Volume 67, Issue 12

The cubic structure of the sodium chromium alum [NaCr(SO 4 ) 2 (H 2 O) 12 ] has been published in 1968 with a lattice parameter a which is by 0.17 Å larger than the one of the potassium chromium alum. In order to investigate this “lattice parameter anomaly”, the growth of Na-Cr alum crystals was attempted with the aim to re-determine their structure. However, instead of cubic alum crystals, monoclinic crystals of composition NaCr(SO 4 ) 2 (H 2 O) 6 were obtained. Their structure consists of onedimensionally infinite [Na(SO 4 ) 2 ] 3- chains and “isolated” [Cr(H 2 O) 6 ] 3+ complexes, held together by electrostatic attraction and numerous hydrogen bonds. The compound is erroneously addressed as the sodium chromium alum in the Powder Diffraction File PDF-2. Graphical Abstract In Search of the True Structure of the Sodium Chromium Alum: Crystal Growth and Structure of the Double Salt NaCr(SO 4 ) 2 (H 2 O) 6

Dithiocarbamic acid reacts in the superacidic media HF/MF 5 (M = As, Sb) under formation of the corresponding salts H 2 NC(SH) 2 + MF 6 - . The colorless compounds are stable in an inert gas atmosphere up to -20 °C. The salts have been characterized by NMR, IR and Raman spectroscopy. Reactions in DF/AsF5 were carried out to obtain D 2 NC(SD) 2 + AsF 6 - in order to confirm the assignments of the observed vibrational modes. Additionally, quantum-chemical calculations of the free cation, [A 2 NC(SA) 2 ] + (A=H, D), and of the [A 2 NC(SA) 2 ( 3 HF)] + unit on the PBE1BPE/6-311G(3df,3pd) level of theory are discussed. Graphical Abstract The Protonation of Dithiocarbamic Acid in Superacids HF/MF5: Synthesis and Characterization of H 2 NC(SH) 2 + MF 6 – (M = As, Sb)

Single crystals of the germanides CeRh6Ge4 and CeRh2Ge2 were synthesized from the elements in bismuth fluxes. Polycrystalline samples are available by arc-melting. The structures were refined on the basis of single-crystal X-ray diffractometer data. CeRh 6 Ge 4 : LiCo 6 P 4 type, P 6 m 2 , a=715.4(2), c=385:5(1) pm, wR2=0.0554, 273 F 2 values, 19 variables; CeRh 2 Ge 2 : ThCr 2 Si 2 type, I4/mmm, a=415.69(6), c=1048:5(2) pm, wR2=0.0391, 131 F 2 values, 9 variables. The rhodium and germanium atoms build three-dimensional, covalently bonded [Rh 6 Ge 4 ] and [Rh 2 Ge 2 ] networks with Rh-Ge distances ranging from 246 to 255 pm. The cerium atoms are located in larger cavities within these networks: Ce@Ge 6 Rh 12 in CeRh 6 Ge 4 and Ce@Ge 8 Rh 8 in CeRh 2 Ge 2 . Temperature-dependent magnetic susceptibility data of CeRh6Ge4 show Curie-Weiss behavior above 70 K with an experimental magnetic moment of 2:35(1) μ B per Ce atom. Low-field measurements are indicative of magnetic ordering below 2:5 K. Graphical Abstract Bismuth Flux Growth of CeRh 6 Ge 4 and CeRh 2 Ge 2 Single Crystals

Hydrothermal reactions of (E)-4-(2-(1H-imidazol-4-yl)vinyl)benzoic acid (HL) with Cd(II) and Mn(II) salts yield the complexes [Cd(L) 2 ] (1) and [Mn(L) 2 ] (2), which have been characterized by single-crystal and powder X-ray diffraction, IR spectroscopy, and elemental and thermogravimetric analyses. Complexes 1 and 2 are isomorphous and isostructural, displaying an uninodal 4-connected 8-fold interpenetrating 3D dia framework architecture with (6 6 ) topology. These frameworks exhibit high thermal stability up to 400 °C. The luminescence and non-linear optical (NLO) properties were investigated. Graphical Abstract Eight-fold Interpenetrating Diamond-like Metal-Organic Frameworks Constructed with an N- and O-Donor Ligand for Cadmium(II) and Manganese(II)

