X-ray crystal structure and raman spectrum of tribromine(1+) hexafluoroarsenate(V), Br3+AsF6−, and raman spectrum of pentabromine(1+) hexafluoroarsenate(V), Br5+AsF6−

A single crystal of Br₃⁺AsF₆^? was isolated from a sample of BrF₂⁺AsF₆^? which had been stored for 20 years. It was characterized by x-ray diffraction and Raman spectroscopy. It is shown that Br₃⁺AsF₆^? (triclinic, a = 7.644(7) Å, b = 5.641(6) Å, c = 9.810(9) Å, α = 99.16(8)°, β = 86.61(6)°, γ = 100.11(7)°, space group P1 R(F) = 0.0608) is isomorphous with I₃⁺AsF₆^?. The structure consists of discrete Br₃⁺ and AsF₆^? ions with some cation-anion interaction causing distortion of the AsF₆^? octahedron. The Br₃⁺ cation is symmetric with a bond distance of 2.270(5) Å and a bond angle of 102.5(2)°. The three fundamental vibrations of Br₃⁺ were observed at 297 (ν₃), 293 (ν₁), and 124 cm^?1 (ν₂). The Raman spectra of Cl₃⁺AsF₆^? and I₃⁺AsF₆^? were reinvestigated and ν₃(B₁) of I₃⁺ was reassigned. General valence force fields are given for the series Cl₃⁺, Br₃⁺, and I₃⁺. Reactions of excess Br₂ with either BrF₂⁺AsF₆^? or O₂⁺AsF₆^? produce mixtures of Br₃⁺AsF₆^? and Br₅⁺AsF₆^?. Based on its Raman spectra, the Br₅⁺ cation possesses a planar, centrosymmetric structure of C_2h symmetry with three semi-ionically bound, collinear, central Br atoms and two more covalently, perpendicularly bound, terminal Br atoms.     

Fluorierung von Cyanurchlorid und Tieftemperatur-Kristallstruktur von [(ClCN)3F]+ [AsF6]−

Fluorination of Cyanuric Chloride and Low-Temperature Crystal Structure of [(ClCN)₃F]⁺[AsF₆]^? The low-temperature fluorination of cyanuric chloride, (ClCN)₃, with F₂/AsF₅ in SO₂F₂ solution yielded the salt [(ClCN)₃F]⁺ [AsF₆]^? ( 1 ) essentially in quantitative yield. Compound 1 was identified by a low-temperature single crystal X-ray structure determination: R 3 c, trigonal, a = b = 10.4246(23) Å, c = 15.1850(24) Å, V = 1429.1(4) Å 3, Z = 6, R_F = 0.056, R_w = 0.076 (for significant reflections), R_F = 0.088, R_w = 0.079 (for all reflections). Fluorination of neat (ClCN)₃ with [NF₄]⁺ [Sb₂F₁₁]^? yielded NF₃, CClF₃, SbF₃, N₂ and traces of CF₄. A qualitative scale for the oxidizing strength of the oxidative fluorinators NF₄⁺ and (XCN)₃F⁺ (X = H, F, Cl) has been computed ab initio.     

Über die oxidative Fluorierung von (CF3)(R) (R = CF3, Cl) und die Kristallstruktur von (CF3)(Cl)F+ AsF6−

Oxidative Fluorination of (CF₃)(R) (R = CF₃, Cl) and the Crystal Structure of (CF₃)(Cl) F⁺ AsF₆^? Oxidative fluorination of (CF₃)(R) (R = CF₃, Cl) with XeF⁺MF₆^? (M = As, Sb) in anhydrous HF results in formation of monofluorsulfonium hexafluorometalates. The salts are characterized by vibrational, NMR, and mass spectra. (CF₃)(Cl)F⁺ AsF₆^? crystallizes in the monoclinic space group P2₁/c with a = 9.955(10) Å, b = 11.050(5) Å, c = 12.733(15) Å, β = 97.77(5)°, and Z = 4.     

