Volume 64, Issue 3

Beryllium difluoride BeF 2 reacts with liquid ammonia forming discrete diammine difluoro beryllium( II) [BeF 2 (NH 3 ) 2 ] molecules. The colorless compound crystallizes in the monoclinic space group P2 1 /c with a = 4.8815(2), b = 6.8528(3), c = 10.3690(5) Å, β = 92.01(1)◦, V = 346.65(3) Å 3 at 123 K with Z = 4. [BeF 2 (NH 3 ) 2 ] is the first structurally characterized example of a berylliumammonia complex. The compound has been investigated further by Raman, IR, and DTA-TG measurements and by quantum chemical ELF, AIM and NBO calculations. Graphical Abstract Beryllium Diammine Difluoride [BeF 2 (NH 3 ) 2 ]

While aging the reaction mixture of gadolinium tri-isopropoxide with acetylacetone (pentane-2,4- dione, acacH) in a 1 : 2 molar ratio in toluene for crystalisation, crystals of Gd 6 (μ 3 -OH) 6 (acac) 12 ・1.25 CHCl 3 (1) were obtained in high yield. The crystal structure analysis reveals that 1 has a M 6 O 12 core which is constituted of two distorted, tricapped, face-sharing cubane units (each with one missing edge) wherein the metal atoms are octacoordinated with a distorted square-antiprismatic geometry. In a sol-gel treatment the amorphous xerogel obtained from 1 was transformed into a nano-crystalline product at 600 °C while the xerogel of Gd(OPri) 3 under similar conditions required a heat treatment up to 900 °C for the same development. Graphical Abstract Synthesis and Structural Characterisation of a Hexanuclear Gd III Compound Gd 6 (μ 3 -OH) 6 (acac) 12 ·1.25 CHCl 3 as a Potential Precursor for Gd 2 O 3 Nanomaterials

A new polyoxotungstate complex [Na 2 (H 2 O) 8 ][Na 8 (H 2 O) 20 ][Cu(en) 2 ][W 12 O 42 ] ・3H 2 O (1) (en = ethylenediamine) has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy and TG analysis, together with a single crystal X-ray diffraction study. In compound 1, the Cu(en) 2 2+ complex cation links the [W 12 O 42 ] 12− anions to form a 1D chain, and the 1D chains are further interconnected with Na 8 (H 2 O) 20 8+ and Na 2 (H 2 O) 8 2+ cations to construct a new 3D framework. Graphical Abstract Synthesis and Crystal Structure of a New 3D Copper B-Paradodecatungstate Compound: [Na 2 (H 2 O) 8 ][Na 8 (H 2 O) 20 ][Cu(en) 2 ][W 12 O 42 ] · 3H 2 O

A new crown ether-POM (POM = polyoxometalate) adduct with the molecular formula [(C 14 - H 20 O 5 ) 4 (H 3 O) 3 ]PMo 12 O 40 ・ 0.5CH 3 CN (1) was isolated from the mixed solvent of acetonitrile and methanol. The adduct is constructed from Keggin [PMo 12 O 40 ] 3− anions and [(C 14 H 20 O 5 ) - (H 3 O + )] and [(C 14 H 20 O 5 ) 2 (H 3 O + )] cations via electrostatic and hydrogen bonding interactions. The supramolecular interactions combine the crown ether with oxonium ions. In the [(C 14 H 20 O 5 ) - (H 3 O + )] moieties, the oxonium ions reside out of the planes defined by the oxygen atoms of the crown ether. The [(C 14 H 20 O 5 ) 2 (H 3 O + )] moieties exhibit a sandwich structure. There exist hydrogen bonds between the oxonium ions of the [(C 14 H 20 O 5 )(H 3 O)] + cations and the acetonitrile molecules and the terminal and bridging oxygen atoms of the [PMo 12 O 40 ] 3− anions. The adduct has been used as a bulk-modifier to fabricate a chemically modified carbon paste electrode (MCPE), which displays well-defined cyclic voltammograms with three reversible two-electron redox couples in acidic aqueous solution, and electrocatalytic activities towards the reduction of H 2 O 2 and NO 2− . Graphical Abstract Synthesis, Crystal Structure and Electrochemical Properties of a New Adduct of Benzo-15-crown-5 and H 3 PMo 12 O 40

