Zur Koordination des Aluminiums in den Calciumaluminathydraten 2 CaO · Al2O3 · 8 H2O und CaO · Al2O3 · 10 H2O

On the Coordination of Al in the Calcium Aluminate Hydrates 2 CaO · Al₂O₃ · 8 H₂O and CaO · Al₂O₃ · 10 H₂O By investigations with high-resolution ²⁷Al-NMR in solids it is shown that in the compound 2 CaO · Al₂O₃ · 8 H₂O the Al merely exist in octahedral coordination. According to this and considering its structural relationship with 4 CaO · Al₂O₃ · 19 H₂O the dicalcium aluminate hydrate is proposed to be formulated as [Ca₂Al(OH)₆][Al(OH)₃ (H₂O)₃]OH. Likewise for the compound CaO · Al₂O₃ · 10 H₂O the octahedral coordination of the Al is proved by ²⁷Al-NMR. This result corresponds with literature according to which a constitution as cyclohexaaluminate Ca₃[Al₆(OH)₂₄] · 18 H₂O is proposed.     

Zur Kenntnis von Na5HI2O10 · 14 H2O

On Na₅HI₂O₁₀ · 14 H₂O Single crystals of Na₅HI₂O₁₀ · 14 H₂O were obtained for the first time. According to the results of an X-ray crystal structure determination (P1 , a = 8.450(7), b = 8.533(6), c = 9.066(6) Å, α = 76.96(6), β = 62.94(5), γ = 86.98(6°, Z = 1, 4970 diffractometer data) iodine is in a distorted octahedral coordination. Two IO₆ polyhedra are connected by a common edge forming dimeric anions H₂I₂O₁₀^4?, the site symmetry is 1 . Sodium exhibits C.N. 6 (mainly hydrate). A 3-d network is formed largely by H-bonds.     

Zur Kenntnis des Bariumhexahydroxoplatinats BaPt(OH)6 · H2O

On Barium Hexahydroxoplatinate BaPt(OH)₆ · H₂O The crystal structure of BaPt(OH)₆ · H₂O, monoclinic, space group P2₁/m, a = 628.4, b = 624.6, c = 857.4 pm, β = 108.19°, Z = 2, contains octahedral Pt(OH)₆ groups and ninefold-coordinated barium. The water molecules are not coordinated to metal atoms but connected with Pt(OH)₆ groups only by very weak hydrogen bonds with oxygen-oxygen distances of 292—296 pm. The compound is dehydrated readily when dried gently. This explains contradictory evidence concerning its water content.     

Zur Kenntnis von Polymetaarseniten Darstellung und Kristallstruktur von BaAs2O4 · H2O

Concerning Polymetaarsenites. Preparation and Crystal Structure of BaAs₂O₄. H₂O BaAs₂O₄·H₂O was prepared by hydrothermal reaction of BaO with As₂O₃ at a temperatur of 200°C. An X-ray structural analysis demonstrated that the phase contains polymetaarsenite anions [As₄O₈^4?]_n, which adopt vierer single chains in the lattice. The relationship between the conformation of metaarsenite chains and cation size is discussed.     

Zur Abhängigkeit der Hydratation des CaO · Al2O3 von der Temperatur

On the Temperature Dependence of the Hydration of CaO · Al₂O₃ Using differential calorimetric analysis, ¹H-NMR spin-lattice-relaxation time measurements, and X-ray powder characterization of the hydration products it has been shown that the CaO · Al₂O₃ hydration in the range of 4 to 83°C proceeds via three different successively occurring principles.     

Kristallstrukturen von Säurehydraten und Oxoniumsalzen. XVI Zur Kenntnis der Verbindung H2TeI6 · 8 H2O

Crystal Structures of Acid Hydrates and Oxonium Salts. XVI. On the Compound H₂TeI₆ · 8 H₂O Crystals of H₂TeI₆ · 8H₂O are obtained as dark-brown needles with a metallic lustre in incident light from solutions of tellurium iodides in concentrated hydroiodic acid on cooling. Under standard conditions the phase is stable only in contact with its saturated solution; decomposition by formation of HI, H₂O, and TeI₄ takes place in vacuo. H₂TeI₆ · 8 H₂O is orthorhombic, space group Pnnm, Z = 2, with a = 12.672(15) Å, b = 10.825(14) Å, c = 8.322(8) Å. Structurally, the compound is to be described as bis(diaquooxonium)-hexaiodotellurate dihydrate, (H₇O⁺₃)₂[TeI^2?₆] · 2 H₂O. Isolated TeI^2?₆ octahedra are surrounded by a water structure which consists of disordered chains of hydrogen-bonded H₂O and H₇O⁺₃ species.     

