Über das Jod(V,VII)-oxid J2O6

On the Iodine(V, VII) Oxide I₂O₆ The existence of the compound I₂O₆ is confirmed. It has been prepared by dehydration of a solution of H₅IO₆ and HIO₃ in 95% H₂SO₄ by addition of oleum. Following an earlier method the compound has also been obtained by thermal decomposition of H₅IO₆. I₂O₆ is a chemical species as concluded from its individual Raman spectrum. Diamagnetism proves the formulation as a mixed-valence iodine(V, VII) oxide. According to the vibrational spectrum the compound is nearly described as an iodyl periodate IO₂⁺IO₄^?.     

Neue Quecksilber(II)-perjodate

New Mercury(II) Periodates From Hg(NO₃)₂ and H₅IO₆ soluted in nitric acid of variated concentration, the long known Hg₅(IO₆)₂ and the new salts Hg₂HIO₆ (brown), Hg₃(H₂IO₆)₂ (yellow), Hg₃(IO₅)₂ (black), and HgH₃IO₆ (colourless) have been prepared. Dehydration of HgH₃IO₆ leads to the brown salt HgHIO₅. The structure of the new compounds has been deduced from their i.r. spectra. The existence of the earlier reported salts Hg(IO₄)₂, Hg₄I₂O₁₁, Hg₇(IO₇)₂ · 18 H₂O and Hg₆I₂O₁₃ · 20 H₂O has not been confirmed.     

Präparation,Kristallstruktur, Schwingungsspektren und thermische Analyse von Kupfer‐tetrahydrogen‐decaoxo‐diperiodat‐hexahydrat CuH4I2O10·6H2O

On Copper‐tetrahydrogen‐decaoxo‐diperiodate‐hexahydrate CuH₄I₂O₁₀·6H₂O: Crystal Structure, Vibrational Spectroscopy and Thermal Analysis By crystallization from a strongly acidic aqueous solution copper‐tetrahydrogen‐decaoxodiperiodate‐hexahydrate CuH₄I₂O₁₀· 6H₂O has been obtained. In the structure of this compound (S.G. P 2₁/c, Nr.14), Z = 2, a = 1060.2(2) pm, b = 551.1(1) pm, c = 1164.7(2) pm, β = 111, 49(3)°) centrosymmetric [H₄I₂O₁₀]^2— anions in the form of two edge sharing octahedra form layers via hydrogen bonds originating from the acidic, trans‐configurated OH groups of the anions. Raman spectra are given and analyzed with respect to the internal vibrations of the periodate anion. The dehydration of the compound takes place via CuH₄I₂O₁₀·3H₂O and Cu(H₂IO₅)₂ which decomposes at 170 °C to Cu(IO₃)₂.     

Reindarstellung,Kristallzüchtung und Kristallstrukturbestimmung von Iodtrioxid

Synthesis, Crystal Growth, and Crystal Structure Determination of Iodine Trioxide For the first time, pure and single crystalline iodine trioxide has been obtained and its identity proven by a crystal structure determination, unambigously. It forms at slow decomposition of orthoperiodic acid in concentrated sulfuric acid at 70°C during 3–6 weeks. The crystal structure (triclinic, P1 ; a = 500.6(2), b = 674.1(3), c = 679.5(3) pm, α = 97.31(3), β = 96.43(3), γ = 105.36(3)°; 1754 independent reflections, R = 0.064) contains one I₄O₁₂ molecule per unit cell. The oxide can be regarded as a mixed anhydride formed by condensation of two molecules H₅IO₆ and HIO₃, each. The axial atoms in an I₂O₁₀ doubleoctahedron are bridged by two IO groups. The pointsymmetry is C_2h. The molecules are connected via short intermolecular oxygen iodine bridges to form twodimensional infinite layers. The crystal structure thus represents an intermediate between molecular and polymeric.     

Li2H4I2O10, das erste Tetrahydrogendimesoperiodat

Li₂H₄I₂O₁₀, the First Tetrahydrogendimesoperiodate Li₂H₄I₂O₁₀ has been obtained as an intermediate during the dehydration of LiH₄IO₆ · H₂O to LiIO₄, for the first time. According to the results of an X-ray structure determination (monoclinic, P2₁/n, a = 533.98(4), b = 471.85(4), c = 1431.48(10) pm, β = 91.614(7)°, Z = 2, 726 diffractometer data, R = 0.056), Li₂H₄I₂O₁₀ contains the previously unknown tetrahydrogendimesoperiodate ion H₄I₂O₁₀^2?, consisting of two edge-shared IO₆ octahedra. They are connected with LiO₆ octahedra via common edges and vertices. The crystals are non-merohedrally twinned along (100).     

