Published by De Gruyter

Volume 70 Issue 12

Issue of Zeitschrift für Naturforschung B

Contents
Journal Overview

Publicly Available November 26, 2015

Frontmatter

Page range: i-iii

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Publicly Available November 26, 2015

In this Issue

Page range: i-iii

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Publicly Available September 24, 2015

Helical chain Ag(I) complexes with a tridentate N-donor ligand: syntheses, structural characterization, and properties

Chun-Hua Dai, Fu-Lin Mao

Page range: 851-856

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Abstract

The tridentate N-donor ligand 2,6-di(2-oxazolyl)pyridine (L) reacts with AgClO 4 and AgPF 6 to yield two new complexes, {[Ag 5 (L) 5 ](ClO 4 ) 5 } n ( 1 ) and {[Ag 5 (L) 5 ](PF 6 ) 5 } n ( 2 ), which have been characterized by single-crystal and powder X-ray diffractions, IR spectroscopy, and elemental and thermogravimetric analyses. Complexes 1 and 2 are isotypic, displaying helical chain structures. The fluorescence properties of 1 and 2 were investigated.

Publicly Available October 13, 2015

A 3D mixed-valence Cu(I)/Cu(II) coordination polymer constructed by 2-(2-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline and 1,3-benzenedicarboxylate

Zhi-Guo Kong, Sheng-Nan Guo, Bo Sun, Seik Weng Ng

Page range: 857-861

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Abstract

A mixed-valence Cu(I)/Cu(II) coordination polymer, namely, [Cu 2 (L)(1,3-BDC)] n ( 1 ), has been synthesized under hydrothermal conditions (HL = 2-(2-fluorophenyl)-1 H -imidazo[4,5- f ][1,10]phenanthroline and 1,3-H 2 BDC = 1,3-benzenedicarboxylic acid). Its structure has been determined by single crystal X-ray diffraction analysis and powder X-ray diffraction. The crystals are the monoclinic space group P 2 1 / c with a = 10.686(4), b = 17.376(8), c = 11.759(4) Å, β = 92.072(14)°, C 27 H 14 Cu 2 FN 4 O 4 , M r = 604.50, V = 2182.1(15) Å 3 , Z = 4, D calcd. = 1.84 g cm –3 , R = 0.0588 and wR = 0.1202 (all data). In complex 1 , the mixed-valence Cu(I)/Cu(II) atoms are linked by L and 1,3-BDC to give a rare 3D (3,3,4)-connected (4.7.9)(7.8.9)(4.7.8.9 3 ) framework. The temperature-dependent magnetic susceptibility of 1 was investigated in the temperature range of 2–300 K.

Publicly Available October 13, 2015

1,8-Naphthalimide derivative-based turn-off fluorescent probe for the detection of picrate in organic aqueous media

Huilu Wu, Cuiping Wang, Jiawen Zhang, Yanhui Zhang, Chengyong Chen, Zaihui Yang, Xuyang Fan

Page range: 863-869

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Abstract

The synthesis of a simple fluorescent naphthalimide-based receptor N -allyl-4-iminodi( N -butylacetamide)-1,8-naphthalimide 3 was carried out as a selective picrate (Pic – ) anion probe, and the detecting behavior of this probe was studied by fluorescence spectroscopy. In DMF solution, the interaction of compound 3 with different anions, including Pic – , F – , Cl – , Br – , I – , OH – , Ac – , NO 3 – , ClO 4 – , SCN – , SO 3 2– , SO 4 2– , H 2 PO 4 – , and HPO 4 2– , revealed significant fluorescence quenching only with the Pic – anion. By adding the picrate anions, green-yellow fluorescence emission quenches, which is easily observed by naked eyes under a 365 nm UV light irradiation. This phenomenon is essential for producing a highly selective and sensitive fluorescent probe for picrate anions. The probe can be applied to the quantification of Pic – with a linear range covering from 4.97 × 10 –6 to 6.82 × 10 –5 m and a detection limit of 5.8 × 10 –7 m . Most importantly, probe 3 has a high selectivity for picrate over competitive anions and picrate-containing analytes, which meet the selective requirements for practical application. Thus, the present results would be inspiring findings in the future design of reaction-based fluorescent turn-off probes for the environmentally relevant picrate probe.

