Volume 64, Issue 5

Following the observation that the binary dicadmides and diaurides of calcium and strontium (A) both form the KHg 2 structure type, the two sections A II Cd x Au 2−x have been studied systematically by means of synthetic, X-ray structural and theoretical investigations. The binary border compound CaCd 2 is dimorphic forming the KHg 2 structure at elevated temperatures (orthorhombic, space group Imma, a = 488.63(9), b = 754.1(2), c = 851.3(2) pm, Z = 4, R1 = 0.0498) and the MgZn 2 -type Laves phase at ambient conditions (hexagonal, space group P6 3 /mmc, a = 599.71(9), c = 962.7(2) pm, Z = 4, R1 = 0.0309). Starting from the known binary calcium auride CaAu 2 only a very small amount of Au can be replaced by Cd. Around the 1 : 1 ratio of Au and Cd the TiNiSi structure type (orthorhombic, space group Pnma), an ordered variant of the KHg 2 type, has a small homogeneity range (CaCd x Au 2−x with x = 1/0.76(2): a = 735.0(1)/731.7(1), b = 433.66(6)/431.43(7), c = 873.7(2)/869.9(2) pm, Z = 4, R1 = 0.0482/0.0539). The analogous structure type is also observed in the Sr compounds with the difference that in this case a continuous transition from the KHg 2 type of SrAu 2 (i. e. x = 0) towards the distorted TiNiSi structure type (up to x = 0.86) is observed in the series SrCd x Au 2−x (for x = 0.86(1)/0.45(1): a = 764.0(1)/758.4(1), b = 458.07(7)/474.6(1), c = 872.16(12)/829.2(2) pm, Z = 4, R1 = 0.0446/0.0410). Attempts to prepare the Ca compounds of intermediate composition around a Cd content of x ≈ 0.5 resulted in the formation of the Aurich phase Ca 5 Cd 2 Au 10 crystallizing with the Zr 7 Ni 10 structure type (orthorhombic, space group Cmca, a = 1390.6(4), b = 1015.7(3), c = 1025.6(2) pm, Z = 4, R1 = 0.0657). In this compound, Cd and Ca occupy common crystallographic sites, which are occupied by In in the isotypic ternary compound Ca 4 In 3 Au 10 . Similarly, at the Cd-rich parts of the sections A II Cd x Au 2−x no simple phase width of the KHg 2 structure type exists. In the case of the calcium series the new compound Ca 11 Cd 18 Au 4 , which shows only a very small phase width, is formed instead. This compound crystallizes with a new structure type (Ca 11 Cd 18 +xAu 4−x with x = 0.6/0: tetragonal, space group I4 1 /amd, a = 1030.83(6)/1029.39(6), c = 3062.5(3)/3051.0(3) pm, Z = 4, R1 = 0.0475/0.0379) exhibiting a complicated Cd/Au polyanion with four-, five- and six-bonded Cd/Au atoms. The results of FPLAPWband structure calculations are used to explain the electronic stability of the compounds. The calculated Bader charges of cadmium and gold atoms (and In and Au atoms for comparison) are used to discuss the transition between Cd-rich cadmides (like CaCd 2 and Ca 11 Cd 18 Au 4 ), auridocadmates (like CaCdAu) and the Cd-poor cadmium aurides (like Ca 5 Cd 2 Au 10 ). Graphical Abstract Cadmium-Auride A II Cd x Au 2– x (A II = Ca, Sr) Synthese, Kristallstruktur, chemische Bindung/ Cadmium-Aurides A II Cd x Au 2−x (A II = Ca, Sr) – Synthesis, Crystal Structure, Chemical Bonding

The title compound has been synthesized under 4 GPa and at 500 ◦C from Na 2 O andMnO as starting materials. Rietveld refinement of the X-ray powder pattern indicates that Na 6 MnO 4 is isostructural to Na 6 ZnO 4 and thus is representing the second manifestation of an “isolated” [MnO 4 ] 6− anion after Na 14 Mn 2 O 9 . The compound crystallizes in the hexagonal system in space group P6 3 mc (no. 186) with a = 7.6631(2) and c = 5.9013(2) ° A, V = 300.1 °A 3 , and Z = 2. Graphical Abstract High-pressure – High-temperature Synthesis of Na 6 MnO 4

