Published by De Gruyter

Volume 75 Issue 11 - Special issue dedicated to Professor Robert Glaum of the University of Bonn on the occasion of his 60th birthday

Issue of Zeitschrift für Naturforschung B

Contents
Journal Overview

Publicly Available November 12, 2020

Frontmatter

Page range: i-iv

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Publicly Available November 12, 2020

Editorial

August 6, 2020

Robert Glaum zum 60. Geburtstag gewidmet

Matthias Weil, Jörg Daniels, Rainer Pöttgen

Page range: 893-894

Research Articles

October 30, 2020

Structural transition and antiferromagnetic ordering in the solid solution CePd_1−xAu_xAl (x = 0.1–0.9)

Fabian Eustermann, Matthias Eilers-Rethwisch, Maximilian K. Reimann, Oliver Janka

Page range: 895-901

Abstract

The intermetallic solid solution CePd 1− x Au x Al ( x = 0.1–0.9) has been synthesized from the elements by arc-melting and subsequent annealing in induction followed by tube furnaces. The samples were characterized using the Guinier powder diffraction technique and the structures of the nominal compositions CeAuAl and CePd 0.2 Au 0.8 Al were refined from single crystal X-ray diffractometer data. For small values of x = 0.1–0.3, the compounds crystallize in the hexagonal ZrNiAl-type structure (space group P 6‾$‾{6}$2 m ), while for x = 0.5–0.9 the orthorhombic TiNiSi-type structure (space group Pnma ) was observed. In both structure types, the transition metal and aluminum atoms form a complex polyanionic network with the cerium atoms filling the respective cavities. The transition metal atoms are in both cases surrounded in the shape of a tri-capped trigonal prism, the connectivity of these units, however, is different. Temperature-dependent magnetic susceptibility measurements of all compounds indicated a stable trivalent oxidation state for the cerium atoms along with antiferromagnetic ordering around T N ∼ 3 K.

July 6, 2020

Ternary plumbides ATPb₂ (A = Ca, Sr, Ba, Eu; T = Rh, Pd, Pt) with distorted, lonsdaleite-related substructures of tetrahedrally connected lead atoms

Steffen Klenner, Judith Bönnighausen, Rainer Pöttgen

Page range: 903-911

Abstract

The plumbides Ca T Pb 2 ( T = Rh, Pd), Eu T Pb 2 ( T = Rh, Pd, Pt), Sr T Pb 2 ( T = Rh, Pd, Pt) and Ba T Pb 2 ( T = Pd, Pt) were obtained by direct reactions of the elements in sealed tantalum tubes in an induction furnace. The moisture sensitive polycrystalline samples were characterized by X-ray powder diffraction. They crystallize with the orthorhombic MgCuAl 2 -type structure, space group Cmcm . The structures of CaRhPb 2 ( a = 433.78(3), b = 1102.06(8), c = 798.43(6) pm, wR = 0.0285, 432 F 2 values and 16 variables) and EuPdPb 2 ( a = 457.24(5), b = 1158.27(13), c = 775.73(8), wR = 0.0464, 464 F 2 values and 16 variables) were refined from single crystal X-ray diffractometer data. The characteristic structural motif is the distorted tetrahedral substructure built up by the lead atoms with Pb–Pb distances of 326–327 pm in CaRhPb 2 and of 315–345 pm in EuPdPb 2 . With increasing size of the alkaline earth (Eu) cation, the lead substructure becomes more anisotropic with a shift of the [ T Pb 2 ] polyanions from three- to two-dimensional, leading to significantly increased moisture sensitivity. Temperature dependent magnetic susceptibility studies reveal Pauli paramagnetism for SrRhPb 2 , SrPtPb 2 , BaPdPb 2 and BaPtPb 2 . EuRhPb 2 and EuPdPb 2 are Curie–Weiss paramagnets with stable divalent europium as is also evident from 151 Eu Mössbauer spectra. EuRhPb 2 is a ferromagnet with T C = 17.7(2) K, while EuPdPb 2 orders antiferromagnetically at T N = 15.9 K. This is in agreement with the full magnetic hyperfine field splitting of the 151 Eu Mössbauer spectra at T = 6 K.