Ammonolysis of vanadium sulfide leads to the formation of bixbyite-type vanadium oxide nitrides. Small amounts of nitrogen incorporated in the structure result in the stabilization of the bixbyite type not known for vanadium oxides. The crystal structure was investigated using X-ray diffraction and X-ray absorption spectroscopy. At temperatures above 550 °C the powders decompose to corundumtype V 2 O 3 containing no detectable amount of nitrogen. Below 39 K magnetic ordering is observed. Graphical Abstract Synthesis, Crystal Structure and Magnetic Properties of Bixbyite-type Vanadium Oxide Nitrides

A new diimine Cu(I) complex, [Cu(DPEphos)(DPOP)]BF 4 ・CH 2 Cl 2 (1) (DPEphos = bis[2- (diphenylphosphino)phenyl]-ether, DPOP = 2-(11-dipyrido[3,2-a:2ʹ,3ʹ-c]phenazine)-5-p-tolyl-1,3,4- oxadiazole), has been synthesized and characterized by X-ray single-crystal diffraction analysis. In crystals of complex 1, the [Cu(DPEphos)(DPOP)]+ cations are arranged in supramolecular chains, just like a “zipper”. Cation layers and anion layers are alternating in this structure. The photophysical behavior of DPOP and 1 was studied. Graphical Abstract A New Blue-emitting Diimine Copper(I) Complex: Synthesis, Crystal Structure and Photophysical Properties

One-pot simultaneous debrominative decarboxylation and sulfamation of anti-2,3-dibromo-3-(4- chlorosulfonylphenyl)propanoic acid in DMF (for alkylamines) or DMF-pyridine (1/1, for arylamines) using a diverse range of alkyl and aryl amines under microwave irradiation stereoselectively afforded intermediate (Z)-4-(2-bromovinyl)benzenesulfonamides. The intermediates, without isolation and purification, were treated with EtONa to give the desired 4-ethynylbenzenesulfonamides. Graphical Abstract Efficient One-pot Synthesis of 4-Ethynylbenzenesulfonamides

N-Alkylnitrilium and N,N-dialkylcyanamidium salts 1 and 2 undergo ene reactions with cyanamides 4 to afford 2-azoniaallene salts 7 and 9 in which the N-alkylnitrilium salts 1 react as the ene, and the cyanamides 4 react as the enophile components. Competing with the ene reaction, N-alkylnitrilium salts 1 undergo [2++2+2] cycloaddition to furnish triazinium salts 8. 2-Azoniaallene salts react with alcohols to afford alkoxy amino derivatives 10 and 12, which yield iminium salts 11 and ketals/acetals upon further reaction with alcohols. The constitution of the 2-azoniaallene 7 and 9 and triazinium salts 8 was secured by elemental analyses and spectral properties (IR and NMR). Graphical Abstract On the Reaction of Cyanamides with N-Alkylnitrilium and N,N-Dialkylcyanamidium Salts

Triethylammonium 5-[(1,3-dimethyl-2,4,6-trioxo-tetrahydropyrimidin-5(6H)-ylidene)-(methylthio) methyl]-1,3-dimethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olate (5), obtained from 5-[bis (methylthio)methylene]-1,3-dimethyl-2,4,6(1H,3H,5H)-pyrimidinetrione (2) and 1,3-dimethylbarbituric acid in the presence of triethylamine, is protonated by methanesulfonic acid to give 5,5ʹ-(methylthiomethanediylidene)bis(1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione) (6) in good yield. Compound 6 is oxidized in two steps by m-chloroperbenzoic acid to give 5,5ʹ- (methylsulfinylmethanediylidene)bis(1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione) (7) and 5-[(1,3-dimethyl-2,4,6-trioxo-tetrahydropyrimidin-5(6H)-ylidene)(methylsulfinyl)methyl]-5-hydroxy- 1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione (8), respectively. Excess pyridine eliminates methanesulfinic acid from 8 to give the zwitterionic 5-[(1,3-dimethyl-2,4,6-trioxo-tetrahydropyrimidin- 5(6H)-ylidene(pyridinium-1-yl)methyl]-1,3-dimethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin- 4-olate (9). The crystal structures of compounds 6, 8, and 9 are reported. Graphical Abstract Elimination of a Thiomethyl Substituent from an Anionic 5-Methylenebarbituric Acid Derivative by Oxidation and Substitution

3-Substituted isocoumarins were prepared in a short and efficient way from 2-iodobenzoic acid and terminal alkynes in a one-pot Sonogashira reaction. Catalytic hydrogenation gave the corresponding dihydroisocoumarins. The cytotoxic activities of the resulting compounds against human leukaemia cell line (HL 60) were determined in a MTT assay, and structure-activity relationships are discussed. Graphical Abstract Short Approach Towards New Isocoumarins and Dihydroisocoumarins and Investigation of their Cytotoxic Activities

