Band 67, Heft 2

A metal-organic framework (MOF) was prepared from 1,2-di(pyridin-4-yl)ethyne, terephthalic acid and zinc(II) nitrate in dimethylformamide, water and ethanol at 80 °C. The cavities of the MOF are occupied by disordered molecules of dimethylformamide. The crystals are monoclinic, space group P2 1 /c with Z = 4. Graphical Abstract A Metal-Organic Framework Constructed of 1,2-Di(pyridin-4-yl)ethyne, Terephthalic Acid, and Zinc(II) Nitrate

The gold-rich indide Eu 5 Au 17.7 In 4.3 was synthesized from the elements in a sealed tantalum ampoule that was heated in a high-frequency furnace. Eu 5 Au 17.7 In 4.3 crystallizes with a new monoclinic structure type: C2/m, a = 902.7(2), b = 722.8(3), c = 1734.1(4) pm, β = 94.31(3)°, wR2 = 0.0907, 2640 F 2 values and 74 variables. Eu 5 Au 17.7 In 4.3 has a pronounced gold substructure with Au-Au distances ranging from 278 to 300 pm. The striking structural motifs in the gold substructure are networks of Au6 hexagons and discrete units of corner- and edge-sharing Au 4 tetrahedra. Eu 5 Au 17.70 In 4.30 exhibits a small homogeneity range with In/Au mixing on two Wyckoff sites. Geometrically, the Eu 5 Au 17.7 In 4.3 structure can be explained as an intergrowth variant of slightly distorted SrAu 4.76 In 1.24 - and BaL i4 -related slabs. The europium coordination in the BaL i4 slabs is similar to binary EuAu 2 . Graphical Abstract The Gold-rich Indide Eu 5 Au 17.7 In 4.3 and its Relation with the Structures of SrAu 4.76 In 1.24 and BaLi 4

Single crystals of the laser host material Sc 2 SiO 5 as well as thulium- (4 at.-%) and ytterbium- (5 at.-%) doped samples were prepared by the Czochralski technique. The structures of Sc 2 SiO 5 , Tm 3 +:Sc 2 SiO 5 , and Yb 3+ :Sc 2 SiO 5 were refined on the basis of high-quality single-crystal X-ray diffraction data: monoclinic Y 2 SiO 5 type, space group C2/c. The X-ray data unambiguously show that the larger rare earth cations exclusively occupy the 8 f site with oxygen coordination number 7. Graphical Abstract Rare Earth Site Preference in the Doped Laser Host Material Sc 2 SiO 5 . A Single-Crystal X-Ray Study

The geometries and harmonic vibration frequencies of the Cu + ·O 2 and Cu + ·N 2 are determined by various density functional theory (DFT) methods employing different basis sets. The potential energy surfaces (PES) are examined. The Cu + ·O 2 adduct exhibits a bent structure with a binding energy of 12.4 kcal mol −1 , whereas Cu + ·N 2 exhibits a linear configuration with a binding energy of 23.5 kcal mol −1 . The binding energy values for the two adducts agree well with the available published experimental and theoretical data and hence are reliable. Graphical Abstract A Density Functional Theory Study of the Cu + · O 2 and Cu + · N 2 Adducts

Mixed sulfido/oxidomolybdate anions [MoO x S 4−x ] 2 − (x = 1, 2, 3) have been prepared by passing H2S gas through a solution of oxidomolybdates. The alkali salts of K + , Rb + , Cs + , and NH + 4 precipitate as crystalline salts from these solutions depending on the pH, the polarity of the solvent, the educt concentrations and the temperature. Their structures have been determined by means of X-ray single-crystal diffraction data. All trisulfidomolybdates A 2 [MoOS 3 ] (A = NH 4 /K/Rb/Cs) are isotypic with the tetrasulfido salts, exhibiting the β -K 2 [SO 4 ] type (orthorhombic, space group Pnma, Z = 4; for A = Rb: a = 940.62(4), b = 713.32(4), c = 1164.56(5) pm, R1 = 0.0281). In contrast, the disulfidomolybdates exhibit a rich crystal chemistry, forming three different structure types depending on the preparation conditions and the size of the A cation: All four cations form salts crystallizing with the (NH 4 )2[WO 2 S 2 ] structure type (monoclinic, space group C2/c, Z = 4, for A = Rb: a = 1144.32(11), b = 732.60(4), c = 978.99(10) pm, β = 120.324(7)°, R1 = 0.0274). For the three alkali metal cations a second polymorph with a new structure type (monoclinic, space group P2 1 /c, Z = 4) is observed in addition (for A = Rb: a = 674.83(2), b = 852.98(3), c = 1383.10(9) pm, β = 115.19(1)°, R1 = 0.0216). The cesium salt also crystallizes with a third modification of another new structure type (orthorhombic, space group Pbcn, Z = 4, a = 915.30(6), b = 777.27(7), c = 1120.02(7) pm, R1 = 0.0350). Only for K, an anhydrous monosulfidomolybdate could be obtained (K 2 [MoO 4 ] structure type, monoclinic, space group C2/m, Z = 4, a = 1288.7(3), b = 615.7(2), c = 762.2(1) pm, β = 109.59(1)°, R1 = 0.0736). The intramolecular chemical bonding in the molybdate anions is discussed and compared with the respective vanadates. Hereby aspects like bond lengths, bond strengths and force constants derived from Raman spectroscopy, are taken into account. Especially for the polymorphic disulfido salts, in-depth analyses of the local coordination numbers and the packing of the ions are presented. The gradual bathochromic shift of the crystal color with increasing S content and increasing size of the counter cations A and molar volumes (for the polymorphic forms), respectively, is in accordance with the increase of the experimental (UV/Vis spectroscopy) and calculated (FP-LAPW band structure theory) band gaps. Graphical Abstract Gemischte Alkalimetall-Oxidosulfidomolybdate A 2 [MoO x S 4– x ] (x = 1, 2, 3; A = K, Rb, Cs, NH 4 ). Synthesen, Kristallstrukturen und Eigenschaften / Mixed Alkali Oxidosulfidomolybdates A 2 [MoO x S 4−x ] (x = 1, 2, 3; A = K, Rb, Cs, NH 4 ).Synthesis, Crystal Structure and Properties