October 15, 2020

Intergrowth of niobium tungsten oxides of the tetragonal tungsten bronze type

Frank Krumeich

Page range: 913-919

Abstract

Since the 1970s, high-resolution transmission electron microscopy (HRTEM) is well established as the most appropriate method to explore the structural complexity of niobium tungsten oxides. Today, scanning transmission electron microscopy (STEM) represents an important alternative for performing the structural characterization of such oxides. STEM images recorded with a high-angle annular dark field (HAADF) detector provide not only information about the cation positions but also about the distribution of niobium and tungsten as the intensity is directly correlated to the local scattering potential. The applicability of this method is demonstrated here for the characterization of the real structure of Nb 7 W 10 O 47.5 . This sample contains well-ordered domains of Nb 8 W 9 O 47 and Nb 4 W 7 O 31 besides little ordered areas according to HRTEM results. Structural models for Nb 4 W 7 O 31 and twinning occurring in this phase have been derived from the interpretation of HAADF-STEM images. A remarkable grain boundary between well-ordered domains of Nb 4 W 7 O 31 and Nb 8 W 9 O 47 has been found that contains one-dimensionally periodic features. Furthermore, short-range order observed in less ordered areas could be attributed to an intimate intergrowth of small sections of different tetragonal tungsten bronze (TTB) based structures.

Open Access October 14, 2020

FeBiS₂Cl – A new iron-containing member of the MPnQ₂X family

Ina Remy-Speckmann, Thomas Bredow, Martin Lerch

Page range: 921-925

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Abstract

The new sulfochloride FeBiS 2 Cl is obtained as a black powder following a mechanochemical synthesis procedure. The product crystallizes in the orthorhombic space group Cmcm (no. 63) with lattice parameters a = 3.82142(7), b = 12.2850(2) and c = 9.2911(2) Å. While the iron atom has an octahedral coordination environment, the bismuth atom is coordinated in the form of a bicapped trigonal prism. Both cation polyhedra form alternating layers, for iron built up of corner sharing octahedra along the c axis and edge sharing ones along the a axis. The bismuth polyhedra are connected through shared faces along the c axis and common edges along the a axis. Because of the distribution of sulfur and chlorine on a mixed anion site, the bismuth atoms occupy split positions. Experimental observations are supported by theoretical calculations.

October 13, 2020

Thallium diphosphates

Matthias Weil, Berthold Stöger

Page range: 927-937

Abstract

Three thallium(I) diphosphates with compositions Tl 4 P 2 O 7 , Tl 2 H 2 P 2 O 7 , Tl 2 H 2 P 2 O 7 (H 2 O) 0.5 and the mixed-valent thallium(I,III) diphosphate Tl 2 P 2 O 7 (= Tl I Tl III P 2 O 7 ) were obtained from aqueous solutions using an ion-exchange resin (Tl 4 P 2 O 7 ), through thermal treatment of TlH 2 PO 4 at 190 °C and subsequent crystallization from aqueous solutions (Tl 2 H 2 P 2 O 7 , Tl 2 H 2 P 2 O 7 (H 2 O) 0.5 ), and from a phosphate flux at 220 °C (Tl 2 P 2 O 7 ). The crystal structures of monoclinic Tl 4 P 2 O 7 ( C 2/ c , Z = 4) and orthorhombic Tl 2 H 2 P 2 O 7 ( Pbca , Z = 8) are unique, whereas monoclinic Tl 2 H 2 P 2 O 7 (H 2 O) 0.5 ( C 2/ c , Z = 8) is isotypic with its potassium analogue, and triclinic Tl 2 P 2 O 7 ( P 1‾$‾{1}$, Z = 4) crystallizes in the TlInAs 2 O 7 structure type. The crystal structure of Tl 2 P 2 O 7 is related to that of In 2 P 2 O 7 (= In I In III P 2 O 7 ; P 2 1 / c , Z = 4) by a translationengleiche group-subgroup relationship ( t 2). IR spectra of Tl 4 P 2 O 7 , Tl 2 H 2 P 2 O 7 and Tl 2 P 2 O 7 are reported and discussed.

October 20, 2020

Behavior of beryllium halides and triflate in acetonitrile solutions

Nils Spang, Matthias Müller, William Augustinov, Magnus R. Buchner

Page range: 939-949

Abstract

The solution behavior of beryllium halides and triflate in acetonitrile was studied by NMR, IR and Raman spectroscopy. Thereby mononuclear units [(MeCN) 2 Be X 2 ] ( X = Cl, Br, I, OTf) were identified as dominant species in these solutions. The solid state structure of [(MeCN) 2 Be(OTf) 2 ] has been determined by X-ray diffraction. If only one equivalent of MeCN is used the dinuclear compounds [(MeCN)Be X 2 ] 2 ( X = Cl, Br, I) are formed. Partial halide and triflate dissociation into the monomeric complexes as well as the formation of hetero-halide complexes [(MeCN) 2 BeClBr], [(MeCN) 2 BeClI] and [(MeCN) 2 BeBrI] was observed.