Three new sulfated oleanane-type saponins were isolated from the roots of Gypsophila trichotoma Wend. (Caryophyllaceae). Their structures were established as 3-O-sulfoechinocystic acid 28-β -glucopyranosyl ester (1), 3-O-sulfooleanolic acid 28-β -glucopyranosyl ester (2) and 3-Osulfoquillaic acid 28-β -glucopyranosyl ester (3) on the basis of chemical and spectral evidences. Graphical Abstract 3-O-Sulfo-triterpenoid Saponins from Gypsophila trichotoma Wend

A new bisabolene derivative (1S*, 2R*, 4R*, 7R*, 10R*)-1,7,10,11-tetrahydroxy-1,7,11-trimethyl- 4,10(H)-2-O-cinnamoyl-bisabol-8(9)-ene (1), together with cinnamic acid (2), methyl cinnamate (3), sodium cinnamate (4) and methyl elaidate (5) have been isolated from the leaves and barks of Fissistigma petelotii. Sodium cinnamate (4) was isolated for the first time from the nature. The structures of these compounds were elucidated by analysis of their IR, MS, 1D and 2D NMR spectra. Graphical Abstract Study on Chemical Constituents of the Vietnamese Medicinal Plant Fissistigma petelotii

The title compound (C 12 H 10 O 4 ) crystallizes in the triclinic space group P1̄ with a = 7.367(3), b = 8.1188(3), c = 9.549(5) Å, α = 74.034(1)°, β = 84.374(2)°, γ = 64.581(3)°, Z = 2, and d calc = 1.462 g cm −3 . It exhibits a strong intramolecular O-H··· O hydrogen bond and exists as the exocyclic enolic tautomer as it has been observed in solution. The structure is stabilized by C-H···π, C-O···π and π-π stacking interactions between benzene and pyran rings. Graphical Abstract Crystal Structure of 4-(1-Hydroxypropyl)- isochroman-1,3-dione

It is usually accepted that neutral phospholipids (PLs) generate singly positively charged ions, whereas negative PLs are easily detectable in the negative ion mode when analysed by matrix-assisted laser desorption and ionisation time-offlight mass spectrometry (MALDI-TOF MS). In this study, we demonstrate that some caution is required in the interpretation of MALDI-TOF mass spectra of PLs, since also neutral PLs have appeared to be detectable in the negative ion mode as well. Neutral and negatively charged phospholipids can generate adducts with the most commonly used matrix - 2,5-dihydroxybenzoic acid - yielding singly negatively charged ions that are detectable in the spectra. This further contributes to the complexity of the spectra and potentially leads to severe misinterpretation, particularly when unknown mixtures of PLs are analysed by MALDI-TOF MS. Graphical Abstract Detection of Adducts with Matrix Clusters in the Positive and Negative Ion Mode MALDI-TOF Mass Spectra of Phospholipids

The one-dimensional helical chain-like coordination polymer [Co(bpdc)(H 2 O) 3 ]・H 2 O (1) has been synthesized by hydrothermal reaction of pdon with Co(NO3)2・6H2O and Na2B4O7 (bpdc = 2,2ʹ-bipyridyl-3,3ʹ-dicarboxylate, pdon = 1,10-phenanthroline-5,6-dione). 1 crystallizes in the monoclinic space group P21/n with the cell parameters: a = 9.987(1), b = 9.238(1), c = 16.080(2) Å, β = 97.471(1)°, V = 1471.0(3) Å 3 , Z = 4. The bpdc ligand has resulted from an in situ carbon-carbon bond cleavage in the pdon ligand. The Co(II) atom is surrounded by two nitrogen atoms of the bpdc pyridyl groups and four O atoms, of which three belong to coordinated water molecules and one to a bpdc carboxylate group. The six-coordinated Co(II) atom adopts a distorted octahedral geometry. Compound 1 displays antiferromagnetic interactions. Above 30 K, χm −1 obeys the Curie- Weiss law with C = 3.12 cm 3 K mol −1 andΘ = −10.6 K. Graphical Abstract Structure and Magnetic Properties of a Single-strand Helical Cobalt(II) Coordination Polymer