Zu Herstellung und Konstitution der Verbindung 3 CaO · 3 GeO2 · H2O

On the Preparation and Constitution of the Compound 3 CaO · 3 GeO₂ · H₂O In the temperature range from 100–∽450°C it is possible to prepare under hydrothermal conditions from equimolar mixtures of CaO and GeO₂ the compound 3 CaGeO₃ · H₂O. By n.m.r. measurements of the solid compound it is shown, that there are only OH groups and no molecular water. It seems to be probable that this compound is a trigermanate of the formula Ca₃H₂ [Ge₃O₁₀].     

Zur Thermischen Zersetzung von CaOP3F · 2 H2O

On the Thermal Decomposition of CaPO₃F · 2H₂O . The thermal decomposition of CaPO₃F · 2H₂O was investigated by thermogravimetry under inert conditions. A parallel mass spectrometric analysis of gases produced is made. Using an effusion cell a quasi equilibrium evaporation in the nearness of the ion source of the spectrometer is achieved. The results are comparable with the thermogravimetric analysis under normal pressure. During first state of thermal decomposition one mole H₂O is lost. Then the further course is determined by release of HF and POF₃. The several steps of decomposition leading to α-Ca₂P₂O₇ at temperatures above 360° C are discussed.     

Kristallstrukturen des Sr(BrO3)2 · H2O,Ba(BrO3)2 · H2O,Ba(IO3)2 · H2O,Pb(CIO3)2 · H2O und Pb(BrO3)2 · H2O

Crystal Structure of Sr(BrO₃)₂ · H₂O, Ba(BrO₃)₂ · H₂O, Ba(IO₃)₂ · H₂O, Pb(ClO₃)₂ · H₂O, and Pb(BrO₃)₂ · H₂O The crystall structures of the isostructural halates Sr(BrO₃)₂ · H₂O, Ba(BrO₃)₂ · H₂O, Ba(IO₃)₂ · H₂O, Pb(ClO₃)₂ · H₂O, and Pb(BrO₃)₂ · H₂O were determined using X-ray single crystal data (monoclinic space group C2/c? C, Z = 4), The mean bond lengths and bond angles of the halate ions in the Ba(ClO₃)₂ · 1 H₂O-type compounds, which correspond to those of other halates, are Cl? O, 149.0, Br? O, 165.9, I? O, 180.2 pm, ClO₃^?, 106.4, BrO₃^?, 104.0, and IO₃^?, 99.6°. The structure data obtained are discussed in terms of possible orientational disorder of the water molecules, strengths of the hydrogen bonds, influence of the lead ions on the structure, and site group distortion of the halate ions.     

Zur Darstellung und Kristallstruktur von CrSO4 · 3 H2O

Preparation and Crystal Structure of CrSO₄ · 3 H₂O Evaporating a solution of Cr²⁺ in dilute sulphuric acid at 70°C light blue crystals of CrSO₄ · 3 H₂O were grown. Its x-ray powder diffraction pattern is quite similar to that of CuSO₄ · 3 H₂O. The crystal structure refinement of CrSO₄ · 3 H₂O (space group Ce, a = 5.7056(8) Å, b = 13.211(2) Å, c = 7.485(1) Å, β = 96.73(1)°, Z = 4) from single crystal data, using the parameters of the copper compound as starting values, results in a final R-value of R = 3.8%. The surrounding of the Cr²⁺ ion can be described as a strongly elongated octahedron. The basal plane of the CrO₆-octahedron consists of three hydrate oxygen atoms and one sulphate oxygen atom. The two more distant axial oxygen atoms also belong to sulphate groups. Thus they are forming chains of alterning CrO₆-octahedra and SO₄-tetrahedra along [110] and [1–10] linked via common corners. These chains are connected via sulphate groups and by bridging hydrogen bonds to a 3-dimensional network.     

