Published by De Gruyter

Volume 75 Issue 8

Issue of Zeitschrift für Naturforschung B

Contents
Journal Overview

Publicly Available September 11, 2020

Frontmatter

Page range: i-iv

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Publicly Available September 11, 2020

Research Articles

August 3, 2020

Na₂MgSnS₄ – a new member of the A₂^IB^IIC^IVX₄ family of compounds

Eva M. Heppke, Martin Lerch

Page range: 721-726

Abstract

A new member of the A 2 I B II C IV X 4 compound family, Na 2 MgSnS 4 , has been synthesized by ball milling of the binary sulfides SnS, Na 2 S, and MgS with elemental sulfur in a high-energy planetary mill, followed by annealing in an atmosphere of H 2 S ( T = 600 °C/3 h). Na 2 MgSnS 4 adopts the NaCrS 2 -type structure (rhombohedral, space group R 3¯$\overline{3}$ m ) with a = 3.7496(11) and c = 19.9130(6) Å. The Na atoms occupy Wyckoff position 3 b , whereas the Mg and Sn atoms are statistically distributed on the cation sites 3 a ; all cations are surrounded by six sulfur atoms.

August 18, 2020

Synthesis, crystal structure, luminescence, and photocatalytic properties of a 2D Cu(II) metal-organic frameworks based on 3,5-di(1H-benzimidazol-1-yl)pyridine and 4,4′-oxybis(benzoate) ligands

Chen Zhang, Jian-Qing Tao

Page range: 727-732

Abstract

A new Cu(II) metal-organic framework, [Cu(L)(OBA)·H 2 O] n ( 1 ) [H 2 OBA = 4,4′-oxybis(benzoic acid), L = 3,5-di(1 H -benzimidazol-1-yl)pyridine] was hydrothermally synthesized and characterized through IR spectroscopy, elemental and thermal analysis and single-crystal X-ray diffraction. Complex 1 is a four-connected uni-nodal 2D net with a (4 4 ·6 2 ) topology which shows an emission centered at λ ∼393 nm upon excitation at λ = 245 nm. Moreover, complex 1 possesses high photocatalytic activities for the decomposition of Rhodamine B (RhB) under UV light irradiation.

August 3, 2020

Synthesis and structural characterization of a three-dimensional two-fold interpenetrated coordination polymer constructed from bis(4-(1H-imidazol-1-yl)phenyl)methanone and 1,1ʹ-biphenyl-2,2ʹ-dicarboxylate ligands for cadmium(II)

Gao-Feng Wang, Shu-Wen Sun, Hong Sun, Bo-Hui Wei, Yan-Fei Zhao, Li-Xin Meng

Page range: 733-737

Abstract

A three-dimensional (3D) two-fold interpenetrated coordination polymer, {[Cd(bipmo)(bpda)]·1.25(H 2 O)} n ( 1 ), (bipmo = bis(4-(1H-imidazol-1-yl)phenyl)methanone, H 2 bpda = 1,1ʹ-biphenyl-2,2ʹ-dicarboxylic acid), was synthesized by a solvothermal method. It has been characterized by elemental analyses, infrared (IR) spectroscopy, and single-crystal X-ray diffraction. The topological structure of 1 consists of uninodal dia nets with two-fold penetration. The thermal stability and the luminescence properties of complex 1 were investigated.

August 22, 2020

Impact of aging on the hydration of tricalcium aluminate (C₃A)/gypsum blends and the effectiveness of retarding admixtures