The diorganotin(IV) complex [Ph 2 Sn(L)(CH 3 COO)] (1), where HL = 2-acetylpyrazine N 4 -methyl thiosemicarbazone, has been synthesized and characterized by elemental analysis, IR, UV/Vis and NMR spectroscopy, mass spectrometry, and single-crystal X-ray diffraction. Complex 1 contains mononuclear neutral molecules composed of one N 2 S tridentate anionic thiosemicarbazone ligand, one acetato group, and one Ph 2 Sn(IV) group with a seven-coordinated tin atom. In vitro biological studies have indicated that complex 1 shows effective cytotoxicity with IC 50 = 5.4 μM against the K562 leukaemia cell line. Graphical Abstract Synthesis, Characterization, Crystal Structure, and Cytotoxicity of a 7-Coordinate Diorganotin(IV) Complex of 2-Acetylpyrazine N 4 -Methylthiosemicarbazone

A one-pot synthesis of dialkyl 2-(diphenoxyphosphoryl)-3-[hydroxy (alkyl)(aryl) sulfanyl] succinate derivatives via the reaction between dialkyl acetylenedicarboxylates, triphenyl phosphite and mercaptoalkanols or mercaptophenols is described. These reactions lead to the formation of dialkyl 2-(diphenoxyphosphoryl)-3-[hydroxy (alkyl)(aryl) sulfanyl] succinates as a mixture of two diastereomers without using any catalyst and in good yields. Graphical Abstract Efficient Synthesis of Succinate Derivatives using Mercaptoalkanols or Mercaptophenols

The primary azo compound 1-(3-formyl-4-hydroxyphenylazo)-4-nitrobenzene reacts with some aliphatic and aromatic diamines and yields the corresponding azo-azomethine compounds. These compounds were characterized by elemental analysis, IR, UV/Vis, and NMR spectroscopy. The primary azo compound exists entirely in the azo form in solution as well as in the solid phase. The tautomeric structure of azo-azomethine compounds heavily depends on the solvent and the substituents. Aliphatic diamine-based compounds favor the enol-imine tautomer while aromatic diamine-based compounds have structures that lie between the two enol-imine and keto-amine tautomers due to a relatively strong intramolecular hydrogen bond. The compounds exhibit positive solvatochromism (bathochromic shift) so that their absorption bands move toward longer wavelengths as the polarity of the solvents increases. In addition, UV/Vis spectrophotometry has shown that the studied compounds have molar extinction coefficients larger than 40000. Graphical Abstract Synthesis, Characterization, and Tautomeric Properties of Some Azo-azomethine Compounds

H 3 PW 12 O 40 ・ xH 2 O efficiently catalyzes the one-pot pseudo three-component reaction of benzofuran- 3(2H)-ones and various alcohols to afford the corresponding bibenzofuran derivatives with various alkoxy groups in 3-position. Graphical Abstract A Clean Synthesis of Novel 3-Alkoxy-2-(benzofuran-3-yl)benzofurans via a One-pot Pseudo Three-component Reaction using H 3 PW 12 O 40 · xH 2 O as a Catalyst

Four new acylated grayanane diterpenoids, pierisformosins E-H (1 - 4), together with two known ones, pierisformosins B and C (5, 6), were isolated from the fruits of Pieris formosa. The structures and relative configurations of the new compounds were elucidated by means of spectroscopic methods, including 1D and 2D NMR and mass spectrometry. Graphical Abstract Grayanane Diterpenoids from the Fruits of Pieris formosa

Four new lignans, curcasinlignan A (1), curcasinlignan B (2), curcasinlignan C (3), and curcasinlignan D (4), together with eight known compounds, (±)-rel-(2α,3β )-7-Omethylcedrusin (5), (±)-7R∗,8S∗-5-methoxydihydrodehydroconiferyl alcohol (6), dehydrodiisoeugeno1 (7), (threo)-1-(4-hydroxy-3-methoxyphenyl)-2-(4-formyl-2-methoxy-phenoxy)-propane- 1,3-diol (8), (±)-machilin D (9), (+)-pinoresinol (10), 5ʹ-methoxypropacin (11), and hemidesmin-2 (12), were isolated from the aerial parts of Jatropha curcas. Their structures were established on the basis of extensive spectroscopic analysis. Graphical Abstract New Lignans from Jatropha curcas Linn.

The crystal structure of the industrially relevant tetrahydroxy ether 2,2,2ʹ,2ʹ-(tetrahydroxymethyl)-dibutylether (technically known as di(trimethylol)propane, Di-TMP; C 12 H 26 O 5 ) was determined from single-crystal X-ray data at 123 K: monoclinic, space group C2/c (no. 15), a = 20.1202(13), b = 5.8169(4), c = 13.0323(8) Å, β = 114.296(3)°, V = 1390.17(16) Å 3 and Z = 4. The adjacent molecules assemble into a two-dimensional framework in the solid state, linked by two intermolecular O-H...O hydrogen bonds. The compound is characterized via spectroscopic methods and mass spectrometry. Graphical Abstract Synthesis and Solid-state Structure of 2,2,2ʹ,2ʹ -(Tetrahydroxymethyl)- dibutylether (Di-TMP), an Environmentally Benign Polymer Crosslinker and High-potential Additive for Lubricants