Zur Chemie des Kanemits [NaHSi2O5 · 3 H2O]x

On the Chemistry of Kanemite [NaHSi₂O₅ · 3 H₂O]_x Starting from δ-Na₂Si₂O₅ Kanemit was prepared by a direct exchange of Na⁺ by H⁺ in water containing reaction mixtures. By ²⁹Si-, ²³Na- and ¹H-MAS-NMR investigations Kanemit was characterized as a layersilicate [NaHSi₂O₅ · 3 H₂O]. By thermal treatment as well as by dehydration at room temperature under vacuum conditions a monohydrate is formed in which the layerstructure remains nearly unchanged. At temperatures between 100 and 110°C under normal conditions a hydrate phase of the composition [NaHSi₂O₅ · 0.25 H₂O]_x is prepared in which a changed silicate-layerstructure exists.     

K2TiSi3O9·H2O

Single crystals of dipotassium titanium trisilicate hydrate were synthesized and the crystal structure was refined using data from single‐crystal X‐ray diffraction. The structure is a three‐dimensional mixed framework and contains channels formed by six‐ and eight‐membered rings. K⁺ ions and water mol­ecules are located in the channels.     

Über die Alkaliselenoarsenate(III) KAsSe3 · H2O,RbAsSe3 · 1/2 H2O und CsAsSe3 · 1/2 H2O

On the Alkali Selenoarsenates(III) KAsSe₃ · H₂O, RbAsSe₃ · 1/2 H₂O, and CsAsSe₃ · 1/2 H₂O The alkali selenoarsenates(III) KAsSe₃ · H₂O, RbAsSe₃ · 1/2 H₂O, and CsAsSe₃ · 1/2 H₂O have been prepared by hydrothermal reaction of the respective alkali carbonate with As₂Se₃ at a temperature of 135°C. Their X-ray structural analyses demonstrated that the compounds contain polyselenoarsenate(III) anions (AsSe₃^?)_n, in wich the basic units are ψ-AsSe₃ tetrahedra, which are linked together through Se? Se bonds into infinite zweier single chains. The Rb and Cs salts are isotypic.     

Zur Darstellung und Kristallstruktur der Thiotellurite BaTeS3 · 2 H2O und (NH4)2TeS3

Preparation and Crystal Structure of the Thiotellurites BaTeS₃·2H₂O and (NH₄)₂TeS₃ The new compounds BaTeS₃ · 2 H₂O and (NH₄)₂TeS₃ have been prepared and their structures determined. According to these the anion of the trithiotelluric acid in these compounds represents a distorted trigonal TeS?pyramid. The Te? S-distances are 2.34–2.36 Å. Crystallographic data see ?Inhaltsübersicht”?.     

Zur Kenntnis der Hydrate des Typs MX2 · 1 H2O mit M = Sr,Ba und X = Cl,Br, I. Kristallstrukturen des Strontiumchlorid-Monohydrats,SrCl2 · 1 H2O,und des Strontiumbromid-Monohydrats,SrBr2 · 1 H2O

On Hydrates of the Type MX₂ · 1 H₂O with M = Sr, Ba and X = Cl, Br, I. Crystal Structures of Strontium Chloride Monohydrate, SrCl₂ · 1 H₂O, and Strontium Bromide Monohydrate, SrBr₂ · 1 H₂O The structures of SrCl₂ · 1 H₂O, orthorhombic, Pnma, a = 1088.1(1), b = 416.2(1), c = 886.4(1) pm, Z = 4, d_c = 2.92 Mg m^?3, R = 0.052 for 755 reflections, and of SrBr₂ · 1 H₂O, orthorhombic, Pnma, a = 1146.4(1), b = 429,5(1), c = 922.9(1) pm, Z = 4, d_c = 3.88 Mg m^?3, R = 0.056 for 762 reflections have been determined from a Patterson synthesis and refined by Fourier and Least Squares methods. The structure consists of [SrX₂ = H₂O]_n-layers normal to [100] and Sr? H₂O? Sr? H₂O-chains parallel [010]. The Sr? O distances are 265.1(3) pm, SrCl₂ · 1 H₂O, and 265.9(4) pm, SrBr₂ · 1 H₂O. The shortest Sr? Cl and Sr? Br distances (298.9(1) and 315.3(1) pm) are within the layers. The environment of oxygen and strontium is a distorted tricapped trigonal prism. The orientation of the water molecules has been determined from vibrational spectroscopic measurements. The hydrogen atoms H₁ and H₂ form bifurcated hydrogen bonds of different strength to neighbouring halide ions. The corresponding O···X distances are 331.9(4) and 320.2(4) pm, SrCl₂ · 1 H₂O, and 340.8(4) and 333.8(4) pm, SrBr₂ · 1 H₂O. The other O? X distances are between 310.3(5) and 323.7(5) pm, SrCl₂ · 1 H₂O, and 323.5(5) and 333.2(6) pm, SrBr₂ · 1 H₂O.     