Florian Andreas Hartmann, Johann Plank

Page range: 739-753

Abstract

In the production of concrete from cement powder and water, setting behavior of the slurry is determined by the formation of ettringite (Ca 6 Al 2 (OH) 12 · (SO 4 ) 3 · 26 H 2 O) from tricalcium aluminate (Ca 9 Al 6 O 18 , abbreviated C 3 A) and gypsum (CaSO 4 · 2 H 2 O). Due to the high reaction potential of cement and water, premature hydration can occur after unintentional exposure to moisture. Model binary mixtures of C 3 A and gypsum stored at 90% relative humidity and 35 °C produced ample amounts of ettringite, which subsequently reacted with atmospheric CO 2 to CaCO 3 , Al(OH) 3 and gypsum. Investigated were the two main polymorphs of tricalcium aluminate encountered in cement, pure, cubic C 3 A and orthorhombic C 3 A in which calcium is partially substituted by sodium or potassium. Alkali substituted C 3 A converted to ettringite faster and more completely than pure C 3 A. Ettringite from prehydration caused a seeding effect, which promotes crystal growth and accelerates bulk hydration of the C 3 A/gypsum mixtures. Set retarders commonly applied in cement were dissolved in the mixing water prior to hydration to investigate their ability to counteract this acceleration. Sodium gluconate merely delayed the crystal growth but does not prolong the hydration process overall. Potassium pyrophosphate retarded much more effectively by suppressing the seeding effect via removal of calcium ions from the hydration reaction.

August 10, 2020

Influence of meso-linker attachment on the formation of core···π interactions in urea-functionalized porphyrins

Keith J. Flanagan, Aoife A. Ryan, Brendan Twamley, Mathias O. Senge

Page range: 755-764

Abstract

The ability to cover the face of a porphyrin macrocycle selectively is an attractive feature for concepts such as catalysis and anion binding that is reliant on porphyrin core interactions. Herein, we have synthesized a family of mono-urea functionalized porphyrin complexes with intent to investigate their potential to form core···π interactions selectively to one face of the porphyrin macrocycle. By altering the distance between the urea moiety and the porphyrin through direct linkage or introducing a linker group we can control the formation of the core interactions. This is clearly seen in the crystal structure of 1-phenyl-3-(2-([10,15,20-triphenylporphyrinato]zinc(II)-5-yl)phenyl)urea where a unique face capping effect is demonstrated. In the crystal of this complex, there is a hydrogen-bonding network between the urea group and the axial methanol ligand forming head-to-tail aggregates with the Zn–O axis all molecules pointing in one direction.

August 26, 2020

Single-crystal investigation of Ce₅Ag_xGe_4−x (x = 0.1−1.08) with Sm₅Ge₄ type

Bohdana Belan, Dorota Kowalska, Mariya Dzevenko, Mykola Manyako, Roman Gladyshevskii

Page range: 765-768

Abstract

The crystal structure of the phase Ce 5 Ag x Ge 4− x ( x = 0.1−1.08) has been determined using single-crystal X-ray diffraction data for Ce 5 Ag 0.1 Ge 3.9 . This phase is isotypic with Sm 5 Ge 4 : space group Pnma (No. 62), Pearson code oP 36, Z = 4, a = 7.9632(2), b = 15.2693(5), c = 8.0803(2) Å; R 1 = 0.0261, w R 2 = 0.0460, 1428 F 2 values and 48 variables. The two crystallographic positions 8 d and 4 c show Ge/Ag mixing, leading to a slight increase in the lattice parameters as compared to those of the pure binary compound Ce 5 Ge 4 .

August 27, 2020

Wirt-Gast-Komplexe von [bfu.bfu.bfu]: Vorhersage von Ionenselektivitäten mittels quantenchemischer Rechnungen XIII

Ursula Palmer, Ralph Puchta

Page range: 769-775

Abstract

The CH 2 –O–C 2 H 4 –O–CH 2 moieties in Lehn’s cryptand [2.2.2] have been substituted by 2,2′-bifurane groups to get the cryptand [bfu.bfu.bfu]. The ion selectivity of this new cryptand was investigated by DFT calculations (RB3LYP/LANL2DZp, RB3LYP/LACVP*, RBP86/LANL2DZp and RBP86/LACVP*) based on model equations and analysis of the [M ⊂ bfu.bfu.bfu] n + cryptate structures. The cryptand [bfu.bfu.bfu] is best suited for the alkali cations Na + and K + , and the alkaline earth cation Sr 2+ followed by Ca 2+ . The cavity of [bfu.bfu.bfu] is thus similar to that in [phen.phen.phen] or [bpy.bpy.bpy]. The selectivity of [bfu.bfu.bfu] is due to the flexibility of the OCCO und CN···NC dihedral angles. The results are independent of the selected DFT methods.