The first organometallic zinc hydrazide-thiolate cluster, [(MeZn) 2 (PhSZn)(HNNMe 2 )(H 2 N-NMe 2 )(SPh) 2 ] 2 (1) has been prepared by alkane elimination from dimethylzinc solutions upon treatment with N,N-dimethylhydrazine and thiophenol and characterised by NMR spectroscopy, elemental analysis and single crystal X-ray diffraction. Compound 1 forms asymmetric aggregates containing a Zn 3 N 4 S 2 core. The core features rings with different connectivities. A seven-membered ZnSZnNNZnS ring comprises three fivemembered rings, two of a ZnSZnNN and one of a ZnNZnNN atom sequence. Intermolecular S···H bonding is observed in the crystal. Graphical Abstract An Organozinc Hydrazide-Thiolate Aggregate with a Zn 3 N 4 S 2 Core

The reaction of lithium 2-(dimethylamino)ethanolate with Me 2 SiCl 2 yielded a lithium chloride adduct of Me 2 Si- (OCH 2 CH 2 NMe 2 ) 2 . Despite the application of an excess of Me 2 SiCl 2 , the formation of ClMe 2 SiOCH 2 CH 2 NMe 2 was not observed. [Me 2 Si(OCH 2 CH 2 NMe 2 ) 2 ・Li 2 Cl 2 ] was characterised by NMR spectroscopy and determination of its crystal structure by X-ray diffraction. In the solid state it forms endless chains consisting of Li2Cl2 rhombi, with the lithium atoms chelated by the O and N atom of one OCH 2 - CH 2 NMe 2 substituent of Me 2 Si(OCH 2 CH 2 NMe 2 ) 2 units. Graphical Abstract A Coordination Polymer of Bis-[2-(dimethylamino)ethanolato]dimethylsilane with a Lithium Chloride Dimer

Nano-TiO 2 as an efficient, eco-friendly and reusable catalyst was applied for the one-pot synthesis of β -acetamido ketones. In this improved procedure, an aryl aldehyde, an aryl ketone, acetyl chloride and acetonitrile were condensed in the presence of the catalyst at room temperature. Graphical Abstract Nano-TiO 2 : an Eco-friendly and Re-usable Catalyst for the One-pot Synthesis of β-Acetamido Ketones

The synthesis of a monoterpene-based para-toluenesulfonamide is reported starting from naturally occurring (R)- (−)-carvone (1), by 1,2-addition of HCN followed by reduction with lithium aluminum hydride to afford the amino alcohols 3a and 3b. Tosylation of thismixture with p-toluenesulfonyl chloride furnished sulfonamide 4 in 55% overall yield. Compound 4 was evaluated in behavior animal models to investigate its effects on the central nervous system. It showed low toxicity and sedative action in mice, indicating it to be psychoactive. It also caused a decrease in the spontaneous motor activity of mice. This depressant effect was confirmed in the acetic acid-induced writhing test, which demonstrated a significant antinociceptive response more potent than 1. The present results provide evidence that sulfonamide 4 has analgesic-like psychopharmacological activity. Graphical Abstract Synthesis and Analgesic-like Effect of (6R, 4S)-p-Mentha-1,8-dien-6-ylmethylene- p-toluenesulfonamide

Five samples of solid solutions GdRu x Cd 1−x extending up to x ≈ 0.25 were synthesized by induction-melting of the elements in sealed tantalum tubes. According to X-ray powder diffraction data, the GdRu x Cd 1−x samples crystallize with the cubic CsCl structure. The structures of two crystals were refined from diffractometer data: Pm3̄m, a = 372.41(4) pm, wR2 = 0.0363, 45 F 2 , 5 variables for GdRu 0.10 (1)Cd 0.90 (1) and a = 367.70(4) pm, wR2 = 0.0301, 39 F 2 , 5 variables for GdRu 0.20 (1)Cd 0.80 (1). The cadmium-ruthenium substitution has a drastic effect on the magnetic properties. All samples order ferromagnetically, however, the Curie temperature decreases drastically from 258 K for GdCd to 63.6 K for GdRu 0.20 Cd 0.80 with a Vegard-type behavior. Graphical Abstract Drastic Decrease of the Curie Temperature in the Solid Solution GdRu x Cd 1–x

CeZnGe crystallizes with the hexagonal YPtAs-type structure, space group P63/mmc, a = 430.0(2), c = 1678.8(10) pm. A phase-pure sample was synthesized from the elements in a sealed tantalum crucible in a high-frequency furnace. Magnetic susceptibility measurements have revealed a trivalent cerium with an experimental magnetic moment of 2.67(1) μ B /Ce atom. Ferromagnetic ordering sets in at T C = 4.6(2) K. Graphical Abstract Magnetic Ordering in CeZnGe