Fe 2 B 2 O 5 , synthesized under mild high-pressure / high-temperature conditions of 3 GPa and 960 ◦C, possesses a structure isotypic to the triclinic pyroborates M 2 B 2 O 5 with M = Mg, Mn, Co, and Cd. Although the parameter pressure is not essential to the synthesis of Fe 2 B 2 O 5 , the specific conditions enhance the crystallinity of the product. Therefore, the crystal structure of the iron pyroborate Fe 2 B 2 O 5 could be determined via single crystal diffraction data [space group P1̄ (Z = 4) with the parameters a = 323.1(1), b = 615.7(2), c = 935.5(2) pm, α = 104.70(3), β = 90.82(3), γ = 91.70(3)◦, V = 0.1799(1) nm 3 , R1 = 0.0409, and wR2 = 0.0766 (all data)]. The structure is built up from layers of isolated pyroborate units ([B 2 O 5 ] 4− ), which are composed of two corner-sharing BO 3 triangles. These pyroborate layers serve to bridge 4×1 ribbons of edge-sharing FeO 6 octahedra by both edgeand corner-sharing. Graphical Abstract Synthesis and Crystal Structure of the Iron Borate Fe 2 B 2 O 5

The title compounds were prepared by melting and annealing of stoichiometric mixtures of the elemental components in a high-frequency furnace. They are isotypic with Yb 2 Ru 3 Ga 10 (P4/mbm, Z = 2). Their lattice constants were determined from X-ray powder data, and their crystal structures were refined from single-crystal X-ray data. Er 2 Os 3 Ga 10 : a = 883.4(1), c = 636.7(1) pm, R = 0.025 for 506 Fo values, and Tm 2 Os 3 Ga 10 : a = 883.2(1), c = 633.6(1) pm, R = 0.023 for 568 Fo values and 25 variable parameters each. The crystal structures of these intermetallic compounds are briefly discussed. Graphical Abstract The Lanthanoid Osmium Gallides Er 2 Os 3 Ga 10 and Tm 2 Os 3 Ga 10 with Yb 2 Ru 3 Ga 10 -type Structure

Two thioindates [M(en) 3 ] 0.5 InS 2 [en = ethylenediamine; M = Ni (1), Co (2)] were prepared by the reaction of In 2 S 3 , Ni (or Co) and S under solvothermal conditions, and their crystal structures have been determined. Both compounds are isostructural and crystallize in the orthorhombic space group Cmcm. The crystal structures consist of a new type of 1-D sinusoidal chain, which complements the reported I - III types of 1-D [InQ 2 − ]n (Q = S, Te) anions built from InQ 4 tetrahedra. The band gaps of 3.47 eV for I and 3.31 eV for 2 have been derived from optical absorption spectra. Graphical Abstract A New Type of 1-D Thioindates, [M(en) 3 ] 0.5 [InS 2 ] (M = Co, Ni), Synthesized by Solvothermal Reaction

Anhydrous MgCl 2 was reacted with 2 equiv. of ethanol to generate the MgCl 2 (EtOH) 2 adduct 1. An appropriate amount of higher alcohol having a long carbon chain, such as 1-decanol, was anchored on the surface of a part of adduct 1 to give a mixture of MgCl 2 adducts having an internal surfactant. A multifunctional polymer/oligomer, e. g. poly(ethylene glycol)-200 (PEG-200), was introduced into this system yielding a composite of liquid inorganics and polymers (CLIP). Under the regulation of the internal surfactant and the multifunctional polymer, this composite was melted and dispersed in an inert hydrocarbon solvent under vigorous agitation at elevated temperatures followed by fast cooling to generate a MgCl 2 -based spherical catalyst support precursor. SEM pictures show that this support precursor has a narrow particle size distribution, and its surface structure is an intricate combination of smaller MgCl 2 -based crystallites. Graphical Abstract Controllable Formation of MgCl 2 -based Spherical Catalyst Support Precursors via Composites of Liquid Inorganics and Polymers