Publicly Available October 13, 2015

Fluxional behaviour of tricyclo[2.2.1.0^2,6]heptaphosphide trisanion: a DFT investigation

Meha Bhargava, Pooja Maheshwari, Manjinder Kour, Raj K. Bansal

Page range: 871-878

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Abstract

The structures of the tricyclo[2.2.1.0 2,6 ]heptaphosphide trisanion, tricyclo[2.2.1.0 2,6 ]heptaphosphane triradical and their carbocyclic analogues have been investigated theoretically at the density functional theory (DFT) (B3LYP/6-31 + G*) level. The existence of negative hyperconjugation in these molecules could be established by natural bond orbital analysis. The weakening of the σ bonds combined with the possibility of the valence-shell expansion at the anionic charge carrying phosphorus atoms in the tricyclo[2.2.1.0 2,6 ]heptaphosphide trisanion induces a degenerate [2,2]sigmatropic rearrangement with a low energy barrier making all the phosphorus atoms equivalent, as detected by 31 P NMR experimentally. This energy barrier is enhanced in the presence of counterions. Its carbocyclic analogue trisanion fails to undergo a [2,2]sigmatropic rearrangement due to the inability of the anionic carbon centres to expand their valence shell. The tricyclo[2.2.1.0 2,6 ]heptaphosphane triradical and its carbocyclic analogue undergo a [2,2]sigmatropic rearrangement, as valence-shell expansion at the carbon atom is not required in this case. A lower activation energy barrier for the [2,2]sigmatropic rearrangement of the tricyclo[2.2.1.0 2,6 ]heptane triradical as compared to that for its phospha-analogue can be rationalised on the basis of the higher ring strain of cyclopropane than triphosphirane.

Publicly Available November 12, 2015

l-Valinate hydrates of nickel, copper and zinc – a structural study

Alexander Kämpfe, Fanny Lindner, Edwin Kroke, Jörg Wagler

Page range: 879-883

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Abstract

The l -valinates M (Val) 2 of M = Ni ( 1 ), M = Cu ( 2 ) and M = Zn ( 3 ) are easily obtained as crystalline hydrates. Their structural reinvestigation resulted in a general enhancement of precision for 1 · 2 H 2 O and 2 · H 2 O, in case of the copper complex in the correction of the previously reported space group and in case of the zinc complex 3 in the determination of the structure of a new hydrate 3 · 2 H 2 O.

Publicly Available October 13, 2015

Pyridinium ylides in the one-pot synthesis of a new quinoline/indolizine hybrid

Roumaissa Belguedj, Abdelmalek Bouraiou, Sofiane Bouacida, Hocine Merazig, Aissa Chibani

Page range: 885-887

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Abstract

The reaction of 1-(quinolin-2-ylmethyl)pyridinium ylide with dimethyl acetylenedicarboxylate was investigated. The X-ray crystallographic characterization of the new dimethyl 3-(quinolin-2-yl)indolizine-1,2-dicarboxylate ( 2 ) shows the formation of a five-membered ring between the pyridine ring and the methylene group.

Publicly Available September 8, 2015

Ternary aurides RE₄Mg₃Au₁₀ (RE = La, Ce, Pr) and RE₄Cd₃Au₁₀ (RE = Y, La–Nd, Sm, Gd–Dy) – ordering variants of the Zr₇Ni₁₀ type

Michael Johnscher, Theresa Block, Oliver Niehaus, Rainer Pöttgen

Page range: 889-896

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Abstract

The intermetallic gold compounds RE 4 Mg 3 Au 10 ( RE = La, Ce, Pr) and RE 4 Cd 3 Au 10 ( RE = Y, La–Nd, Sm, Gd–Dy) were obtained from the elements through high-frequency melting in sealed niobium tubes and subsequent annealing in a muffle furnace. The new aurides crystallize with the Ca 4 In 3 Au 10 -type structure. They were characterized through Guinier powder patterns. The structures of Pr 4.46 Cd 2.54 Au 10 and Tb 4.38 Cd 2.62 Au 10 were refined from single crystal X-ray diffractometer data: Cmce , a = 1396.73(6), b = 1009.38(3), c = 1019.51(3) pm, wR 2 = 0.0423, 1281 F 2 values, 47 variables for Pr 4.46 Cd 2.54 Au 10 and a = 1362.68(3), b = 995.52(4), c = 1003.79(3) pm, wR 2 = 0.0381, 1594 F 2 values, F 2 47 variables for Tb 4.38 Cd 2.62 Au 10 . The 8 e sites of both crystals show substantial Cd/Pr respectively Cd/Tb mixing, indicating small homogeneity ranges for all RE 4+ x Mg 3– x Au 10 and RE 4+ x Cd 3– x Au 10 aurides. The gold atoms in these aurides form a pronounced two-dimensional substructure (275–327 pm Au–Au in Pr 4.46 Cd 2.54 Au 10 ) which encages the Mg1/Cd1 (coordination number 8) and RE 2 (coordination number 11) atoms. These blocks are separated by the Mg2/Cd2 and RE 1 atoms with an intergrowth of Mg2/Cd2@Au 8 and RE 1@Au 10 polyhedra. Temperature dependent magnetic susceptibility and specific heat measurements of Tb 4 Cd 3 Au 10 have shown antiferromagnetic ordering at a Néel temperature of 12(1) K.