Open Access October 12, 2020

Hydroflux syntheses and crystal structures of hydrogarnets Ba₃[RE(OH)₆]₂ (RE = Sc, Y, Ho–Lu)

Ralf Albrecht, Florian Graßme, Thomas Doert, Michael Ruck

Page range: 951-957

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Abstract

Colorless crystals of the barium rare earth hydrogarnets Ba 3 [ RE (OH) 6 ] 2 ( RE = Sc, Y, Ho–Lu) were synthesized under hydroflux conditions with KOH at about T = 200 °C starting from the respective RE 2 O 3 and Ba (NO 3 ) 2 . Single-crystal X-ray diffraction analysis on these distorted rhombic dodecahedra revealed the cubic space group Ia 3‾$‾{3}$ d (no. 230). The crystal structures of the hydrogarnets Ba 3 [ RE (OH) 6 ] 2 are discussed and compared with those of other hydrogarnets. The occurrence of additional reflections, which do not fulfill the reflection conditions of Ia 3‾$‾{3}$ d , is analyzed and described by Renninger or λ /2 effects. A correlation is established between the space group adopted by a hydrogarnet and characteristic interatomic distances. In addition, single-crystal structure data of the strontium indium hydrogarnet Sr 3 [In(OH) 6 ] 2 are provided.

October 28, 2020

Three of a kind? The non-isotypic triple CsCe[P₂Se₆], CsSm[P₂Se₆] and CsEr[P₂Se₆]

Beate M. Schulz, Pia L. Lange, Thomas Schleid

Page range: 959-967

Abstract

Three new compounds of the Cs Ln [P 2 Se 6 ] family with Ln = Ce, Sm and Er have been prepared and structurally characterized. Plate-shaped, amber-colored single crystals of these cesium lanthanoid(III) hexaselenodiphosphates(IV) were obtained by heating stoichiometric amounts of Ln , P and Se with CsCl as a reactive flux in fused silica ampoules at 800 °C for four days. CsCe[P 2 Se 6 ] crystallizes monoclinically in space group P 2 1 / c with a = 1297.86(9), b = 776.24(5), c = 1198.43(8) pm, β = 106.589(3)° and Z = 4. The structure is isotypic with that of KLa[P 2 Se 6 ], the Cs + cations being ten-fold coordinated by selenium atoms to form double layers of condensed [CsSe 10 ] 19− polyhedra. Ce 3+ resides in a nine-fold coordination and the [CeSe 9 ] 15− polyhedra also form double layers parallel to (100). CsSm[P 2 Se 6 ] crystallizes in the orthorhombic space group P 2 1 2 1 2 1 with a = 688.67(5), b = 754.48(5), c = 2215.21(15) pm and Z = 4. Its structure is isotypic with that of KY[P 2 Se 6 ] and the Cs + cations reside in an eleven-fold coordination of selenium atoms constituting monolayers of condensed [CsSe 11 ] 21− polyhedra within the (001) plane. Sm 3+ exhibits an eight-fold coordination sphere of selenium atoms and the [SmSe 8 ] 13− polyhedra are also linked to build up parallel monolayers. CsEr[P 2 Se 6 ] crystallizes in the monoclinic space group P 2 1 / c again, but forms its own structure type with the lattice parameters a = 753.81(5), b = 1281.92(9), c = 1276.47(9) pm and β = 106.898(3)° and Z = 4. The Cs + cations are twelve-fold coordinated by selenium atoms and erects a three-dimensional framework of condensed [CsSe 12 ] 23− polyhedra. The Er 3+ cations show seven selenium atoms as neighbors and the [ErSe 7 ] 11− polyhedra are edge-connected to form discrete dimers [Er 2 Se 12 ] 18− . All three structures have similar ethane-like [P 2 Se 6 ] 4– anions in staggered conformation with bond lengths of 219–226 pm for d (P1–P2) and 213–222 pm for d (P–Se), which connect the Cs + and Ln 3+ coordination polyhedra into three-dimensional crystal structures.

October 13, 2020

The crystal structure of ZrCr₂D_≈4 at 50 K ≤ T ≤ 200 K

Holger Kohlmann

Page range: 969-973

Abstract

Many Laves phases take up considerable amounts of hydrogen to form metallic Laves phase hydrides. They frequently undergo phase transitions driven by ordering phenomena for the hydrogen atom distribution. The cubic Laves phase ZrCr 2 takes up hydrogen to form a hydride with almost four hydrogen atoms per formula unit, which undergoes a phase transition to a monoclinic modification at a critical temperature T c = 250.2 K. Its crystal structure was refined based on neutron powder diffraction data on the deuteride (ZrCr 2 D 3.8 type [ T = 1.6 K, C 2/ c ]) at four temperatures in the range 50 K ≤ T ≤ 200 K. The monoclinic low-temperature modification features a strongly distorted square anti-prism ZrD 8 and three CrD 4 polyhedra with almost fully occupied deuterium sites in saddle-like, distorted tetrahedral and planar configurations. Zr–D distances are in the range 201.4(7) pm ≤ d (Zr–D) ≤ 208.5(8) pm and Cr–D distances in the range 172.9(7) pm ≤ d (Cr–D) ≤ 182.4(8) pm.