August 12, 2020

Untersuchungen zur Polymorphie der Cäsium-Dodekahalogeno-closo-Dodekaborate Cs₂[B₁₂X₁₂] (X = Cl–I)

Ioannis Tiritiris, Kevin U. Bareiß, Thomas Schleid

Page range: 777-790

Abstract

Thermoanalytic DSC and temperature-dependent X-ray diffraction investigations on the cesium dodecahalogeno- closo -dodecaborates Cs 2 [B 12 X 12 ] ( X = Cl–I) have revealed solid-solid phase transitions from their trigonal room-temperature α -forms (e.g. α -Cs 2 [B 12 Cl 12 ]: a = 959.67(3) pm, c = 4564.2(2) pm, Z = 6, space group R 3¯$\overline{3}$) into cubic high-temperature modifications. The isotypic title compounds crystallize in the space group Pm 3¯$\overline{3}$ n (e.g. β -Cs 2 [B 12 Cl 12 ]: a = 1051.98(6) pm, Z = 2) with a W 3 O-type defect structure. The statistic occupation of six possible positions with only four Cs + cations results in a cation-deficient A 2 B arrangement for Cs 2 [B 12 X 12 ]. Upon cooling the β -phase, a third polymorph was observed, which also crystallizes in the cubic system, but now in the space group Ia 3¯$\overline{3}$ d (e.g. γ -Cs 2 [B 12 Cl 12 ]: a = 2102.2(3) pm, Z = 16), and has to be regarded as a phase with only a partially disordered cation substructure. In this crystal structure the [B 12 X 12 ] 2− anions exhibit a NaTl-type arrangement, in which the Cs + cations occupy suitable interstices. The phase transitions of the differently halogenated cesium salts follow no specific trend as the transition from the trigonal α - to the cubic β -form occurs at 178 °C for the chlorinated, at 270 °C for the iodinated and at 325 °C for the brominated examples. On further heating however, β -Cs 2 [B 12 I 12 ] starts to decompose at 945 °C first, followed by β -Cs 2 [B 12 Br 12 ] and β -Cs 2 [B 12 Cl 12 ] at 959 °C and 983 °C, respectively.

August 21, 2020

Das Ytterbium(III)-Oxidbromid-Oxidotellurat(IV) Yb₃O₂Br[TeO₃]₂

Steffen F. Meier, Philip L. Russ, Thomas Schleid

Page range: 791-797

Abstract

The ytterbium(III) oxide bromide oxidotellu-rate(IV) Yb 3 O 2 Br[TeO 3 ] 2 was obtained from a mixture of Yb 2 O 3 , YbBr 3 and TeO 2 in a molar ratio of 2:1:2 along with an excess of KBr as fluxing agent in evacuated fused silica ampoules after 10 days at T = 800 °C and subsequent slow cooling to room temperatures as colorless, plate-shaped single crystals. Its triclinic crystal structure ( a = 663.97(5), b = 697.46(5), c = 1080.15(8) pm, α = 105.102(3), β = 90.931(3), γ = 100.034(3)°; Z = 2, space group: P 1‾$‾{1}$) displays three crystallographically different Yb 3+ cations with coordination numbers of six, seven and eight. Six out of eight distinct oxygen atoms belong to two independent ψ 1 -tetrahedral [TeO 3 ] 2− anions, whereas the other two represent O 2− anions in tetrahedral coordination of four Yb 3+ cations each, not having any contact to tellurium. Condensed via common vertices and edges, these [OYb 4 ] 10+ tetrahedra form cationic layers ∞2${}_{\infty }{}^{2}${[O 2 Yb 3 ] 5+ }, which spread out parallel to the (001) plane. Two discrete [TeO 3 ] 2− groups and one Br − anion per formula unit take care of their three-dimensional interconnection along [001] and the overall charge balance of Yb 3 O 2 Br[TeO 3 ] 2 . Remarkable interactions between the lone pair of electrons at the Te 4+ cations of the ψ 1 -tetrahedral [TeO 3 ] 2− anions and those at the Br − anions are discussed.