The Protonation of Acetamide and Thioacetamide in Super­acidic Solutions: Crystal Structures of [H3CC(OH)NH2]+AsF6– and [H3CC(SH)NH2]+AsF6–

Acetamide and thioacetamide react with the superacid solutions HF/MF₅ (M = As, Sb) under formation of the corresponding salts [H₃CC(OH)NH₂]⁺MF₆^– and [H₃CC(SH)NH₂]⁺MF₆^– (M = As, Sb), respectively. The reaction of DF/AsF₅ with acetamide and thioacetamide lead to the corresponding deuterated salts [H₃CC(OD)ND₂]⁺AsF₆^– and [H₃CC(SD)ND₂]⁺AsF₆^–, respectively_. The salts are characterized by vibrational and NMR spectroscopy, and in the case of [H₃CC(OH)NH₂]⁺AsF₆^– and [H₃CC(SH)NH₂]⁺AsF₆^– also by single‐crystal X‐ray analyses. The [H₃CC(OH)NH₂]⁺AsF₆^– ( 1 ) salt crystallizes in the triclinic space group P$\bar{1}$ with two formula units per unit cell, and the [H₃CC(SH)NH₂]⁺AsF₆^– ( 2 ) salt crystallizes in the monoclinic space group P2₁/c with four formula units per unit cell. In both crystal structures three‐dimensional networks are observed which are formed by intra‐ and intermolecular N–H ··· F and O–H ··· F or S–H ··· F hydrogen bonds, respectively. For the vibrational analyses, quantum chemically calculated spectra of the cations [H₃CC(OH)NH₂ · 3HF]⁺ and [H₃CC(SH)NH₂ · 2HF]⁺ are considered.     

Stereoselective Inclusion and Structure of Equatorial-trans-1,2-dichlorocyclohexane

Abstract

Optically active (R,R)-(-)-trans-1,2-dichlorocyclohexane (DCC) was isolated as an inclusion crystal with the optically active host, (R,R)-(-)-trans-2,3-(hydroxydiphenylmethyl)-1,4-dioxaspiro[4.4]-nonane, and the structure of the 2:1 inclusion crystal has been determined by X-ray analysis. Crystal data: C₇₂H₇₄O₈Cl₂, orthorhombic, P2₁2₁2 (No. 18), a = 17.465(6) Å, b = 20.095(6) Å, c = 8.664(5) Å, V = 3040(2) ų, Z = 2, D_c = 1.24g cm^?3, D_m = 1.23g cm^?3, T = 293 K and final R ₁ = 0.050 for 2766 observed data (I > 2σ(I)). The conformation of DCC in the inclusion crystal has been found to be equatorial and the absolute configuration was definitely determined to be (R,R) on the basis of the known configuration of the host.     

Crystal structure and luminescence of antimony(III) chloride complex with anilinium chloride

Crystal structure of (C₆H₅NH₃)₃[SbCl₅]Cl·H₂O is determined by X-ray analysis (a = 9.4155(13) Å, b = 11.4344(16) Å, c = 13.1584(18) Å, α = 113.483(2)°, β = 90.383(2)°, γ = 97.323(2)°, space group P \(\bar 1\), Z = 2, ρ_calc = 1.642 g/cm³). The crystal structure is based on [SbCl₅]^2? anions, anilinium cations (C₆H₅NH₃)⁺, isolated Cl^? anions, and water molecules. Structural features responsible for spectral and luminescent properties of the complex are discussed.     

The Low and High Temperature Crystal Structures of [Mg(H2O)6]XBr3 Double Salts (X = Rb,Cs

The crystal structures of the alkali double salts [Mg(H₂O)₆]XBr₃ (X = Rb⁺, Cs⁺) were analyzed in dependence on temperature from laboratory and synchrotron X‐ray powder diffraction data. At room temperature, both compounds are isostructural to [Mg(H₂O)₆](NH₄)Br₃ (C2/c; Z = 4; a = 9.64128(6) Å, b = 9.86531(5) Å, c = 13.78613(9) Å, β = 90.0875(5)° for [Mg(H₂O)₆]RbBr₃; a = 9.82304(7) Å, b = 9.98043(6) Å, c = 14.0100(1) Å, β = 90.1430(4)° for [Mg(H₂O)₆]CsBr₃). At a temperature of T = 358 K, [Mg(H₂O)₆]RbBr₃ undergoes a reversible phase transition towards a cubic perovskite type of structure with the [Mg(H₂O)₆]²⁺ octahedron in the cuboctahedral cavity exhibiting 4‐fold disorder ( ; a = 6.94198(1) Å at T = 458 K). In case of [Mg(H₂O)₆]CsBr₃ the lattice parameters in dependence on temperature show a distinct kink at T = 340 K, but no symmetry breaking phase transition occurs before decomposition starts. The dominant role of hydrogen bonding with respect to the stability of the crystal structures is discussed.     