The hydrothermal reaction of cobalt(II) nitrate hexahydrate with 5-(benzimidazol-1- ylmethyl)isophthalic acid (H 2 L) leads to the formation of a complex [Co(L)] (1). In the presence of 2-(pyridin-2-yl)-1H-benzimidazole (pybim) as an auxiliary ligand, a complex [Co(L)(pybim)]·H 2 O (2) was obtained. The complexes 1 and 2 have been characterized by single-crystal and powder X-ray diffraction, IR spectroscopy, and elemental and thermogravimetric analyses. Complex 1 shows a binodal (3,6)-connected 2D kgd network with (4 3 ) 2 (4 6 ·6 6 ·8 3 ) topology; 2 shows a chain structure, further linked together by hydrogen bonding and π-π interactions to give rise to a 3D supramolecular framework. Complexes 1 and 2 are examples of auxiliary ligand-assisted structural diversity. The frameworks of 1 and 2 display high thermal stability up to 400 °C. The magnetic properties of 1 were investigated. Graphical Abstract Synthesis, Characterization, and Magnetic Properties of Two New Co(II) Coordination Polymers with a Carboxylate- and Benzimidazolylcontaining Ligand

We report the first crystal structures of aniline complexes of silver, namely the three anilinecomplexed silver(I) disulfonylamides 1 (aniline)(dimesylamido)silver(I), 2 bis(aniline)(1,1,3,3- tetraoxo-1,3,2-benzodithiazolido)silver(I) and 3 bis(aniline)silver(I) [di(p-bromobenzenesulfonyl)- amide] : aniline (1 : 1). Compound 1 is molecular, with approximately linear coordination at silver; the coordination is extended to T-shaped by an Ag···O contact of 2.7136(11) Å to a neighbouring molecule related by a axis translation. Compound 2 is molecular, with trigonal planar coordination geometry at silver. Compound 3 is ionic, with exactly linear coordination at each of the two independent silver atoms, both of which occupy inversion centres; the third aniline is not coordinated to the silver atoms. Classical hydrogen bonds are the main feature of the packing diagrams for all three compounds. The packing of 1 and 2 can be analysed in terms of hydrogen-bonded dimers, further linked to form ribbons parallel to the a axis. In 3, the cations and anions are linked to form zigzag chains parallel to the b axis, and these are further linked to form a layer structure parallel to (001). The free aniline molecules are hydrogen bonded above and below the layer. Graphical Abstract Aminkomplexe von Silber(I)-disulfonylamiden, Teil II: Anilinkomplexe [1, 2]/ Amine Complexes of Silver(I) Disulfonylamides, Part II: Aniline Complexes

The structures of seven benzene derivatives [1,2,3-tri(bromomethyl)benzene, (1); 3,5- di(bromomethyl)bromobenzene, (2); 2,5-di(bromomethyl)bromobenzene, (3); 4-(bromomethyl)-2,5- dibromotoluene, (4); 4-(bromomethyl)bromobenzene, (5); 2,3-di(bromomethyl)bromobenzene, (6) and (bromomethyl)-p-dibromobenzene, (7)] with bromo and bromomethyl (and in one case methyl) substituents are presented and analysed in terms of Br···Br interactions up to 4.0 A° , supported by hydrogen bonds H···Br. Some interactions of the type Br···π and π···π are encountered and play a subordinate role in the packing. Despite the close chemical similarity of the compounds, some of which are isomers with permuted substituent positions, the packing motifs are highly variable. Compounds 2-5 are based on layer structures with Br n (n=3, 4) and/or mixed Br/C rings. Compounds 1, 6 and 7 display three-dimensional packings of differing complexity, but with interpretable substructures; 1 can be analysed in terms of ribbons of linked Br 3 and Br 4 rings; 6 displays chains of linked Br 3 triangles; 7 consists of ribbons of linked Br 4 quadrilaterals. Graphical Abstract X-Ray Structure Determinations of Bromo- and/or Bromomethylsubstituted Benzenes: C–H···Br, C–Br···Br, and C–Br···π Interactions

A mild and versatile method based on Cu(I)-catalyzed [3+2] cycloaddition (Meldal-Sharpless reaction) was developed to tether biomolecules, such as monosacharides or lipophylic azides, to alkyne functions of spirobenzo[b]thieno[2,3-d]pyrimidine-1´-cyclohexane. The reactions are highlighted by their modularity and high efficiency with excellent yields in most cases. The products are interesting precursors for a variety of applications. Graphical Abstract A Straightforward and Mild Method of Tethering Monosaccharides to Thieno[2,3-d]pyrimidinones via the Copper(I)-catalyzed Azide-Alkyne ‘Click Chemistry’