Synthesis and properties of beryllium iodates IV

The thermal decomposition of Be(IO₃)₂·2HIO₃·6H₂O was studied by means of DTA and DSC methods. The enthalpies of the more important phase transitions were determined. Be(IO₃)₂·I₂O₅ was isolated and identified as an intermediate.     

Transition metal iodates. VI. Preparation and characterization of the larger lanthanide iodates

In the continuation of this work, the Ln^III(IO₃)₃xH₂O type N compounds (abbreviated x_N) of La through Sm were prepared by precipitation, thermal decomposition, and by crystallization from the gel, from ambient and boiling water, and from boiling HNO₃. A total of 36 different compounds with 6 ? x ? 0 were obtained occurring in 12 structural types including one amorphous; in addition La₅(IO₆)₃ and four isostructural double salts of the type Ln(IO₃)₃·HIO₃ were obtained.Characterization techniques used included powder X-ray diffraction, differential thermal analysis, thermogravimetric analysis, second harmonic generation, and infrared spectroscopy.Out of the total of 16 crystalline iodate structures occurring for all the lanthanides, single crystals were obtainable in 11, comprising a total of 54 compounds.Including all the lanthanides (plus Y, less Pm), the x_N groups of isostructural compounds, with the number of compounds in parentheses, were the following: 6(1), 5_I(4), 5_II(2), 4(9), amorphous with 5 ? x ? 0 (15), 2_I(3), 2_II(9), 1(4), $\text{1}\text{2}\text{(2)}$, O_I(14), O_II(2), O_III(4), O_IV(3), O_V(4), and O_VI(1).     

Ein neuartiges Iod(III,V) Gemischtvalentes Iodoxopolykation in (IO2)3 HSO4

A Novel Iodine(III, V) Mixed Valent Iodinepolyoxocation in (IO₂)₃HSO₄ Previously unknown (IO₂)₃HSO₄ is formed by action of firstly conc. H₃PO₄ upon HIO₃ or H₅IO₆ at 310–330° C, and subsequently of conc. H₂SO₄ at room temperature. Its crystal structure (Pna2₁; a = 8.907(3), b = 20.464(6), c = 9.784(4) Å; Z = 8; 4354 diffractometer data; R = 0.087, R_w = 0.056) contain the novel polymeric cation (IO₂0_3nⁿ⁺. Iodine(III) is coordinated square-planar by oxygen, iodine(V trigonal- pyramidal. The HSO₄- anions are interconnected via hydrogen bonds. Raman and IR spectra are reported.     

REI5O14 (RE=Y and Gd): Promising SHG Materials Featuring the Semicircle‐Shaped I5O143− Polyiodate Anion

The first examples of rare‐earth polyiodates, namely, REI₅O₁₄ (RE=Y and Gd), have been prepared by hydrothermal reactions of RE₂O₃ and H₅IO₆ in H₃PO₄ (≥85 wt % in H₂O), with extremely high yields (>95 %). They crystalize in the polar space group Cm and feature a brand‐new semicircle‐shaped [I₅O₁₄]^3? pentameric polyiodate anion composed of two IO₃ and three IO₄ polyhedra. Remarkably, both compounds exhibit very large second‐harmonic generation (SHG) signals (14× and 15×KH₂PO₄ (KDP) upon 1064 nm laser radiation for Y and Gd compounds, respectively). Our work shows that the hydrothermal reaction in a phosphoric acid medium facilitates the formation of rare‐earth polyiodates.     

New thallium iodates—Synthesis, characterization, and calculations of Tl(IO3)3 and Tl4(IO3)6, [Tl3Tl(IO3)6]

Two new thallium iodates have been synthesized, Tl(IO₃)₃ and Tl₄(IO₃)₆ [Tl⁺₃Tl³⁺(IO₃)₆], and characterized by single-crystal X-ray diffraction. Both materials were synthesized as phase-pure compounds through hydrothermal techniques using Tl₂CO₃ and HIO₃ as reagents. The materials crystallize in space groups R-3 (Tl(IO₃)₃) and P-1 (Tl₄(IO₃)₆). Although lone-pairs are observed for both I⁵⁺ and Tl⁺, electronic structure calculations indicate the lone-pair on I⁵⁺ is stereo-active, whereas the lone-pair on Tl⁺ is inert.     

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.     

Über die Existenz Polymerer Jodylionen (JO2+)x in den Verbindungen J2O5· n SO3 (n = 1,2,3) und JO2SO3F

On the Existence of Polymeric Iodyl Ions (IO₂⁺)_x in the Compounds I₂O₅ · n SO₃ (n = 1, 2, 3) and IO₂SO₃F The Raman spectra of I₂O₅ · SO₃, I₂O₅ · 2 SO₃ and I₂O₅ · 3 SO₃ are reported and interpreted together with the known spectrum of IO₂SO₃F. In first approximation the structure of the compounds is described by the existence of polymeric iodyl ions (IO₂⁺)_x. The bonds between cation and anion are not purely ionic but are in part covalent. These are formulated as coordinative bonds.     

