Single crystals of the title compound, CaNa(2)(P(2)S(6))·8H(2)O, were obtained by adding calcium hydroxide to an aqueous solution of Na(4)(P(2)S(6))·6H(2)O. The structure is isotypic with that of its strontium analogue and consists of one Ca(2+) cation, two Na(+) cations, one-half of a centrosymmetric (P(2)S(6))(4-) anion with staggered confirmation and four water mol-ecules in the asymmetric unit. The crystal structure can be described as being built up from layers of cations and anions extending parallel to (101). Within a layer, each CaO(8) polyhedron is connected via edge-sharing to two NaO(4)S(2) octa-hedra and to one NaO(2)S(4) octa-edron. The NaO(4)S(2) octa-hedra are, in turn, linked with two (P(2)S(6))(4-) anions through common corners. Various O-H⋯S hydrogen-bonding inter-actions lead to cohesion of adjacent layers. The Ca(2+) and one Na(+) cation are situated on a twofold rotation axis and the second Na(+) cation is situated on an inversion centre.

The crystal structure of SrNa(2)(P(2)S(6))·8H(2)O is isotypic with that of its calcium analogue. The asymmetric unit consists of one Sr(2+) cation (2 symmetry), two Na(+) cations (2 and symmetry, respectively), one-half of a centrosymmetric (P(2)S(6))(4-) anion with a staggered confirmation and four water mol-ecules. The crystal structure is built up from layers of cations and anions extending parallel to (101). Each SrO(8) polyhedron is connected via edge-sharing to two NaO(4)S(2) octa-hedra and to one NaO(2)S(4) octa-hedron. The NaO(4)S(2) octa-edra are, in turn, connected with two (P(2)S(6))(4-) anions through common corners. Adjacent layers are held together by several O-H⋯S hydrogen-bonding inter-actions.

The thermal decomposition of Ni(NO3)2·6H2O (1), Ca(NO3)2·4H2O (2) and nitryl/nitrosyl nitrato nickelate(II), NO2/NO[Ni(NO3)3] (3), was investigated by thermogravimetric measurements with quasi-isothermal conditions and compared to Co(NO3)2·6H2O. The respective decomposition processes of 1 and 2 differ from each other showing that at one hand anhydrous Ca(NO3)2 was obtained whereas anhydrous nickel dinitrate has not be formed due to redox and condensation reactions. Instead basic nickel compounds have been formed. In reducing atmosphere nickel metal can be obtained. Anhydrous Ni(NO3)2 results by the thermal degradation of nitryl/nitrosyl nitrato nickelate. FT-Raman spectra have been of help in the judgement of the decomposition processes.

The new hexathiodiphosphate(IV) hydrates K-4[p(2)S(6)] (.) 4 H2O (1), Rb-4[P2SI] (.) 6 H2O (2), and CS4[P2S6] (.) 6 H2O (3) were synthesized by soft chemistry reactions from aqueous solutions of Na-4[P2S6] (.) 6 H2O and the corresponding heavy alkali-metal hydroxides. Their crystal structures were determined by single crystal Xray diffraction. K-4[P2S6] (.) 4 H2O (1) crystallizes in the monoclinic space group P2(1)/n with a 803.7(1), b = 1129.2(1), c = 896.6(1) pm, beta = 94.09(1)degrees, Z = 2. Rb-4[P2S6] (.) 6 H2O (2) crystallizes in the monoclinic space group P2(1)/c with a = 909.4(2), b = 1276.6(2), c = 914.9(2) pm, beta = 114.34(2)degrees, Z = 2. CS4[P2S6] (.) 6 H2O (3) crystallizes in the triclinic space group P 1 with a = 742.9(2), b = 929.8(2), c = 936.8(2) pm, alpha = 95.65(2), beta = 112.87(2), gamma = 112.77(2)', Z = 1. The structures are built up by discrete [P2S6](4-) anions in staggered conformation, the corresponding alkali-metal cations and water molecules. O (...) S and O (...) O hydrogen bonds between the [P2S6](4-) anions and the water molecules consolidate the structures into a three-dimensional network. The different water-content compositions result by the corresponding alkali-metal coordination polyhedra and by the prefered number of water molecules in their coordination sphere, respectively The FT-Raman and FT-IR/FIR spectra of the title compounds have been recorded and interpreted, especially with respect to the [P2S6](4-) group. The thermogravimetric analysis showed that K-4[P2S6] (.) 4 H2O converted to K-4[P2S6] as it was heated at 100 degrees C.