An HPLC monitoring protocol has been developed to follow the reaction of flavanone [(±)-1] with thallium(III) nitrate, lead tetracetate, phenyliodonium diacetate (PIDA) or [hydroxyl( tosyloxy)iodo]benzene in trimethyl orthoformate. Besides the major ring-contraction product, the 2,3-dihydrobenzo[b]furan derivative (±)-4a, minor components were also identified, and their structures including the relative stereochemistry and a plausible mechanism of formation are reported and compared with literature data. The oxidation reactions were monitored by HPLC at different conditions, and the structure and the ratio of the products were determined and compared. The preferred formation of flavone (5) from (±)-flavanone (1) by PIDA is explained by quantum-chemical calculations on the intermediate formed by the addition of this reagent to the enol ether derivative of (±)-1. Graphical Abstract Oxidative Rearrangement of Flavanones with Thallium(III) Nitrate, Lead Tetraacetate and Hypervalent Iodines in Trimethyl Orthoformate and Perchloric or Sulfuric Acid

A previously unknown dimer of the well-established analgesic flupirtine has been found, and its structure was revealed by ESI-MS, NMR spectroscopy and an independent synthesis. Thus, starting from 2-amino-6-chloro-3-nitro-pyridine the target compound was obtained in a four-step synthesis. Key-step of this synthesis is a nickel-mediated aryl-aryl coupling. The dimer 4 did not show any cytotoxicity, and its IC 50 values were > 30 μm for all six human cancer cell lines and mouse fibroblasts used in this study Graphical Abstract Isolation, Structure, Synthesis and Cytotoxicity of an Unprecedented Flupirtine Dimer

The possible conformations in the most stable structure of cyclophosphamide were investigated at the DFT-B3LYP and MP2/6-311G** levels of calculation. The axial structure is calculated to be lower in energy than the equatorial form of cyclophosphamide by 5 (MP2) to 6 (DFT) kcal mol -1 because of a very weak anomeric effect and weak conjugation. Further it is the same structure as the one found in the X-ray investigations both of the hydrate and of the anhydrous form. The computed DFT vibrational frequencies of the axial structure were used to analyze the infrared and Raman spectra using normal-coordinate calculations to provide reliable assignments to the normal modes of the molecule. Graphical Abstract DFT and MP2 Study of the Molecular Structure and Vibrational Spectra of the Anticancer Agent Cyclophosphamide

Two new stilbenoids cajanotone and cajanamide A (1-2), together with another six known ones (3- 8) and four known dihydroflavones (9-12), have been isolated from the leaves of Cajanus cajan. Their structures were elucidated based on spectroscopic studies. A possible pathway to the new compounds 1 and 2 has been proposed. In vitro cytotoxicities of selected compounds against cancer cell lines HepG2, MCF-7 and A549 have been evaluated. Compounds 7 and 8 show strong cytotoxity against all the tested cell lines (with IC 50 values in the range of 3.5 - 6.0 μM), and compounds 1 and 3 showed strong to moderate activity against the three cell lines. Graphical Abstract Two New Stilbenoids from Cajanus cajan

A new Zn(II) complex [Zn 2 (bimt) 2 (Ac)(OH)] n (1) has been synthesized by the reaction of the flexible ligand 2-(benzoimidazol-2-yl-methyl)-1H-tetrazole (Hbimt) with Zn(Ac) 2 · 2H 2 O and characterized by single-crystal X-ray diffraction and IR spectra. In complex 1, Zn1 and Zn2 ions are connected by μ 2 -bridging acetate and hydroxide groups to form a 6-membered ring. The bimt units coordinate to Zn1 and Zn2 ions in a bidentate bridging mode with two nitrogen atoms from the same benzoimidazole ring and connect the 6-membered rings resulting in the formation of a 2D network structure. Adjacent layers are further packed to a threedimensional network through van der Waals bonds. A thermogravimetric analysis was carried out, and the photoluminescent behavior of the complex was investigated. Graphical Abstract Syntheses, Structures and Properties of a New Zn(II) Complex Based on the 2-(Benzoimidazol-2-yl-methyl)-1Htetrazole Ligand