2-Hydroxy-4-methylbenzenesulfonic acid dihydrate: Crystal structure, vibrational spectra, proton conductivity, and thermal stability

The crystal and molecular structure of 2-hydroxy4-methylbenzenesulfonic acid dihydrate C₆H₃(CH₃)(OHSO^? ₃ H₅O₂ ⁺ (I) was studied by X-ray diffraction and vibrational spectroscopy. The compound crystallized in the monoclinic crystal system; crystal data: a=10.853(2) Å, b=7.937(2) Å, c=12.732(3) Å, β=112.13(3)°, V=1015.9(4)ų,Z=4,d_calc=1.466g/cm³,spacegroupP2₁/c,R_f=0.0486,GOOF=1.161.The S-O distances in the sulfonate group differed substantially (S1-O2 1.439(2) Å, S1-O3 1.455(2) Å, and S1-O4 1.464(2) Å. The symmetry of the H₅O₂ cation decreased due to proton displacement toward one of the two water molecules. XRD data on the asymmetry of H5O2 were confirmed by IR and Raman spectral data. The strong triplet at 2900, 3166, 3377 cm^?1 in the IR spectrum of I corresponds to different types of H-bond and shifted to 2185, 2363, 2553 cm^?1 after deuteration. The proton conductivity of the compound was measured by impedance spectroscopy: 6 × 10^?7 S/cm at 298 K (32 rel %), E _act=0.4±0.01 eV. The conductivity increased to 10^-3 S/cm, E_act=0.1 eV when ambient humidity increased to 60 rel %.     

Two Modifications of NH4HPO3F: Synthesis and Crystal Structure

The α and β modifications of NH₄HPO₃F were synthesized and characterized with single crystal X‐ray diffraction. The crystal structure of α‐NH₄HPO₃F determined at 180 K is monoclinic, space group P2₁/n, with a = 7.4650(1), b = 15.586(2), c = 7.5785(9) Å, β = 108.769(9)°, V = 834.9(2) ų, Z = 8, and R₁ = 0.0376 and wR₂ = 0.0818. β‐NH₄HPO₃F measured at 310 K crystallizes in the triclinic space group, P 1, with a = 7.481(1), b = 7.511(1), c = 7.782(1) Å, α = 84.31(1), β = 84.20(1), γ = 68.67(2)°, V = 404.31(9) ų, Z = 4, and R₁ = 0.0254 and wR₂ = 0.0735. A phase transition was not observed between 180 and 310 K for β‐NH₄HPO₃F. Both modifications of NH₄HPO₄F consist of HPO₃F^– and NH₄⁺ units. Two pairs of two unique anions are linked to each other by O–H…O hydrogen bonds to form cyclic tetramers held together by N–H…O bonds. No O–H…F or N–H…F bonds were observed.     

Syntheses and characterization of ANi(AsF6)3 (A = H3O, O2, NO, NH4, K, Rb, and Cs) compounds

ANi(AsF₆)₃ (A = O₂⁺, NO⁺, NH₄⁺) compounds could be prepared by reaction between corresponding AAsF₆ salts and Ni(AsF₆)₂. When mixtures of AF (A = Li, Na, K, Rb, Cs) and NiF₂ are dissolved in aHF acidified with an excess of AsF₅ the corresponding AAsF₆ and Ni(AsF₆)₂ were formed in situ. For A = Li and Na only mixtures of AAsF₆ and Ni(AsF₆)₂ were obtained, while for A = K, Rb and Cs, the final products were ANi(AsF₆)₃ (A = K-Cs) compounds contaminated with AAsF₆ (A = K-Cs) and Ni(AsF₆)₂.ANi(AsF₆)₃ (A = H₃O⁺, O₂⁺, NO⁺, NH₄⁺ and K⁺) compounds are structurally related to previously known H₃OCo(AsF₆)₃. The main features of the structure of these compounds are rings of NiF₆ octahedra sharing apexes with AsF₆ octahedra connected into infinite tri-dimensional network. In this arrangement cavities are formed where single charged cations are placed.In O₂Ni(AsF₆)₃ the vibrational band belonging to O₂⁺ vibration is found at 1866 cm⁻¹, which is according to the literature data one of the highest known values, and it is only 10 cm⁻¹ lower than the value for free O₂⁺.     