Synthese und Kristallstruktur von Blei(II)‐oxidhalogenid‐Alkoholaten mit unterschiedlichen Verknüpfungsvarianten von Pb4O4‐Heterokubaneinheiten

Synthesis and Crystal Structure Determination of Lead(II) Oxide Halide Alcoholates with Different Connectivity of Pb₄O₄ Heterocubane‐like Subunits The reaction of red lead(II) oxide (Litharge) and lead(II) halide (Cl^? and Br^?) with diethylene glycole at a temperature of 180 °C leads to the isotypic compounds [Pb₆(C₄H₈O₃)O₂Cl₆] (1) and [Pb₆(C₄H₈O₃)O₂Br₆] (2) . In a similar synthesis with PbI₂ as educt at temperature of 160 °C the two modifications β‐[Pb₆(C₄H₈O₃)O₂I₆] (3) and α‐[Pb₆(C₄H₈O₃)O₂I₆] (4) were found, whereas at a reaction temperature of 180 °C [Pb₉(C₂H₄O₂)(C₄H₈O₃)O₃I₈] (5) was surprisingly obtained as product. The X‐ray diffraction data show that at a temperature of 180 °C a splitting of the ether took place. The cited compounds show cubane like subunits built by lead and oxygen atoms. These fragments are connected by alkoholate molecules. In 5 additionally an I₆ octahedra centered by lead is observed.     

Zur Kenntnis des Calciumbromats und - iodats,Kristallstruktur, röntgenographische,IR- und Raman-spektroskopische und thermoanalytische Untersuchungen

On Calcium Bromated and Iodates – Crystal Structure, X-Ray, IR and Raman Spectroscopical and Thermoanalytical Investigations The phase relationships (and both decomposition and disproportionation)of bromates and iodates of alkaline earth metals are studied by means of thermal analyses (DTA, DSC, TG) and (high-temperature) X-Ray, IR-, and (high-temperature) Raman spectroscopic measurements. The following compounds have been established: Ca(IO₃)₂ · 6 H₂O oF 216, the isotypic Ca(BrO₃)₂ · H₂O and Ca(IO₃)₂ · H₂O mP 48, Ca(IO₃)₂ I (Lautarit) mP 36, Ca(IO₃)₂ II and Ca(BrO₃)₂. The Crystal structure of Ca(IO₃)₂ · H₂O (brüggenite) (space group P2₁/c, Z = 4) has been determined by single crystal X-ray diffraction (MoKα). The final R value for 3888 reflections with I_o > 3σ₁ is 0.0487. The structures of bromates and iodates of alkaline earth metals known so far are discussed with respect to the energetic (mode frequencies) and geometric (bond lengths) distortion of the XO₃–ions as well as the strengths of H-bonds present in the respective hydrates.     

Synthesis and Structure of Ln2(H4IO6)(I2O10)·H3O·5 H2O (Ln=Pr,Nd, Sm), a Lanthanide Periodate Diperiodate

By slow evaporation of solutions containing Ln(ClO₄)₃ (Ln=Pr, Nd, Sm), H₅IO₆ and an excess of HClO₄, crystals of the title compounds could be obtained. Their structures were determined by single‐crystal X‐ray diffraction. The compounds crystallize in the monoclinic crystal system, space group I2/a. They contain two types of periodate ions: octahedral H₄IO₆ groups and two crystallographically different I₂O₁₀ groups, which consist of two edge‐sharing octahedra. These anions coordinate to the cations as bridging groups yielding a three‐dimensional network. Together with some water of crystallization, a coordination number of 9 is achieved around the lanthanide ions with a tri‐capped trigonal prismatic geometry.     

Syntheses, structures, and vibrational spectroscopy of the two-dimensional iodates Ln(IO3)3 and Ln(IO3)3(H2O) (LnYb, Lu)

