °C as coarsely crystalline colourless crystals by the reaction of SrCO₃ with poly(boron amide imide) using a radiofrequency furnace. The structure was solved by single‐crystal X‐ray diffractometry (Sr₃[B₃O₃N₃], Z = 4, P2₁/n, a = 663.16(2), b = 786.06(2), c = 1175.90(3) pm, η = 92.393(1)°, R1= 0.0441, wR2 = 0.1075, 1081 independent reflections, 110 refined parameters). Besides Sr²⁺ there are hitherto unknown cyclic [B₃O₃N₃]^6— ions (B—N 143.7(10) — 149.1(9) pm, B—O 140.5(8) — 141.4(8) pm).     

LiSr2[TaN3]F – a Single Chain Nitridotantalate

The chain type nitridotantalate LiSr₂[TaN₃]F was synthesized by reaction of strontium with AlF₃, Eu(NH₂)₂, LiN₃ and lithium metal as fluxing agent in weld shut tantalum ampoules. Single crystals were obtained as byproduct from reaction with the ampoule material. The crystal structure (Pbca (no. 61), a = 10.768(2), b = 5.5913(11), c = 15.891(3) Å, Z = 8) was solved on the basis of single‐crystal X‐ray diffraction data. LiSr₂[TaN₃]F contains infinite chains of vertex sharing TaN₄ tetrahedra running along [010]. The structure can be understood as an intercalation of Li⁺ and F^– into Sr₂TaN₃. Lattice energy calculations (MAPLE) and EDX measurements confirmed the electrostatic bonding interactions and the chemical composition.     

Thermodynamic Phase Transition Through Crystal‐to‐Crystal Process of Photochromic 1,2‐Bis(5‐phenyl‐2‐propyl‐3‐thienyl)perfluorocyclopentene

A photochromic diarylethene, 1,2‐bis(5‐phenyl‐2‐propyl‐3‐thienyl)perfluorocyclopentene ( 1a ), was found to have two polymorphic crystal forms, α‐ and β‐crystals. From X‐ray crystallographic analysis, the space groups of α‐ and β‐crystals were determined to be P2₁/c and C2/c, respectively. The difference between two crystal forms is ascribed to the orientation of two of four molecules in the unit cell. The thermodynamic phase transition from α‐ to β‐forms occurred via a crystal‐to‐crystal process, as confirmed by differential scanning calorimetry measurements, optical microscopic observations in the reflection mode and under crossed Nicols, and powder X‐ray diffraction measurements. The movement of the molecules in the crystal was evaluated by analyzing the change of face indices before and after the phase transition.     

Dimeric Structure of [(η2‐NO3)2(tpy)Bi(μ‐OH)2Bi(tpy)(η2‐NO3)2]

The synthesis and single crystal X‐ray structure determination are reported for the 2,2′ : 6′,2″‐terpyridine (= tpy) adduct of bismuth(III) nitrate. The hydroxide‐bridged dimer [(η²‐NO₃)₂(tpy)Bi(μ‐OH)₂Bi(tpy)(η²‐NO₃)₂] with nine‐coordinate geometry about Bi was the only isolable product from all crystallization attempts in varying ratios of Bi(NO₃) : terpy.; [(η²‐NO₃)₂(tpy)Bi(μ‐OH)₂Bi(tpy) · (η²‐NO₃)₂] is triclinic, P 1, a = 7.941(8), b = 10.732(9), c = 11.235(9) Å; α = 63.05(1), β = 85.01(1), γ = 79.26(1)°, Z = 1, dimer, R = 0.058 for N₀ = 2319.     

N‐Methylimidazolkomplexe des Berylliums: [Be(Me‐Im)4]I2 und [Be3(μ‐OH)3(Me‐Im)6]Cl3

Tetra(N‐methylimidazole)‐beryllium‐di‐iodide, [Be(Me‐Im)₄]I₂ ( 1 ), was prepared from beryllium powder and iodine in N‐methylimidazole suspension to give yellow single crystal plates, which were characterized by X‐ray diffraction and IR spectroscopy. Compound 1 crystallizes tetragonally in the space group I 2d with four formula units per unit cell. Lattice dimensions at 100(2) K: a = b = 1784.9(1), c = 696.2(1) pm, R₁ = 0.0238. The structure consists of homoleptic dications [Be(Me‐Im)₄]²⁺ with short Be–N distances of 170.3(3) pm and iodide ions with weak interionic C–H ··· I contacts. Experiments to yield crystalline products from reactions of N‐methylimidazole with BeCl₂ and (Ph₄P)₂[Be₂Cl₆], respectively, in dichloromethane solutions were unsuccessful. However, single crystals of [Be₃(μ‐OH)₃(Me‐Im)₆]Cl₃ ( 2 ) were obtained from these solutions in the presence of moisture air. According to X‐ray diffraction studies, two different crystal individuals ( 2a and 2b ) result, depending on the starting materials BeCl₂ and (Ph₄P)₂[Be₂Cl₆], respectively [ 2a : Space group P2₁/n, Z = 4; 2b : Space group P , Z = 2]. As a side‐product from the reaction of N‐methylimidazole with (Ph₄P)₂[Be₂Cl₆] single crystals of (Ph₄P)Cl·CH₂Cl₂ ( 3 ) were identified crystallographically (P2₁/n, Z = 4) which are isotypical with the corresponding known bromide (Ph₄P)Br·CH₂Cl₂.     

Synthesis and Characterization of [Mn3(ppi)2(μ‐OAc)4(H2O)2] · 2MeOH — Unusual Structural Properties of a Trinuclear Oxygen‐Rich Manganese Complex

The trinuclear manganese(II) complex [Mn₃(ppi)₂(μ‐OAc)₄(H₂O)₂]·2MeOH ( 1 ) (Hppi = 2‐pyridylmethyl‐2‐hydroxyphenylimine) is prepared by dissolving two equivalents of Hppi (from the Schiff Base reaction of aminophenol and pyridine‐2‐carboxaldehyde) in acetonitrile and three equivalents of Mn(OAc)₂·4H₂O in methanol and combining both solutions. The resulting red precipitate was recrystallized to yield red crystals suitable for single crystal X‐ray diffraction. Compound 1 crystallizes in the triclinic space group P1¯ (no. 2), with a = 9.691(2), b = 10.683(2), c = 11.541(2)Å, α = 63.19(3)°, β = 67.47(3)°, γ = 69.11(3)°, V = 960.2(3)ų, and Z = 1. The binding mode of carboxylate in 1 represents a model for a transition state between symmetric syn, syn, anti‐μ₂‐carboxolato‐O‐ and syn, anti‐μ₂‐carboxylato‐O, O′‐coordination. Therefore a rare binding mode for the phenomenon of the carboxylate shift is realized. Furthermore the complex is stabilized by a distinctive hydrogen bonding pathway.