Open Access October 12, 2020

High-pressure synthesis and crystal structure of HP-Al₂B₃O₇(OH)

Daniela Vitzthum, Ingo Widmann, Markus Plank, Bastian Joachim-Mrosko, Hubert Huppertz

Page range: 975-981

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Abstract

Orthorhombic HP-Al 2 B 3 O 7 (OH) was synthesized in a Walker-type multianvil apparatus under high-pressure/high-temperature conditions of 12.4 GPa and 1200 °C, respectively. Its structure is isotypic to that of Ga 2 B 3 O 7 (OH) and has been determined via single-crystal X-ray diffraction at room temperature. HP-Al 2 B 3 O 7 (OH) crystallizes in the space group Cmce ( Z = 8) with the lattice parameters a = 10.3124(4), b = 7.3313(3), c = 10.4801(5) Å, and V = 792.33(6) Å 3 . The compound has also been characterized by IR and Raman spectroscopy.

October 15, 2020

New layered supertetrahedral compounds T2-MSiAs₂, T3-MGaSiAs₃ and polytypic T4-M₄Ga₅SiAs₉ (M = Sr, Eu)

Valentin Weippert, Arthur Haffner, Dirk Johrendt

Page range: 983-989

Abstract

The new supertetrahedral compounds M SiAs 2 , M GaSiAs 3 and mC / tI - M 4 Ga 5 SiAs 9 ( M = Sr, Eu) have been synthesized by solid-state reactions at high temperatures. The structures were determined by single crystal or powder X-ray diffraction. M SiAs 2 and M GaSiAs 3 crystallize in the monoclinic TlGaSe 2 - and RbCuSnS 3 -type structures, respectively (space group C 2/ c ). These are topologically hierarchical variants of the tetragonal HgI 2 -type structure with stacked layers of T2 or T3 supertetrahedra. The T4 compounds M 4 Ga 5 SiAs 9 are dimorphic and form new structure types in the space groups C 2/ c and I 4 1 / amd , respectively. The latter exhibits coinciding layer stacking as known from tetragonal HgI 2 . The T4 compounds close the gap between the longer known T2 types and the recently reported compounds with T5 and T6 supertetrahedra. Measurements of the optical band gap, electrical resistivity and Hall Effect support the semiconducting nature of M 4 Ga 5 SiAs 9 . Magnetization measurements confirm Eu 2+ in Eu 4 Ga 5 SiAs 9 and indicate ferromagnetism below T = 2 K.

November 4, 2020

Comparative photophysical study of Pt(II) complex-nanoclay hybrid materials as dry powders and hydrogels

Sathish Chatnahalli Gangadharappa, Cristian A. Strassert

Page range: 991-996

Abstract

The excited state properties of Pt(II) complexes are strongly influenced by their microenvironment and by intermolecular interactions. In this work, we investigated the photoluminescence of six Pt(II) complexes adsorbed onto a layered nanoclay, namely Laponite ® ( LAP ). The excellent water dispersibility and gel-forming nature of the LAP was exploited to achieve a class of versatile materials. In particular, we report on the comparative photophysics of the dry powders and the hydrogels. Steady-state and time-resolved photoluminescence spectroscopy were used to assess the role of structural features at molecular level on the interaction between the nanodiscs, which in turn affects the intermolecular coupling of the coordination compounds in the excited state.

November 4, 2020

Carbon subsulfide C₃S₂ – synthesis by flash vacuum pyrolysis and crystal structure determination

