Volume 68, Issue 11

Bis(triphenylphosphine)gold(I) perrhenate [Ph 3 PAuPPh 3 ] + ReO 4 - has been prepared in high yield from Ph 3 PAuCl, Ph 3 P and AgReO4 in a mixed solvent. The compound is stable in air and decomposes at 235 °C. In the crystal structure, the two independent perrhenate anions are not approaching the gold centers of the two independent cations, but weak interionic interactions are entertained via π-π stacking of phenyl groups and C-H···O contacts. As three-blade chiral rotors, the Ph 3 P ligands of the cations are in a staggered conformation at the gold atoms with only slightly bent P-Au-P axes. IR and NMR data show no anomalies and are close to those of alkali or onium perrhenates. Graphical Abstract Bis(triphenylphosphine)gold(I) Perrhenate

Powderous crystalline materials of the composition Fe 3-x Mn x C have been prepared by first synthesizing Fe 3 C via mechanical alloying in a planetary mill followed by the addition of elemental manganese and arc-plasma melting or via the classic ceramic route in an electric furnace. The milling time for the synthesis of Fe 3 C was significantly reduced through adjusting the parameters of the planetary ball mill. When the ball-to-powder ratio was lowered, significantly larger batches were possible. Sintering in a fired tubular furnace was found to be the method of choice for the aftertreatment of the nanocrystalline Fe 3-x Mn x C powders as exemplified by X-ray Rietveld refinements. Graphical Abstract Tribosynthesis of Fe 3–x Mn x C Phases via Mechanical Alloying and Annealing

Single crystals of the new arsenide Eu 4 Ir 8 As 7 were grown from a lead flux. The structure was refined on the basis of single-crystal X-ray diffractometer data: Ca 4 Ir 8 P 7 type, P2 1 =m, a=1311.3(1), b = 408:4(1), c = 1360:3(1) pm, β = 98:45(1)°, wR2=0.0640, 1985 F 2 values, 95 variables. The iridium and arsenic atoms in the Eu 4 Ir 8 As 7 structure build up a complex three-dimensional, covalently bonded [Ir 8 As 7 ] network with Ir-As distances ranging from 239 to 260 pm. Each iridium atom has three or four arsenic neighbors in slightly distorted trigonal-planar or tetrahedral coordination. The four crystallographically independent europium atoms fill cavities of coordination numbers 12, 13, and 15 (2) within the [Ir 8 As 7 ] network. Parts of the Eu 4 Ir 8 As 7 structure resemble known simpler structure types, and one can describe the Eu 4 Ir 8 As 7 structure as an intergrowth variant of CaBe 2 Ge 2 -, TiNiSi- and AlB 2 -related slabs. Graphical Abstract Lead-flux Growth of Eu 4 Ir 8 As 7 Crystals

The ternary stannides PrZnSn and NdZnSn were synthesized by induction-melting of the elements in sealed tantalum tubes. They were characterized by powder and single-crystal X-ray diffraction: YPtAs-type structure, P6 3 =mmc, a = 455:4(1) and c = 1650:3(2) pm, wR2=0.0266, 297 F 2 for PrZnSn and a = 453:7(1) and c = 1637:0(4) pm, wR2=0.1558, 234 F 2 for NdZnSn with 12 variables per refinement. PrZnSn and NdZnSn are AlB 2 superstructures with slightly puckered and ordered [Zn 3 Sn 3 ] hexagons in AA´BB´ stacking sequence along the crystallographic c axis. Hydrogenation results in the new hexagonal hydrides PrZnSnH 1:5 (a = 447:98(8) and c = 1707:5(5) pm) and NdZnSnH 1:5 (a = 448:28(8) and c = 1689:8(2) pm). Filling of RE 3 Zn tetrahedra by hydrogen leads to anisotropic changes of the lattice parameters and a drastic flattening of the [Zn 3 Sn 3 ] layers. Temperature-dependent magnetic susceptibility measurements show Curie-Weiss behavior for PrZnSn and NdZnSn with experimental magnetic moments close to the free-ion values of RE 3+ . Magnetic ordering is detected at 4.7 (PrZnSn) and 6:5 K (NdZnSn). Hydrogenation induces ferromagnetism with increased ordering temperatures of 12.0 (PrZnSnH 1:5 ) and 14:5 K (NdZnSnH 1:5 ). Graphical Abstract From REZnSn to REZnSnH 1:5 (RE = Pr, Nd) – Inducing Ferromagnetism through Hydrogenation