Abstract Single crystals of rubidium hexathiodiphosphate(V), Rb2P2S6, have been obtained and investigated by single crystal X-ray diffraction, and IR/FIR and Raman spectroscopy. The title compound crystallizes isotypically to the potassium, caesium and thallium analogues in the orthorhombic space group Immm (no. 71) with a = 8.485(3), b= 6.953(3), c =9.259(3 Å , and Z = 2, final R1= 0.0579 and wR2 = 0.0987. The crystal structure is characterized by discrete [P2S6]2− anions (edge-sharing double-tetrahedra) with D2h symmetry. Rubidium is coordinated by ten sulfur atoms forming a slightly distorted two-capped tetragonal prism with a coordination number CNRb 10. The FT-Raman and FT-IR/FIR spectra have been recorded and a factor group analysis was carried out.

H20O10P2S6Sr2, triclinic, P (1) over bar (no. 2), a = 8.353(1) angstrom, b = 9.130(1) angstrom, c = 12.788(2) angstrom, alpha = 92.29(1)degrees, beta = 101.47(1)degrees, gamma = 92.59(1)degrees, V = 953.6 angstrom(3), Z = 2, R-gt(F) = 0.034, wR(ref)(F-2) = 0.070, T = 223 K.

The thermal decomposition of Co(NO3)2·6H2O (1) as well as that one of NO[Co(NO3)3] (Co(NO3)2·N2O4) (2) was followed by thermogravimetric (TG) measurements, X-ray recording and Raman and IR spectra. The stepwise decomposition reactions of 1 and 2 leading to anhydrous cobalt(II)nitrate (3) were established. In N2 atmosphere, cobalt oxides are finally formed whereas in H2/N2 (10% H2) cobalt metal is produced. Rapid heating of cobalt(II)nitrate hexahydrate causes melting (formation of a hydrate melt) and therefore side reactions in the hydrate melt by incoupled reactions and evolution/evaporation of different species as, e.g., HNO3, NO2, etc. In case of larger amounts in dense packing in the sample container, the formation of oxo(hydoxo)nitrates is possible at higher temperature. For 2, its thermal decomposition to 3 was followed and its decomposition mechanism is proposed.

Graphite intercalation compounds (GICs) with the trichlorides of Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu have been prepared and characterized by chemical analysis and X-ray diffraction. Attempts to synthesize binary GICs with LaCl(3), CeCl(3), PrCl(3), and NdCl(3) failed. By heating mixtures Of YCl(3) + LnCl(3) (Ln = La - Lu) with graphite ternary GICs were obtained. The molar ratios LnCl(3):YCl(3) in the GICs were found to increase from La to Dy which runs parallel to the decrease in the ionic radii of the Ln(3+) ions.

Abstract Well-defined stage-1 nickel chloride-graphite intercalation compounds have been synthesized starting with stage-1 cadmium chloride-GIC and proceeding with a displacement reaction. Analysis of the samples gives the composition C 5.5 Ni Cd 0.01 Cl 2.13 and from X-ray diffraction d i = 933 pm. ESR measurements at X-band have been carried out on single crystals, as well as magnetization measurements with a SQUID magnetometer. The data are typical of a classical antiferromagnetic behavior ( T N = 21 K ), comparable to that of pristine NiCl 2 with lowered AF interactions and showing some peculiarities due to the presence of islands.

New graphite bi-intercalation compounds with BiCl3/H2SO4, InCl3/H2SO4 and BiCl3/AuBrx have been prepared. It could be proved that the insertion of bisulfate starts at each free interlayer gap at the same time. Furthermore two tri-intercalation compounds with BiCl3/AuBrx/H2SO4 and BiCl3/AuBrx/TlCl3, respectively, and a quadri-intercalation compound with BiCl3/AuBrx/TlCl3/H2SO4 could be obtained.