Pure samples of Na2TeS3 and Na2TeSe3 were synthesized by the reactions of stoichiometric amounts of the elements Na, Te, and Q (Q = S, Se) in the ratio 2:1:3. Both compounds are highly air- and moisture-sensitive. The crystal structures were determined by single-crystal X-ray diffraction. Yellow Na2TeS3 crystallizes in the space group P21/c. Na2TeSe3 exists in a low-temperature modification (Na2TeSe3-mP24, space group P21/c) and a high-temperature modification (Na2TeSe3-mC48, space group C2/c); both modifications are red. Density functional theory calculations confirmed the coexistence of both modifications of Na2TeSe3 because they are very close in energy (ΔE = 0.18 kJ mol(-1)). To the contrary, hypothetic Na2TeS3-mC48 is significantly less favored (ΔE = 1.8 kJ mol(-1)) than the primitive modification. Na2TeS3 and Na2TeSe3-mP24 are isotypic to Li2TeS3, whereas Na2TeSe3-mC48 crystallizes in its own structure type, which was first described by Eisenmann and Zagler. The title compounds have two common structure motifs. Trigonal TeQ3 pyramids form layers, and the Na atoms are surrounded by a distorted octahedral environment of chalcogen atoms. Raman spectra are dominated by the vibration modes of the TeQ3 units. The activation energies of the total conductivity of the title compounds range between 0.68 eV (Na2TeS3) and 1.1 eV (Na2TeSe3). Direct principal band gaps of 1.20 and 1.72 eV were calculated for Na2TeSe3 and Na2TeS3, respectively. The optical band gaps are in the range from 1.38 eV for Li2TeSe3 to 2.35 eV for Na2TeS3.

Li3SbS3 was synthesized by solid-state reaction of stoichiometric amounts of Li2S and Sb2S3 in the ratio 3:1. The product is air and moisture sensitive. The crystal structure was determined from single crystals at room temperature. Pale grey Li3SbS3 crystallizes in the orthorhombic space group Pna21 (no. 33) with a = 7.9671(5) angstrom, b = 6.7883(5) angstrom, c = 10.0912(8) angstrom, V = 545.76(7) angstrom 3, and Z = 4 (data at 20 degrees C). Antimony and sulfur atoms build isolated, trigonal pyramidal [SbS3]3 units, which are stacked along [100]. These [SbS3]3 units are connected by [LiSx]-polyhedra. The lithium ions have either a distorted tetrahedral coordination by sulfur in the case of Li2 and Li3 or a distorted square pyramidal environment in the case of Li1. The crystal structure is isotypic with Li3AsS3, which was obtained by reaction of stoichiometric amounts of lithium, arsenic, and sulfur in the ratio 3:1:3 in an excess of LiI. LiI serves only as a flux and is not incorporated in the crystal structure. Li3AsS3 crystallizes as colorless rods, space group Pna21 (no. 33) with a = 8.090(1) angstrom, b = 6.658(1) angstrom, c = 9.868(1) angstrom, V = 531.5(1) angstrom 3, and Z = 4 (data at 20 degrees C). Both compounds are confirmed as semiconductors with bandgaps close to 3 eV from DFT-calculations with GGA and hybrid functionals. Impedance spectroscopic measurements of Li3SbS3 show a specific conductivity of s = 1.6?x?109 O1 cm1 at 323 K and of s = 5.4?x?105 O1 cm1 at 573 K. The activation energy is EA = 0.72 eV. Raman spectra of Li3SbS3 are dominated by the stretching modes of the [SbS3]3 units at 333, 317, and 301 cm1 at room temperature.

AbstractSolvothermal Synthesis and Crystal Structure Determination of AgBiI4 and Ag3BiI6AgBiI4 and Ag3BiI6 were synthesized by solvothermal reaction from AgI and BiI3 in diluted HI‐solution (20 %) at a temperature of 160 °C. The greyish‐black crystals grow as octahedra (AgBiI4) or hexagonal/trigonal platelets (Ag3BiI6). AgBiI4 crystallizes in space group Fd3¯m with a = 1222.3(1) pm (300 K) and Z = 8 whereas Ag3BiI6 shows the space group R3¯m with a = 435.37(6) pm, c = 2081.0(4) pm (300 K) and Z = 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.The part of silver which could be localized varies with temperature. This behaviour indicates mobility of silver within the crystal structure. The ionic conductivity of AgBiI4 is explored. AgBiI4 and Ag3BiI6 show close structural relationship, with AgBiI4 as a variant with a higher degree of order.

Li2TeS3 and Li2TeSe3 were synthesized by the reaction of stoichiometric amounts of Li, Te and Q (Q = S, Se) in the ratio 2 : 1 : 3. Both products are extremely air and moisture sensitive. The crystal structures were determined by single crystal X-ray diffraction at room temperature. Red Li2TeS3 and metallic black Li2TeSe3 crystallize isotypically in the monoclinic space group P2(1)/c (no. 14) with four formula units per unit cell and the lattice parameters: Li2TeS3: a = 5.437(1) angstrom, b = 11.564(1) angstrom, c = 7.907(1) angstrom, beta = 91.57(1)degrees, V = 496.96(1) angstrom(3); Li2TeSe3: a = 5.658(1) angstrom, b = 12.032(1) angstrom, c = 8.278(1) angstrom, beta = 92.690(1)degrees, V = 562.93(1) angstrom(3) (data at 20 degrees C). The atomic arrangements persist of isolated trigonal pyramidal [TeQ(3)](2-) anions which are arranged in layers. Li is coordinated by six Q atoms from four (Li1) or five (Li2) different thiotellurate or selenidotellurate units, respectively. Impedance spectroscopic measurements in the temperature range 90 - 200 degrees C show that Li2TeS3 is a semiconductor with an activation energy of 0.71 eV Li2TeSe3 is a mixed conductor with an activation energy of 0.68 eV.