The new rare-earth fluoride borates RE 2 (BO 3 )F 3 (RE=Tb, Dy, Ho) were synthesized under highpressure/ high-temperature conditions of 1:5 GPa=1200 °C for Tb 2 (BO 3 )F 3 and 3:0 GPa=900 °C for Dy 2 (BO 3 )F 3 and Ho 2 (BO 3 )F 3 in a Walker-type multianvil apparatus from the corresponding rareearth sesquioxides, rare-earth fluorides, and boron oxide. The single-crystal structure determinations revealed that the new compounds are isotypic to the known rare-earth fluoride borate Gd 2 (BO 3 )F 3 . The new rare-earth fluoride borates crystallize in the monoclinic space group P2 1 /c (Z = 8) with the lattice parameters a=16:296(3), b=6:197(2), c=8:338(2) Å , b =93:58(3)° for Tb 2 (BO 3 )F 3 , a= 16:225(3), b = 6:160(2), c = 8:307(2) Å , b = 93:64(3)° for Dy 2 (BO 3 )F 3 , and a = 16:189(3), b = 6:124(2), c = 8:282(2) Å , β= 93:69(3)° for Ho 2 (BO 3 )F 3 . The four crystallographically different rare-earth cations (CN=9) are surrounded by oxygen and fluoride anions. All boron atoms form isolated trigonal-planar [BO 3 ] 3- groups. The six crystallographically different fluoride anions are in a nearly planar coordination by three rare-earth cations. Graphical Abstract High-pressure Syntheses and Characterization of the Rare-earth Fluoride Borates RE 2 (BO 3 )F 3 (RE=Tb, Dy, Ho)

Using a hydrothermal synthesis method, two silver(I) complexes, [Ag(bbbm)(1,3-HBDC)] n (1) and [Ag(bbbm)(1,2-HBDC)] n (2) (bbbm = 1,1´-(1,4-butanediyl)bis-1H-benzimidazole, 1,3-H 2 BDC = 1,3-benzenedicarboxylic acid, 1,2-H 2 BDC = 1,2-benzenedicarboxylic acid), have been synthesized and characterized by elemental analysis, IR spectra, thermogravimetric (TG) analysis and singlecrystal X-ray diffraction. The silver centers display different environments with a distorted T-shaped geometry in 1, and a linear geometry in 2. Both chain structures of 1 and 2 are bridged by bbbm in a bis-monodentate coordination mode. 1 is further linked to generate a 3D supramolecular architecture via p-p stacking interactions and intermolecular O-H· · ·O hydrogen bonding. In 2, the ribbon-like chains are additionally assembled by two p-p stacking modes to form a layer motif. The photoluminescence of 1 and 2 was investigated in the solid state. 1 and 2 possess a remarkable activity for degradation of methyl orange by persulfate in a Fenton-like process. Graphical Abstract Synthesis, Structures, and Catalytic Properties of Two Silver(I) Coordination Polymers Constructed from 1,4-Bis(benzimidazolyl)butane

A heterometallic metal-organic complex (MOC), K[Co(1,10-phen) 2 (H 2 O)] 2 [BW 12 O 40 ]·2H 2 O (phen=1,10-phenanthroline) (1), has been synthesized hydrothermally and characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction. The complex exhibits cobaltbisupported tungstoborate units and potassium cations. The luminescence of the title complex has been investigated. Graphical Abstract A Heterometallic MOC Assembled from Cobalt-bisupported Keggin Subunits