Publicly Available September 24, 2015

The structure of a coordination polymer constructed of manganese(II) biphenyl-4, 4′-dicarboxylate

Alexey Smeyanov, Martin Nieger, René Gustus, Wolfgang Maus-Friedrichs, Andreas Schmidt

Page range: 897-902

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Abstract

Manganese(II) biphenyl-4,4′-dicarboxylate, prepared by crystallization of a mixture of biphenyl-4,4′- dicarboxylic acid, manganese(II) chloride, and di(4-pyridyl)acetylene as base in a mixture of dimethylformamide, ethanol and water in a closed vessel at elevated temperatures forms a 3D network of {[Mn(bpdc)(H 2 O) 2 ][Mn(bpdc)(H 2 O)]} containing one five-fold coordinated and one six-fold coordinated Mn metal center (X-ray structure determination). Scanning tunneling microscopic (STM) measurements of manganese biphenyl-4,4′-dicarboxylate adsorbed on highly oriented pyrolytic graphite showed strands, the averaged diameter of which amounts to 18±1 nm, whereas the apparent height is about 0.5±0.02 nm.

Publicly Available September 10, 2015

Alkaline earth-gold-aluminides: synthesis and structure of SrAu₃Al₂, SrAu_2.83Al_2.17, BaAu_2.89Al_2.11 and BaAu_7.09Al_5.91

Birgit Gerke, Rainer Pöttgen

Page range: 903-909

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Abstract

New alkaline earth-gold-aluminides were synthesized from the elements in sealed tantalum or quartz ampoules in muffle furnaces at maximum annealing temperatures of 1325 K. The structures were refined from single crystal X-ray diffractometer data. SrAu 3 Al 2 crystallizes in an ordered version of the LT-SrZn 5 structure: Pnma , a = 1315.9(3), b = 549.0(1), c = 684.5(3) pm, wR 2 = 0.0232, 930 F 2 values, 35 variables. SrAu 2.83 Al 2.17 ( a = 1065.0(2), b = 845.0(2), c = 548.1(1) pm, wR 2 = 0.0416, 452 F 2 values, 22 variables) and BaAu 2.89 Al 2.11 ( a = 1096.1(3), b = 835.7(3), c = 554.0(1) pm, wR 2 = 0.0280, 501 F 2 values, 22 variables) both adopt the BaZn 5 type, space group Cmcm with Au/Al mixing on the 4 c site. The gold and aluminum atoms in both types form three-dimensional networks of condensed tetrahedra with the strontium and barium atoms in large cavities. BaAu 7.09 Al 5.91 is a new member of the NaZn 13 type: Fm 3̅ c , a = 1257.6(2) pm, wR 2 = 0.0267, 168 F 2 values, 12 variables. Both the 96 i and 8 b sites show Au/Al mixing. The crystal chemical details are discussed.

Publicly Available November 17, 2015

Phosphanchalkogenide und ihre Metallkomplexe. III. Halogenierungsprodukte der Gold(I)komplexe Ph₃PEAuX (E = S oder Se; X = Cl, Br oder I)

Christina Taouss, Peter G. Jones, Daniel Upmann, Dirk Bockfeld

Page range: 911-927

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Abstract

The complexes Ph 3 P E AuI ( E = S, Se; 1 , 2 ) were obtained from the reaction of Ph 3 P E AuCl with KI; they are appreciably less stable than their chloro and bromo analogues. The X-ray structures were determined, whereby 1 proved to be contaminated by a small amount of Ph 3 PS·I 2 . Oxidation of 1 and 2 with elemental iodine led to the adducts Ph 3 P E AuI·0.5I 2 ( 3 and 4 ), but X-ray investigation of a crystal initially assumed to be 3 proved it to be a 1:1 mixture of 3 with the adduct Ph 3 PS·1.5I 2 , while in 4 the iodine molecule was severely disordered, which prevented successful refinement of the structure. Decomposition of 4 by loss of gold led to Ph 3 PSeI 2 ·1.5I 2 4a . Complexes Ph 3 P E Au X ( E = S, Se; X = Br, Cl) were oxidized by elemental bromine ( X = Br) or PhICl 2 ( X = Cl) to Ph 3 P E Au X 3 ( 5 , 6 , 9 , 10 ); none of these X-ray structures could be refined satisfactorily because of diffuse scattering phenomena. Further oxidation led to the ionic compounds [Ph 3 P EX ] + [Au X 4 ] – ( X = Br, E = S, Se: 7 , 8 ; X = Cl, E = S, 11 ) or [Ph 3 PSeCl] + 0.5[Au 4 Cl 10 Se 2 ] 2– ( 12 ), containing the novel groupings P– E – X . X-ray structures confirmed the nature of all four of these compounds, which display longer P– E bonds than the gold(I) starting materials and short X···X and/or E···X contacts between cations and anions.