Li2TeS3 and Li2TeSe3 were synthesized by the reaction of stoichiometric amounts of Li, Te and Q (Q S, Se) in the ratio 2 : 1 : 3. Both products are extremely air and moisture sensitive. The crystal structures were determined by single crystal X-ray diffraction at room temperature. Red Li2TeS3 and metallic black Li2TeSe3 crystallize isotypically in the monoclinic space group P21/c (no. 14) with four formula units per unit cell and the lattice parameters: Li2TeS3: a 5.437(1) Å, b 11.564(1) Å, c 7.907(1) Å, β 91.57(1)°, V 496.96(1) Å3; Li2TeSe3: a 5.658(1) Å, b 12.032(1) Å, c 8.278(1) Å, β 92.690(1)°, V 562.93(1) Å3 (data at 20 °C). The atomic arrangements persist of

AgBiI4 and Ag3BiI6 were synthesized by solvothermal reaction from AgI and BiI3 in diluted HI-solution (20 %) at a temperature of 160 degrees C. The greyish-black crystals grow as octahedra (Ag-BiI4) or hexagonal/trigonal platelets (Ag3BiI6). AgBiI4 crystallizes in space group Fd (3) over barm with a = 1222.3(1) pm (300 K) and Z = 8 whereas Ag3BiI6 shows the space group R (3) over barm with a = 435.37(6) pm, c = 2081.0(4) pm (300 K) and Z = 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. The part of silver which could be localized varies with temperature. This behaviour indicates mobility of silver within the crystal structure. The ionic conductivity of AgBiI4 is explored. AgBiI4 and Ag-3. BiI6 show close structural relationship, with AgBiI4 as a variant with a higher degree of order.

Zeitschrift für anorganische und allgemeine ChemieVolume 630, Issue 11 p. 1753-1753 Poster Li2TeS3 und Li2TeSe3: Darstellung, Kristallstruktur und Impedanzspektroskopie Christian Preitschaft, Christian Preitschaft Institut für Anorganische Chemie, Universität Regensburg, Universitätsstraße 31, D-93040 RegensburgSearch for more papers by this authorArno Pfitzner, Corresponding Author Arno Pfitzner Institut für Anorganische Chemie, Universität Regensburg, Universitätsstraße 31, D-93040 RegensburgInstitut für Anorganische Chemie, Universität Regensburg, Universitätsstraße 31, D-93040 RegensburgSearch for more papers by this author Christian Preitschaft, Christian Preitschaft Institut für Anorganische Chemie, Universität Regensburg, Universitätsstraße 31, D-93040 RegensburgSearch for more papers by this authorArno Pfitzner, Corresponding Author Arno Pfitzner Institut für Anorganische Chemie, Universität Regensburg, Universitätsstraße 31, D-93040 RegensburgInstitut für Anorganische Chemie, Universität Regensburg, Universitätsstraße 31, D-93040 RegensburgSearch for more papers by this author First published: 31 August 2004 https://doi.org/10.1002/zaac.200470120Citations: 1AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article.Citing Literature Volume630, Issue11September 2004Pages 1753-1753 RelatedInformation

(LiL)(2)Li3SbS3 was prepared by solid-state reaction of stoichiometric amounts of Lil, Li, Sb, and S in the ratio 2 : 3 : I : 3. The product is air and moisture sensitive. The crystal structure was determined from single crystals at room temperature. Colourless to pale yellow (Lil)(2)Li3SbS3 crystallizes in the orthorhombic system, space group Pnnm (no. 58) with a = 10.436(l) Angstrom, b = 13.509(l) Angstrom, c = 7.530(l) Angstrom. V = 1061.6(l) Angstrom(3), and Z = 4 (data at 20 degreesC). The crystal structure of (Lil)(2)Li3SbS3 is closely related to that of (CuI)(2)Cu3SbS3 and (AgI)(2)Ag3SbS3, at least for the positions of 1, Sb, and S. Thus, iodine forms an eutactic arrangement which resembles the structure of hexagonal diamond. [SbS3](3-) units are embedded in this framework in a way that the sulphur atoms of two adjacent trigonal pyramids form distorted octahedral voids. The lithium ions are tetrahedrally coordinated and fully ordered within the anionic framework. The three-dimensional connectivities in (Lil)(2)Li3SbS3 are significantly different from the homologous copper and silver compound due to the bonding necessities of Li and slightly different radii of the monovalent cations. Thus, a novel three-dimensional network of edge sharing tetrahedra is observed in (Lil)(2)Li3SbS3. It exhibits strands of eight-membered rings of edge sharing tetrahedra which are linked by common vertices and cross linked by double tetrahedra.