Petra Krieger-Beck, Jörg Daniels, Johannes Beck

Page range: 997-1004

Abstract

Carbon subsulfide C 3 S 2 can be produced on a preparative scale by flash vacuum pyrolysis (FVP). The precursor 5-(methylthio)-3 H -1,2-dithiole-3-thione (C 4 H 4 S 4 ) proved to be particularly suitable and yields up to 8% could be achieved on evaporation at T = 180 °C and pyrolysis of the vapour at 950 °C. The other precursors tested, C 4 S 6 and C 6 S 8 , were far less productive. Insight into the thermal conversion of C 4 S 6 was gained by isolation and structure determination of a new isomer of the sulur-carbon compound C 8 S 8 , which is formed on thermal treatment of C 4 S 6 at T = 330 °C. The formation of C 8 S 8 can be interpreted by sulfur cleavage from C 4 S 6 . Crystal growth by sublimation below 0 °C allowed for the determination of the crystal structure of C 3 S 2 . The five-atomic molecules are linear and arranged in a typical pattern analogous to the crystal structures of I 2 , CS 2 and CSe 2 . The reaction of C 3 S 2 with bromine is known to give C 3 Br 6 S 2 of yet unknown structure. By sublimation of C 3 Br 6 S 2 in air, 4,5-dibromo-1,2-dithiol-3-one (C 3 Br 2 OS 2 ) was obtained, representing the product of bromine abstraction and oxidation. This substantiates the former suggestion for C 3 Br 6 S 2 to have the structure of a hexabromodithiolane.

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Objective
Zeitschrift fuer Naturforschung B (ZNB) publishes novel research in all areas of inorganic chemistry, organic chemistry, and analytical chemistry. In particular, the journal focuses on solid state chemistry, coordination chemistry, main group element chemistry, synthetic organic chemistry, natural product chemistry and, to a lesser extent, on analytical chemistry. For more than 65 years Zeitschrift fuer Naturforschung B has been open to contributions from all fields of experimental and theoretical chemistry. Zeitschrift fuer Naturforschung B publishes 12 issues per volume/year. Sometimes double issues occur.

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Solid state chemistry
Coordination chemistry
Main group element chemistry
Organic chemistry
Natural product chemistry

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Volume 75 Issue 11 - Special issue dedicated to Professor Robert Glaum of the University of Bonn on the occasion of his 60th birthday

Issue of Zeitschrift für Naturforschung B

Frontmatter

In this issue

Robert Glaum zum 60. Geburtstag gewidmet

Structural transition and antiferromagnetic ordering in the solid solution CePd1−xAuxAl (x = 0.1–0.9)

Abstract

Ternary plumbides ATPb2 (A = Ca, Sr, Ba, Eu; T = Rh, Pd, Pt) with distorted, lonsdaleite-related substructures of tetrahedrally connected lead atoms

Abstract

Intergrowth of niobium tungsten oxides of the tetragonal tungsten bronze type

Abstract

FeBiS2Cl – A new iron-containing member of the MPnQ2X family

Abstract

Thallium diphosphates

Abstract

Behavior of beryllium halides and triflate in acetonitrile solutions

Abstract

Hydroflux syntheses and crystal structures of hydrogarnets Ba3[RE(OH)6]2 (RE = Sc, Y, Ho–Lu)

Abstract

Three of a kind? The non-isotypic triple CsCe[P2Se6], CsSm[P2Se6] and CsEr[P2Se6]

Abstract

The crystal structure of ZrCr2D≈4 at 50 K ≤ T ≤ 200 K

Abstract

High-pressure synthesis and crystal structure of HP-Al2B3O7(OH)

Abstract

New layered supertetrahedral compounds T2-MSiAs2, T3-MGaSiAs3 and polytypic T4-M4Ga5SiAs9 (M = Sr, Eu)

Abstract

Comparative photophysical study of Pt(II) complex-nanoclay hybrid materials as dry powders and hydrogels

Abstract

Carbon subsulfide C3S2 – synthesis by flash vacuum pyrolysis and crystal structure determination

Abstract

Structural transition and antiferromagnetic ordering in the solid solution CePd_1−xAu_xAl (x = 0.1–0.9)

Ternary plumbides ATPb₂ (A = Ca, Sr, Ba, Eu; T = Rh, Pd, Pt) with distorted, lonsdaleite-related substructures of tetrahedrally connected lead atoms

FeBiS₂Cl – A new iron-containing member of the MPnQ₂X family

Hydroflux syntheses and crystal structures of hydrogarnets Ba₃[RE(OH)₆]₂ (RE = Sc, Y, Ho–Lu)

Three of a kind? The non-isotypic triple CsCe[P₂Se₆], CsSm[P₂Se₆] and CsEr[P₂Se₆]

The crystal structure of ZrCr₂D_≈4 at 50 K ≤ T ≤ 200 K

High-pressure synthesis and crystal structure of HP-Al₂B₃O₇(OH)

New layered supertetrahedral compounds T2-MSiAs₂, T3-MGaSiAs₃ and polytypic T4-M₄Ga₅SiAs₉ (M = Sr, Eu)

Carbon subsulfide C₃S₂ – synthesis by flash vacuum pyrolysis and crystal structure determination