Calcium and strontium thio­sulfate,CaS2O3·6H2O and SrS2O3·5H2O

In contrast to former morphological studies, the results presented here show that calcium(II) thio­sulfate hexahydrate, CaS₂O₃·6H₂O, crystallizes centrosymmetrically in the pinacoidal class (point group ). The structure is characterized by chains, parallel to [100], of alternating S₂O₃ and Ca(H₂O)₆O₂ groups sharing common O atoms. The composition of each chain link is [Ca(H₂O)₆(S₂O₃)]. The geometry is analysed and compared in detail with the structural features of monoclinic strontium(II) thio­sulfate pentahydrate, SrS₂O₃·5H₂O, which forms layers, parallel to (100), of alternating S₂O₃ and Sr(H₂O)₄O₅ groups connected via common O atoms and O–O edges. Each layer contains [Sr(H₂O)₃O(S₂O₃)]_∞ as the unique repeat unit.     

Zur Struktur von zwei Hydraten des Natriumphenolats: C6H5ONa · H2O und C6H5ONa · 3 H2O

The Structures of two Hydrates of Sodium Phenoxide: C₆H₅ONa · H₂O and C₆H₅ONa · 3 H₂O In the monohydrate of sodium phenoxide sodium is coordinated by 4 oxygen atoms having an average distance Na? O of about 2.631 Å being arranged in form of a distorted tetrahedron. The oxygen atoms of water and phenoxid serve as bridging ligands. Hence, the structure can be considered as a network with a general formula [Na^[4]O]. Moreover, the oxygen atoms are linked via hydrogen bonding. In the trihydrate of sodium phenoxide sodium is surrounded with 5 oxygen atoms with an average distance of 2.39 Å forming a tetragonal pyramide. The oxygen of the phenoxide, however, does not participate in the coordination of the sodium ion. The coordination polyhedrons are connected by sharing edges and verteces. The resulting layer can be described by the general formula [Na^[5]O₂^[2]O^[2]O^[1]]. Via hydrogen bonding the phenoxide ions are attached to this layer.     

Crystal structures of hydrates of simple inorganic salts. III. Water‐rich aluminium halide hydrates: AlCl3·15H2O,AlBr3·15H2O,AlI3·15H2O,AlI3·17H2O and AlBr3·9H2O

Water‐rich aluminium halide hydrate structures are not known in the literature. The highest known water content per Al atom is nine for the perchlorate and fluoride. The nonahydrate of aluminium bromide, stable pentadecahydrates of aluminium chloride, bromide and iodide, and a metastable heptadecahydrate of the iodide have now been crystallized from low‐temperature solutions. The structures of these hydrates were determined and are discussed in terms of the development of cation hydration spheres. The pentadecahydrate of the chloride and bromide are isostructural. In AlI₃·15H₂O, half of the Al³⁺ cations are surrounded by two complete hydration spheres, with six H₂O in the primary and 12 in the secondary. For the heptadecahydrate of aluminium iodide, this hydration was found for every Al³⁺.     

MoCu3TeO7Cl2·0.5H2O

Single crystals of molybdenum(VI) tricopper(II) tellurium(IV) hepta­oxide dichloride hemihydrate, MoCu₃TeO₇Cl₂·0.5H₂O, were synthesized via a transport reaction in sealed evacuated silica tubes. All atoms occupy general positions within the triclinic () unit cell. The building units are irregular CuO₄Cl and CuO₃Cl₂ square pyramids, distorted TeO₃₊₁E trigonal bipyramids (E is the lone pair of Te^IV) and irregular MoO₅ pyramids. The TeO₃₊₁E, CuO₄Cl and CuO₃Cl₂ polyhedra form (110) layers bridged by Mo atoms. The water mol­ecules are located in [100] channels.