An organic-inorganic hybrid based on the α-Keggin anion [BW 12 O 40 ] 5- , [Cu(BIIM) 2 ] {[Cu(BIIM) 2 (H 2 O)][Cu(BIIM) 2 BW 12 O 40 ]·3H 2 O} 2 (BIIM=2,2´biimidazole) (1) was hydrothermally prepared and characterized by elemental analysis, IR and UV spectra. Compound 1 is composed of [Cu(BIIM) 2 ] 2+ and [Cu(BIIM) 2 (H 2 O)] 2+ cations and a [Cu(BIIM) 2 BW 12 O 40 ] 3- polyanion, in which the [BW 12 O 40 ] 5- anion is decorated by one [Cu(BIIM) 2 ] 2+ cation through one terminal oxygen atom. These components are finally arranged through hydrogen bonds into a twodimensional network. Investigations of the intermolecular interactions by Hirshfeld surface and fingerprint plots indicate that besides the classical N-H···O hydrogen bonds, there are rare W- O(terminal)···π(imidazole ring) interactions stabilizing the structure. Graphical Abstract Synthesis, Structural Investigation and Characterization of an α-Keggin-based Organic-Inorganic Hybrid, [Cu(BIIM) 2 ]{[Cu(BIIM) 2 (H 2 O)][Cu(BIIM) 2 BW 12 O 40 ]·3H 2 O} 2 (BIIM = 2,2´-Biimidazole)

Two new isostructural complexes based on 2-(1H-imidazolyl-1-methyl)-1H-benzimidazole (imb) and di-anionic 1,4-benzenedicarboxylate (bdic), namely, {[Co(bdic)(imb) 2 (H 2 O) 2 ]·2H 2 O} n (1) and {[Ni(bdic)(imb) 2 (H 2 O) 2 ]·2H 2 O} n (2), have been synthesized and characterized by single-crystal Xray diffraction. Both complexes possess a chain structure with the di-anionic bdic groups bridging the metal ions. The imb ligands coordinate the metal ions in a monodentate mode at two sides of the main chain. These chains are further packed into 3D networks through five kinds of hydrogen bonds. The in vitro effect of 1 and 2 on cultured cardiac fibroblasts (CF) proliferation in the presence or absence of excessive angiotensin II (AngII) have been investigated by a flow cytometric assay. The results have indicated that both complexes have no obvious effect on the cell cycle distribution of CF, but they can suppress the CF proliferation induced by AngII. Graphical Abstract Syntheses of Two Co(II) and Ni(II) Complexes with 2-(1H-Imidazolyl-1- methyl)-1H-benzimidazole and 1,4-Benzenedicarboxylate Ligands and Their Effect on Cardiac Fibroblasts Proliferation

Three new lanthanide-organic frameworks {[Ln(L)(OClO 3 )(H 2 O)]·0.5H 2 O} n [Ln=Sm (1), Eu (2), Er (3)] have been prepared by hydrothermal reactions of the corresponding lanthanide oxide (Ln 2 O 3 ), silver perchlorate (AgClO 4 ) and 5-(imidazol-1-ylmethyl)isophthalic acid. The complexes have been characterized by single-crystal and powder X-ray diffraction, IR spectroscopy, and elemental analyses. In 1-3, the metal centers are eight-coordinated to show polyhedral coordination geometries with an LnO 8 donor set. The imidazolyl groups are free of coordination, and the perchlorate and carboxylate groups bridge the Ln 3+ cations leading to the formation of wave-like layer structures containing metal-chains. The fluorescence properties of complex 2 were investigated. Graphical Abstract Synthesis, Structure and Properties of Lanthanide-Organic Frameworks with Imidazolylmethylisophthalate Ligands