Publicly Available November 17, 2015

Synthesis and structural characterization of the new rare-earth borosilicates Pr₃BSi₂O₁₀ and Tb₃BSi₂O₁₀

Sebastian Bräuchle, Hubert Huppertz

Page range: 929-934

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Abstract

The rare-earth borosilicates RE 3 BSi 2 O 10 ( RE = Pr, Tb) were synthesized under high-temperature conditions of 1600 °C in a radio frequency furnace from praseodymium oxide, terbium oxide, silicon dioxide, silicon nitride, boron trioxide, and boric acid. The structure determinations based on powder diffraction data revealed that both phases RE 3 BSi 2 O 10 ( RE = Pr, Tb) are isotypic to Gd 3 BSi 2 O 10 [L. Chi, H. Chen, X. Lin, H. Zhuang, J. Huang, Jiegou Huaxue 1998 , 17 , 297]. The compounds crystallize in the orthorhombic space group Pbca (no. 61) with eight formula units and the lattice parameters a = 982.9(2), b = 714.2(2), c = 2314.4(4) pm, V = 1.6247(4) nm 3 , R p = 0.0231, and R wp = 0.0354 (all data) for Pr 3 BSi 2 O 10 and a = 960.5(5), b = 692.1(3), c = 2272.4(1) pm, V = 1.5106(2) nm 3 for Tb 3 BSi 2 O 10 . The lattice parameters of Tb 3 BSi 2 O 10 could be determined, but a final refinement of the powder data has not proved satisfactory. The structure of Pr 3 BSi 2 O 10 exhibits eight- (Pr1) and ninefold coordinated rare-earth cations (Pr2 and 3). Layers of ortho-silicate anions [SiO 4 ] 4– and borosilicate anions [BSiO 6 ] 5– are arranged alternatingly along the c axis and the RE cations are located in between.

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 70 Issue 12

Issue of Zeitschrift für Naturforschung B

Frontmatter

In this Issue

Helical chain Ag(I) complexes with a tridentate N-donor ligand: syntheses, structural characterization, and properties

Abstract

A 3D mixed-valence Cu(I)/Cu(II) coordination polymer constructed by 2-(2-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline and 1,3-benzenedicarboxylate

Abstract

1,8-Naphthalimide derivative-based turn-off fluorescent probe for the detection of picrate in organic aqueous media

Abstract

Fluxional behaviour of tricyclo[2.2.1.02,6]heptaphosphide trisanion: a DFT investigation

Abstract

l-Valinate hydrates of nickel, copper and zinc – a structural study

Abstract

Pyridinium ylides in the one-pot synthesis of a new quinoline/indolizine hybrid

Abstract

Ternary aurides RE4Mg3Au10 (RE = La, Ce, Pr) and RE4Cd3Au10 (RE = Y, La–Nd, Sm, Gd–Dy) – ordering variants of the Zr7Ni10 type

Abstract

The structure of a coordination polymer constructed of manganese(II) biphenyl-4, 4′-dicarboxylate

Abstract

Alkaline earth-gold-aluminides: synthesis and structure of SrAu3Al2, SrAu2.83Al2.17, BaAu2.89Al2.11 and BaAu7.09Al5.91

Abstract

Phosphanchalkogenide und ihre Metallkomplexe. III. Halogenierungsprodukte der Gold(I)komplexe Ph3PEAuX (E = S oder Se; X = Cl, Br oder I)

Abstract

Synthesis and structural characterization of the new rare-earth borosilicates Pr3BSi2O10 and Tb3BSi2O10

Abstract

Fluxional behaviour of tricyclo[2.2.1.0^2,6]heptaphosphide trisanion: a DFT investigation

Ternary aurides RE₄Mg₃Au₁₀ (RE = La, Ce, Pr) and RE₄Cd₃Au₁₀ (RE = Y, La–Nd, Sm, Gd–Dy) – ordering variants of the Zr₇Ni₁₀ type

Alkaline earth-gold-aluminides: synthesis and structure of SrAu₃Al₂, SrAu_2.83Al_2.17, BaAu_2.89Al_2.11 and BaAu_7.09Al_5.91

Phosphanchalkogenide und ihre Metallkomplexe. III. Halogenierungsprodukte der Gold(I)komplexe Ph₃PEAuX (E = S oder Se; X = Cl, Br oder I)

Synthesis and structural characterization of the new rare-earth borosilicates Pr₃BSi₂O₁₀ and Tb₃BSi₂O₁₀