Syntheses and structures of nine-coordinate NH4[HoIII(Edta)(H2O)3] · 1.5H2O, (NH4)4[Ho 2 III (Dtpa)2] · 9H2O, and (NH4)3[HoIII(Ttha)] · 5H2O complexes

The three title complexes, NH₄[Ho^III(Edta)(H₂O)₃] · 1.5H₂O (I) (H₄Edta = ethylenedianine-N,N,N′,N′-tetraacetic acid), (NH₄)₄[Ho ₂ ^III (Dtpa)₂] · 9H₂O (II) (H₅Dtpa = diethylenetriamine-N,N,N′,N″,N″-entaacetic acid), and (NH₄)₃[Ho^III(Ttha)] · 5H₂O (III) (H₆ Ttha = triethylenetetramine-N,N,N′,N″,N?,N?-hexaacetic acid), have been prepared and characterized by FT-IR, elemental analyses, and single-crystal X-ray diffraction technique. Complex I has a nine-coordinate mononuclear structure with distorted monocapped square antiprismatic conformation and its crystal structure belongs to orthorhombic system and Fdd2 space group. The crystal data are as follows: a = 19.343(9), b = 35.125(17), c = 12.364(6) Å, V = 8400(7) ų, Z = 16, M = 552.26, ρ_calcd = 1.747 g cm^?3 μ = 3.828 mm^?1, and F(000) = 4368. Complex II has a binuclear nine-coordinate pseudomonocapped square antiprismatic conformation and its crystal structure belongs to triclinic system and space P1 group. The crystal data are as follows: a = 9.7637(16), b = 9.9722(16), c = 12.945(2) Å, α= 85.853(2)°, β = 77. 140(2)°, γ = 77.140(2)°, V = 1198.4(3) ų, Z = 1, M = 1340.80, ρ_calcd = 1.858 g cm^?3, μ = 3.380 mm^?1, and F(000) = 674. As for complex III, it also has nine-coordinate mononuclear structure with distorted tricapped trigonal prism and its crystal structure belongs to monoclinic system andP2₁/c space group. The crystal data are as follows: a = 10.349(3), b = 12.760(4), c = 23.142(7) Å, β = 91.020(6)°, V = 3055.6(16) ų, Z = 2, M = 797.55, ρ_calcd = 1.734 g cm^?3, μ = 2.674 mm^?1, and F(000) = 1624. The results showed that although the ligands are different from one another in the shape and the numbers of coordination atoms, they all have nine-coordinate structures. However, one of them has binuclear structure and the other two have mononuclear structures because of the difference of the ligands.     

The crystal structure of Solid Perrhenic Acid Monohydrate

Solid perrhenic acid monohydrate has been characterized by X-ray single crystal structure analysis (300 K). HReO₄ · H₂O, M_r = 269.23, tetragonal, I4₁/a, Scheelite-type (CaWO₄), a = 5.8320(2) Å, c = 12.9384(6) Å, V = 440.06(5) ų, Z = 4, D_x = 4.063 g cm^?3, X-ray wavelength λ (MoKα) = 0.71069 Å The structure consists of [ReO₄]^?-tetrahedra and oxonium ions linked by hydrogen bridges to form a three-dimensional network.     

X-ray diffraction study of the monoclinic modification of [Cu(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>](ReO<Subscript>4</Subscript>)<Subscript>2</Subscript> in the range 100-410 K

The monoclinic modification of [Cu(NH₃)₄](ReO₄)₂ complex salt in the range 100-410 K is studied by single crystal X-ray diffraction. The crystallographic data for 300 K are as follows: a = 10.6123(3) Å, b = 7.5443(2) Å, c = 15.2261(4) Å, β = 108.406(1)°, V = 1156.67(5) ų, space group Р2₁/n, Z = 4, d_x = 3.623 g/cm³. The coordination environment of the Cu atom, being a distorted square formed by four nitrogen atoms with Cu–N of 1.997-2.018 Å, is completed by the contacts with two oxygen atoms Cu…O of 2.472 Å and 2.598 Å. The comparative crystal chemical analysis with the triclinic modification of [Cu(NH₃)₄](ReO₄)₂ known in the literature is performed.     