The reaction of Lu³⁺ or Yb³⁺ and H₅IO₆ in aqueous media at 180 °C leads to the formation of Yb(IO₃)₃(H₂O) or Lu(IO₃)₃(H₂O), respectively, while the reaction of Yb metal with H₅IO₆ under similar reaction conditions gives rise to the anhydrous iodate, Yb(IO₃)₃. Under supercritical conditions Lu³⁺ reacts with HIO₃ and KIO₄ to yield the isostructural Lu(IO₃)₃. The structures have been determined by single-crystal X-ray diffraction. Crystallographic data are (MoKα, λ=0.71073 Å): Yb(IO₃)₃, monoclinic, space group P2₁/n, a=8.6664(9) Å, b=5.9904(6) Å, c=14.8826(15) Å, β=96.931(2)°, V=766.99(13), Z=4, R(F)=4.23% for 114 parameters with 1880 reflections with I>2σ(I); Lu(IO₃)₃, monoclinic, space group P2₁/n, a=8.6410(9), b=5.9961(6), c=14.8782(16) Å, β=97.028(2)°, V=765.08(14), Z=4, R(F)=2.65% for 119 parameters with 1756 reflections with I>2σ(I); Yb(IO₃)₃(H₂O), monoclinic, space group C2/c, a=27.2476(15), b=5.6296(3), c=12.0157(7) Å, β=98.636(1)°, V=1822.2(2), Z=8, R(F)=1.51% for 128 parameters with 2250 reflections with I>2σ(I); Lu(IO₃)₃(H₂O), monoclinic, space group C2/c, a=27.258(4), b=5.6251(7), c=12.0006(16) Å, β=98.704(2)°, V=1818.8(4), Z=8, R(F)=1.98% for 128 parameters with 2242 reflections with I>2σ(I). The f elements in all of the compounds are found in seven-coordinate environments and bridged with monodentate, bidentate, or tridentate iodate anions. Both Lu(IO₃)₃(H₂O) and Yb(IO₃)₃(H₂O) display distinctively different vibrational profiles from their respective anhydrous analogs. Hence, the Raman profile can be used as a complementary diagnostic tool to discern the different structural motifs of the compounds.     

Mixed Salt Cs2[I(OH)3O3] · CsSO4(H)H5IO6: Synthesis,Crystal Structure,and Properties

The mixed salt Cs₂[I(OH)₃O₃] · CsSO₄(H)H₅IO₆ (I) was synthesized for the first time, and its structure and properties were studied by X-ray diffraction, IR and Raman spectroscopies, impedance measurements and DTA method. It crystallizes in trigonal system: a = 7.503(2) Å, c = 16.631(3) Å, space group P3, Z = 2. The crystal structure consists of octahedral IO₆ and tetrahedral SO₄ fragments, linked by a three-dimensional network of hydrogen bonds, and of the Cs⁺ ions.     

Kristallstruktur,Infrarot‐ und Ramanspektren von Kupfertrihydrogenperiodatmonohydrat,CuH3IO6 · H2O

Crystal Structure, Infrared and Raman Spectra of Copper Trihydrogenperiodate Monohydrate, CuH₃IO₆ · H₂O The hitherto unknown compound CuH₃IO₆ · H₂O was studied by X‐ray, IR‐ and Raman spectroscopic methods. The crystal structure was determined by X‐ray single‐crystal studies (space group P2₁2₁2₁, Z = 4, a = 532.60(10), b = 624.00(10), c = 1570.8(3) pm, R1 = 1.85%, 1559 unique reflections (I > 2σ(I))). Isolated, meridionally configurated H₃IO₆^2– ions are coordinated to the copper ions forming double‐ropes in [100]. These ropes are connected in [010] and [001] by hydrogen bonds. The copper ions possess a square pyramidal co‐ordination with the hydrate H₂O on top. The infrared and Raman spectra as well as group theoretical treatment are presented and discussed with respect to the strength of the hydrogen bonds and the co‐ordination of the CuO₅₍₊₁₎ polyhedra and the H₃IO₆^2– ions at the C₁ lattice sites. The hydrogen bonds of the H₂O molecules and H₃IO₆^2– ions (HO–H…O–IO₅H₃ and H₂IO₅O–H…O–IO₅H₃) greatly differ in strength, as shown from both the respective O…O distances: 282.6 and 298.6 pm (H₂O), and 258.8, 259.7, and 270.9 pm (H₃IO₆^2–) and the OD stretching modes of isotopically dilute samples: 2498 and 2564 cm^–1 (90 K) (HDO), and 1786, 2024, and 2188 cm^–1 (H₂DIO₆^2–). The IO stretching modes of the H₃IO₆^2– ions (696–788 cm^–1 and 555–658 cm^–1, 295 K) display the different strength of the respective I–O and I–O(H) bonds (r_I–O: 181.1–188.3 pm and 189.2–194.5 pm).     

Quantum-Chemical Simulation of the Proton Transport in Mono- and Disubstituted Salts with Octahedral Anions

Salts Rb₂H₃IO₆, Rb₄H₆I₂O₁₂, and Rb₄H₂I₂O₁₀ and adducts CsHSO₄· H₆TeO₆ and Cs₂SO₄· H₆TeO₆ of the salt · acid type are calculated within density functional theory B3LYP. Calculations for Te, I, Rb, and Cs atoms make use of basis set LanL2DZ complemented by polarization d,p-functions and pseudopotential LanL2; for Li, O, and H atoms, basis set 6-31G** is used. The activation energy for the proton migration is commensurate with that for the water molecule abstraction in the salts and is smaller in rubidium salts than in cesium salts.