Two methods (MeOH/K 2 CO 3 , pyridine/Et 3 N) were assessed for the introduction of sulfur into the 2-position of 1,3-disubstituted quaternary imidazolium salts 1-9 (Cl, I, BF 4 , PF 6 , CH 3 OSO 3 were used as anions) to yield nine 1,3-disubstituted imidazoline-2-thiones 10-18 (1, 10: R 1 = CH 3 , R 2 = CH 3 ; 2, 11: R 1 = OCH 2 Ph, R 2 = CH 3 ; 3, 12: R 1 = OCH 3 , R 2 = CH 3 ; 4, 13: R 1 = OCH 3 , R 2 = OCH 3 ; 5, 14: R 1 = NH 2 , R 2 = CH 2 Ph; 6, 15: R 1 = NCHPh, R 2 = CH 3 ; 7, 16: R 1 = NH 2 , R 2 = CH 3 ; 8, 17: R 1 = NCHPh, R 2 = NCHPh; 9, 18: R 1 = NH 2 , R 2 = OCH 3 ). Compounds 11-18 represent N-alkyloxy and N-amino imidazoline-2-thiones, whereas 10 served as reference compound. The first method was advantageous for the conversion 1 → 10 due to faster reaction, whereas in the reaction 2 → 11 considerable amounts of by-products were formed. Pure thiones 11, 14, 16, 17, and 18 were obtained only by the second method. Both methods worked for the synthesis of the methoxy derivatives 12 and 13 from 3 and 4, and the benzylideneamino derivative 15 from 6. 1-Amino-3- methylimidazoline-2-thione (16) was also prepared by hydrolysis of the benzylideneamino derivative 15. Crystal structures of seven 1,3-disubstituted imidazoline-2-thiones were determined by singlecrystal X-ray diffraction. Intermolecular C-H···S contacts were identified and, additionally, N-H···S interactions in aminothiones 14 and 16. The 1H NMR shifts of 10 and 13 were satisfactorily correlated with the Kamlet-Abboud-Taft π* and b parameters in ten solvents. From the lack of correlation with the a parameter and from the C=S bond length (average 1.68 Å ) a significant contribution of a mesoionic imidazolium-2-thiolate resonance structure seems unlikely. Graphical Abstract Synthesis and Crystal Structures of New 1,3-Disubstituted Imidazoline-2-thiones

A series of previously unknown pyrimidin-2(1H)-ones containing chiral amino acid fragments was synthesized from 1,1,3,3-tetramethoxypropane and N-carbamoyl derivatives of amino acids under acidic conditions. Graphical Abstract Synthesis of Chiral Pyrimidin-2(1H)-ones from N-Carbamoyl Amino Acids

A new depsidone, namely chaetosidone A (1), together with six known fungal metabolites were obtained from a culture of Chaetomium sp., an endophytic fungus isolated from Zanthoxylum leprieurii leaves. The structure of the new compound 1 was elucidated using MS and NMR experiments, and by biosynthetic considerations. Chaetosidone A (1) is the missing link in the series of orsellinic acid-derived depsidones. Compound 1, corynesidone B (2) and corynether (3) displayed inhibitory effects on two Gram-positive bacteria, Bacillus subtilis and Staphylococcus aureus, at concentrations of 40 mg per paper disk and moderate toxicity towards brine shrimp larvae (Artemia salina). Graphical Abstract Depsidones from an Endophytic Fungus Chaetomium sp. Associated with Zanthoxylum leprieurii

The crystal structure of GdZn 3 was refined using singlecrystal X-ray diffraction data: YZn 3 type, space group Pnma, Z = 4, a = 6:7250(13), b = 4:4620(9), c = 10:201(2) Å , R 1 = 0:049, wR 2 = 0:082, 303 F 2 values, 25 variables. The zinc atoms build up a three-dimensional network with short Zn-Zn distances, while the Gd atoms are well separated from each other. The coordination number is 17 for Gd, and 10 and 12 for the Zn atoms. Graphical Abstract The Crystal Structure of GdZn 3

A new Tb(III) complex, [Tb(L) 3 (2,2´-bipy)(DMF)]·(2,2´- bipy) (1), has been synthesized with 2-benzoylbenzoic acid (HL) and 2,2´-bipyridine (2,2´-bipy) as ligands. In 1, the Tb(III) ion is coordinated by nine atoms to give a distorted tri-capped trigonal-prismatic geometry. The magnetic and fluorescence properties of 1 are discussed. Compound 1 is paramagnetic in the temperature range of 300 - 24 K, and when the temperature decreases from 22 to 2 K, it exhibits weak ferromagnetism. The compound shows four intense fluorescence emission bands arising from the transitions of Tb 3+ : 5 D 4 → 7 F 6 (492 nm), 5 D 4 → 7 F 5 (546 nm), 5 D 4 → 7 F 4 (590 nm) and 5 D 4 → 7 F 3 (622 nm) with an excitation wavelength of 315 nm. Graphical Abstract Crystal Structure, and Magnetic and Fluorescence Properties of a New Terbium(III) Complex, [Tb(L) 3 (2,2´-bipy)(DMF)]·(2,2´-bipy)