The Influence of the Counterions [AsF6]– and [GeF6]2– on the Structure of the [ClSO2NH3]+ Cation

Chlorosulfonamide reacts in the superacidic solutions HF/GeF₄ and HF/AsF₅ under the formation of ([ClSO₂NH₃]⁺)₂[GeF₆]^2– and [ClSO₂NH₃]⁺[AsF₆]^–, respectively. The chlorosulfonammonium salts were characterized by X‐ray single crystal structure analysis as well as vibrational spectroscopy and discussed together with quantum chemical calculations. ([ClSO₂NH₃]⁺)₂[GeF₆]^2– crystallizes in the triclinic space group P1 with one formula unit in the unit cell. [ClSO₂NH₃]⁺[AsF₆]^– crystallizes in the monoclinic space group P2₁/n with four formula units in the unit cell. Dependent on the counterion, [AsF₆]^– or [GeF₆]^2–, considerable structural differences of the [ClSO₂NH₃]⁺ cation are observed. Furthermore, the hitherto unknown X‐ray single crystal structure of chlorosulfonamide is determined in the course of this study. Chlorosulfonamide crystallizes in the orthorhombic space group Pmc2 with four formula units per unit cell.     

Synthesis and Characterization of Guanidinium Difluoroiodate, [C(NH2)3]+[IF2O2]– and its Evaluation as an Ingredient in Agent Defeat Weapons‡

Ammonium and guanidinium difluoroiodate(V), [NH₄]⁺[IF₂O₂]^– ( 1a ) and [C(NH₂)₃]⁺[IF₂O₂]^– ( 1b ), and diazidoglyoxime, [N₃C=N–OH]₂ ( 2 ) were synthesized and the molecular structures in the solid state of 1b and 2 were elucidated by single‐crystal X‐ray diffraction. 1b : P$\bar{1}$ , a = 6.6890(5), b = 10.2880(6), c = 10.30.92(8) Å, α = 105.447(6), β = 108.568(7), γ = 91.051(5)°, V = 644.08(8) Å³, ρ = 2.650 g · cm^–3; 2 : P2₁/n, a = 4.4211(3), b = 13.7797(9), c = 4.9750(3) Å, β = 98.735(6), V = 299.57(3) Å³, ρ = 1.886 g · cm^–3. The suitability of compounds 1a and 1b as active ingredients for agent defeat weapons (ADW) with biocidal activity has been shown in detonation tests using geobacillus stearothermophilus spores. In addition, a complete energetic characterization of the promising primary explosive 2 is given.     

Synthesis,Crystal Structure,Bonding, and Properties of (Ba6O)(OsN3)2

The new barium nitridoosmate oxide (Ba₆O)(OsN₃)₂ was prepared by reacting elemental barium and osmium (3:1) in nitrogen at 815–830 °C. The crystal structure of (Ba₆O)(OsN₃)₂ as determined by laboratory powder X‐ray diffraction ( , No 148: a=b=8.112(1) Å, c=17.390(1) Å, V=991.0(1) ų, Z=3), consists of sheets of trigonal OsN₃ units and trigonal‐antiprismatic Ba₆O groups, and is structurally related to the “313 nitrides” AE₃MN₃ (AE=Ca, Sr, Ba, M=V–Co, Ga). Density functional calculations, using a hybrid functional, likewise indicate the existence of oxygen in the Ba₆ polyhedra. The oxidation state 4+ of osmium is confirmed, both by the calculations and by XPS measurements. The bonding properties of the OsN₃^5? units are analyzed and compared to the Raman spectrum. The compound is paramagnetic from room temperature down to T=10 K. Between room temperature and 100 K it obeys the Curie–Weiss law (μ=1.68 μ_B). (Ba₆O)(OsN₃)₂ is semiconducting with a good electronic conductivity at room temperature (8.74×10^?2 Ω^?1 cm^?1). Below 142 K the temperature dependence of the conductivity resembles that of a variable‐range hopping mechanism.     