Note

August 21, 2020

Sc₁₄Co_3.10In_2.59 – the representative of the Lu₁₄Co₃In₃ type with the smallest rare earth element

Nataliya L. Gulay, Yaroslav M. Kalychak, Rainer Pöttgen

Page range: 799-803

Abstract

The scandium-rich phase Sc 14 Co 3.10 In 2.59 has been synthesized by a direct reaction of the elements in a sealed tantalum ampoule in a high-frequency furnace. Single crystals were obtained by slow cooling of the product. The Sc 14 Co 3.10 In 2.59 structure was refined from single-crystal X-ray diffractometer data: Lu 14 Co 3 In 3 type, P 4 2 / nmc , a = 889.13(13), c = 2138.7(4) pm, wR 2 = 0.0483, 1636 F 2 values, and 64 variables. Sc 14 Co 3.10 In 2.59 completes the series of the rare earth metal-rich phases RE 14 Co 3 In 3 . The structure refinement revealed defects on the Co1 site (84.7(5)% occupancy on 8 g ) and a mixed occupancy of 59.1(7)% In1/40.9(7)% Co3 on the 4 c site. The structure is built up by a dense condensation of Co@Sc 6 trigonal prisms and In2@InSc 11 and In1/Co2@Co 2 Sc 10 icosahedra. An interpenetration of the In2@InSc 11 icosahedra leads to dumb-bell formation with an In2–In2 distance of 289 pm. The Sc 14 Co 3.10 In 2.59 structure is stabilized by substantial Sc–Sc bonding (316–360 pm Sc–Sc).

About this journal

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.

Topics

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

Article formats
Original (full) papers, research notes and preliminary communications, reports on specific research topics of current interest (reviews)

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Volume 75 Issue 8

Issue of Zeitschrift für Naturforschung B

Frontmatter

In this issue

Na2MgSnS4 – a new member of the A2IBIICIVX4 family of compounds

Abstract

Synthesis, crystal structure, luminescence, and photocatalytic properties of a 2D Cu(II) metal-organic frameworks based on 3,5-di(1H-benzimidazol-1-yl)pyridine and 4,4′-oxybis(benzoate) ligands

Abstract

Synthesis and structural characterization of a three-dimensional two-fold interpenetrated coordination polymer constructed from bis(4-(1H-imidazol-1-yl)phenyl)methanone and 1,1ʹ-biphenyl-2,2ʹ-dicarboxylate ligands for cadmium(II)

Abstract

Impact of aging on the hydration of tricalcium aluminate (C3A)/gypsum blends and the effectiveness of retarding admixtures

Abstract

Influence of meso-linker attachment on the formation of core···π interactions in urea-functionalized porphyrins

Abstract

Single-crystal investigation of Ce5AgxGe4−x (x = 0.1−1.08) with Sm5Ge4 type

Abstract

Wirt-Gast-Komplexe von [bfu.bfu.bfu]: Vorhersage von Ionenselektivitäten mittels quantenchemischer Rechnungen XIII

Abstract

Untersuchungen zur Polymorphie der Cäsium-Dodekahalogeno-closo-Dodekaborate Cs2[B12X12] (X = Cl–I)

Abstract

Das Ytterbium(III)-Oxidbromid-Oxidotellurat(IV) Yb3O2Br[TeO3]2

Abstract

Sc14Co3.10In2.59 – the representative of the Lu14Co3In3 type with the smallest rare earth element

Abstract

Na₂MgSnS₄ – a new member of the A₂^IB^IIC^IVX₄ family of compounds

Impact of aging on the hydration of tricalcium aluminate (C₃A)/gypsum blends and the effectiveness of retarding admixtures

Single-crystal investigation of Ce₅Ag_xGe_4−x (x = 0.1−1.08) with Sm₅Ge₄ type

Untersuchungen zur Polymorphie der Cäsium-Dodekahalogeno-closo-Dodekaborate Cs₂[B₁₂X₁₂] (X = Cl–I)

Das Ytterbium(III)-Oxidbromid-Oxidotellurat(IV) Yb₃O₂Br[TeO₃]₂

Sc₁₄Co_3.10In_2.59 – the representative of the Lu₁₄Co₃In₃ type with the smallest rare earth element