Abstract. AgBiI 4 and Ag 3 BiI 6 were synthesized by solvothermal reaction from AgI and BiI 3 in diluted HI-solution (20 %) at a temperature of 160°C. The greyish-black crystals grow as octahedra (AgBiI 4 ) or hexagonal/trigonal platelets (Ag 3 BiI 6 ). AgBiI 4 crystallizes in space group Fd3m with a ϭ 1222.3(1) pm (300 K) and Z ϭ 8 whereas Ag 3 BiI 6 shows the space group R3m with a ϭ 435.37(6) pm, c ϭ 2081.0(4) pm (300 K) and Z ϭ 1. Both crystal structures show stacking sequence abcabc... of hexagonal layers containing Iodine. Bismuth and silver are sharing octahedral sites with different mass ratio in both structures.

Structure D 2000Solvothermal Synthesis and Crystal Structure Determination of AgBiI 4 and Ag3BiI6.-Single crystals of the title compounds are prepared by hydrothermal reaction of AgI and BiI3 in the ratios 0.8:2 (AgBiI4) and 1:1 (Ag3BiI6) in 20% aq. HI (evacuated quartz tube, 160°C, 2-3 d). AgBiI4 crystallizes in the cubic space group Fd3m with Z = 8 and Ag3BiI6 in the trigonal space group R3m with Z = 1. Both crystal structures show stacking sequence -A-B-C-A-B-C-of hexagonal layers containing iodine. Bismuth and silver occupy octahedral sites with different mass ratio in both structures. The ionic conductivity of AgBiI4 is explored and the silver ion mobility in the compounds is discussed. -(OLDAG, T.; AUSSIEKER, T.; KELLER*, H.-L.; PREITSCHAFT, C.; PFITZNER, A.; Z. Anorg. Allg. Chem. 631 (2005) 4, 677-682; Anorg. Chem., Univ. Dortmund, D-44227 Dortmund, Germany; Ger., Abstr. Eng.) -Schramke 23-007

Structural Chemistry, Thermo Analysis, Vibration Spectrum of PbBr2 · 2 C2D6O2 and Solubility of PbBr2 in short Chain Polyethylene Glycoles Temperature dependent solubility data of PbBr2 in short chain polyethylene glycoles completed with X‐ray diffraction data of the deposit are discussed. Crystals of PbBr2 · 2 C2D6O2 (1,2‐Ethandiole, furthermore called ethylene glycole) have been synthesized and structurally characterized by single crystal X‐ray investigations and powder‐neutron diffraction. PbBr2 · 2 C2D6O2 crystallizes in the monoclinic space group C2/c (No. 15) with a = 10.0887(2) Å, b = 10.8580(2) Å, c = 9.0997(1) Å, β = 92.382(2)° and Z = 4 (powder‐neutron diffraction data, 193 K). The compound can be described as a rod packing. The rods are built of nearly planar  ∞1[PbBr4/2] units, surrounded by one ethylene glycol perpendicular to each side of the planar units. The linkage of these rods is realized by hydrogen bonds. A detailed description of hydrogen bonding in this compound is given.

The reaction of red lead(II) oxide (Litharge) and lead(II) halide (Cl Ϫ and Br Ϫ ) with diethylene glycole at a temperature of 180°C leads to the isotypic compounds [Pb 6 (C 4 H 8 O 3 )O 2 Cl 6 ] (1) and [Pb 6 (C 4 H 8 O 3 )O 2 Br 6 ] (2). In a similar synthesis with PbI 2 as educt at temperature of 160°C the two modifications β-[Pb 6 (C 4 H 8 O 3 )O 2 I 6 ] (3) and α-[Pb 6 (C 4 H 8 O 3 )O 2 I 6 ] (4) were found, whereas at a reaction temperature of 180°C [Pb 9 (C 2 H 4 O 2 )-(C 4 H 8 O 3 )O 3 I 8 ] (5) was surprisingly obtained as product. The X-ray

Dark grey (dark red with transmitting light) crystals of heptathallium(I) hexadecaiodo‐tribismuthate(III), Tl7Bi3I16, were obtained by slow cooling of a melt from 800 K to ambient temperature and, with higher crystal quality via solvothermal synthesis in aqueous HI by slowly cooling from 428 to 363 K. The compound is diamagnetic and melts congruently at 630(5) K. X‐ray diffraction on single‐crystals revealed that Tl7Bi3I16 crystallizes in the orthorhombic space group Cmcm with lattice parameters a = 2473.4(5), b = 1441.9(2), c = 3616.9(7) pm. The crystal structure can be interpreted as a layered intergrowth of fragments from the CsNiCl3 and K5Dy3I12 structure types with isolated [BiI6]3− octahedra and [Bi2I10]4− double octahedra. Rotation and distortion of the complex anions establish coordination numbers (c.n.) between 7 and 9 for the Tl+ cations. Dark red crystals of trithallium(I) hexaiodo‐bismuthate(III), Tl3BiI6, are only accessible via hydrothermal synthesis in aqueous HI and slowly cooling from 428 to 363 K. Thermal analysis reveals a peritectoid decomposition at 540(5) K into the neighboring phases Tl7Bi3I16 and TlI. Tl3BiI6 crystallizes in the monoclinic space group P21/c with lattice parameters a = 1352.6(3), b = 899.6(2), c = 1353.8(3) pm, and β = 104.18(3)°. In the crystal structure isolated [BiI6]3− octahedra are arranged according to the motif of a face‐centered pseudo‐cubic packing. Due to the tilted orientation of the [BiI6]3− groups the Tl+ cations have c.n. of 8 and 9. Although the crystal structure of Tl3BiI6 looks like a distorted variant of the elpasolith type, there is no symmetry relation according to a group subgroup formalism.