Crystal structure and luminescence of antimony(III) bromide with aniline

The atomic structure of antimony(III) bromide crystals with anilinium was determined by X-ray diffraction analysis of (C₆H₅NH₃)₂SbBr₅ (a = 19.704(3) Å, b = 7.914(1) Å, c = 25.556(4) Å; space group Pbca, Z = 8, ρ_calc = 2.365 g/cm³). The crystal structure consists of infinite chains of [SbBr₅]^2? complex anions formed by sharing six vertices and the anilinium (C₆H₅NH₃)⁺ cations, through which the chains are linked in layers by N-H...Br hydrogen bonds. The geometrical aspects that determine the luminescent spectral properties of the complex are discussed.     

Synthesis,Crystal Structure,and Conductivity Investigation of a New Monophosphate: (2-CH3OC6H4CH2NH 3)H2PO4

Chemical preparation, crystal structure, thermogravimetric and differential analysis, solid state ³¹P MAS NMR characterization, and IR spectroscopic investigations are given for a new organic cation dihydrogenmonophosphate, (2-CH₃OC₆H₄CH₂NH₃)H₂PO₄. This compound is monoclinic C2/c, with unit cell parameters a = 27.740(8), b = 4.827(2), c = 16.435(3) Å, β = 93.79(2)°, V = 2196 (1) ų, Z = 8, and ρ = 1.422 g · cm^?3. The crystal structure has been determined and refined to R = 0.046 (Rw = 0.056), using 1,746 independent reflections with I > 3σ (I). Its atomic arrangement can be described by infinite polyanions [H₂PO₄] _n ^{n ?}, organized in ribbons alternating with organic cations. Strong hydrogen bonds connect the different components. Electrical conductivity measurements show that the [2-CH₃OC₆H₄CH₂NH₃]H₂PO₄ has a low ionic conductivity value at 403 K.     

Conformational Studies of Dibenzo-30-crown-10 Complexes. Syntheses and Crystal Structures of Potassium and Ammonium Hexafluorophosphate Complexes

Abstract

Crown ether complexes formed by the dibenzo–30-crown–10 (DB30C10) with potassium and ammonium hexafluorophosphate have been prepared and their crystal structures have been determined by single crystal X-ray analyses. The potassium complex (compound 1) consists of [K(DB30C10)]⁺ cation and PF₆ ^? anion. Crystals are monoclinic, space group P2/n, with a = 11.9106(3), b = 9.8382(5), c = 14.3062(3) Å, β = 97.581(3)°, V = 1661.7(1) ų, D_c = 1.440 g cm^?3, Z = 4, R = 0.0675 for 2528 unique observed reflections. The potassium atom is coordinated to the ten oxygen atoms of the crown ligand at the distance from 2.859(3) to 2.930(3) Å. The ammonium complex (compound 2) has also 1:1 crown—cation ratio. Crystals are monoclinic, space group P2₁/n, with a = 12.5061(6), b = 19.3724(5), c = 14.2203(9) Å, β = 102.476(5)°, V = 3363.8(3) ų, D_c = 1.501 g cm^?3, Z = 4, R = 0.0677 for 4172 unique observed reflections. The ammonium cation is completely enclosed with crown oxygen atoms forming seven hydrogen bonds. The conformation of previously reported dibenzo-30-crown-10 complexes with potassium salts were investigated using polar coordinate maps.     

Crystal structure and magnetic properties of tetra(monomethylammonium)hexachloroytterbatochloride(CH3NH3)4YbCl7

(CH₃NH₃)₄YbCl₇ has been synthesized from a solution of CH₃NH₃Cl and YbCl₃ in a mixture of ethnole/acetonitrile. The structure was solved from 1464 single crystal data by Patterson methods and refined to a final R_w = 0.035 space group P2, a = 9.972(6) Å, b = 7.605(5) Å, c = 12.866(6) Å, β = 90.53(4)°. The structure consists of alternating [YbCl₆]^3? octahedra and of tetrahedrally arranged [(CH₃NH₃)₄Cl]³⁺ units. Raman spectra display a splitting of frequencies related to the CH₃NH₃⁺ group in agreement with the structure determination. The magnetic susceptibility shows a remarkable deviation from a Curie-Weiss law below 170 K which may be explained by crystal field effects of Yb³⁺.