The crystal structures of four alkali salts of maleic acid have been determined by single crystal X-ray diffraction: crystals of rubidium hydrogen maleate, RbH(C 4 H 2 O 4 ), are very nearly centrosymmetrical, i. e., only one hydrogen atom position in the crystal structure violates the centrosymmetry. Thus, the space group is Pbc2 1 rather than Pbcm. The compound is isotypic with potassium hydrogen maleate, KH(C 4 H 2 O 4 ), which has previously been described in space group Pbcm. It has been reinvestigated to prove that the correct space group is also Pbc2 1 . The isotypic pair of rubidium hydrogen maleate maleic acid, RbH(C 4 H 2 O 4 ) H 2 (C 4 H 2 O 4 ), and caesium hydrogen maleate maleic acid, CsH(C 4 H 2 O 4 )H 2 (C 4 H 2 O 4 ), crystallise in the triclinic space group P1̄. The geometry of the maleate units in these compounds corresponds well to data of other metal maleates. The only significant variation, concerning the intra-anionic hydrogen bond, is discussed. Furthermore, an overview of previously reported metal maleate structures is given, with special regard to the symmetry of the intramolecular hydrogen bond. Graphical Abstract Syntheses, Crystal Structures and an Overview of Alkali Metal Maleates

The reaction of H 2 N-NH 2 with ClSiMe 2 N(SiMe 3 ) 2 in a molar ratio 1 : 2 gave the bis(silylamino) hydrazine [HNSiMe 2 -N(SiMe 3 ) 2 ] 2 (1). Compound 1 forms a monomeric dilithium salt with BuLi. From n-hexane (Me 3 Si-NSiMe 2 -NLiSiMe 3 ) 2 (2) crystallizes while from THF [Me 3 Si-NSiMe 2 - NLi(THF)SiMe 3 ] 2 (3) precipitates. Compounds 2 and 3 are formed from 1 via a silyl group migration. In the rearranged salts, the silyl groups are bonded at the hydrazino nitrogen atoms. Hydrolysis of 2 led to the formation of (Me 3 Si-N-SiMe 2 -NHSiMe 3 ) 2 (4) which is a structural isomer of 1. Ring closure occurs in reactions of 2 or 3 with F 3 B ・ OEt 2 or SiF 4 . The seven-membered rings (Me 3 Si- N-SiMe 2 -NSiMe 3 ) 2 BF (5) and (Me 3 Si-NSiMe 2 -NSiMe 3 ) 2 SiF 2 , (6) were isolated as the products. The crystal structures of 2, 3 and 5 have been determined. Graphical Abstract Acyclic and Cyclic Silylaminohydrazines

A new facile cost-effective method for the oxidation of acetyl and carboethoxy derivatives of 3,4- dihydropyrimidin-2(1H)-ones (DHPMs) by using potassium peroxydisulfate in water as solvent under microwave irradiation has been developed. Whereas the presence of the acetyl group instead of the carboethoxy group in position 5 decreases the rate of oxidation, the nature of the additional subtituent (electron-donating or electron-withdrawing group) and its location on the phenyl ring (ortho-, meta- or para-position) attached to C-4 of the dihydropyrimidinone ring influence the rate of reaction. Increase in the rate of the reaction compared with that of the reaction under reflux condition is the advantage of the use of microwave irradiation for this oxidation method. Graphical Abstract Microwave-assisted Oxidation of 3,4-Dihydropyrimidin-2(1H)-ones

Starting from the corresponding cyclic 1,3-diketones or other precursors (cyclic ketones as well as lactones), several new salts and chelate complexes of fluorinated 1,3-dicarbonyls were obtained. Their preparative significance was demonstrated by straightforward syntheses of fluorinated pyrazoles, benzimidazoles and 1,7-ketoesters. The structure of a boron chelate of 2-(trifluoroacetyl)- cyclohexanone was investigated by X-ray diffraction. Graphical Abstract Metal and Boron Derivatives of Fluorinated Cyclic 1,3-Dicarbonyl Compounds

Four novel cyclotriphosphazene bile acid derivatives (1 - 4) were prepared starting from hexakis[4- (chloromethyl)phenoxy]cyclotriphosphazene (8) as the scaffold. The structures of the compounds were defined by elemental analysis, IR and 1 H, 13 C and 31 P NMR spectroscopy. Graphical Abstract Synthesis and Characterization of Cyclotriphosphazenes Bearing Six Bile Acid Arms

Chloro(phenyl)carbenium hexachloroantimonate salts react with isocyanates to afford either isoindolium (1) or benzoxazinium salts (2). Addition of one equivalent of alcohol to 2 led, after hydrolysis with aq. NaOH, to the formation of benzoxazin-2-ones 3. Treatment with a large excess of alcohol transformed the salts 1 and 2 to the corresponding isoindol-1-ones 11 and the isocyanates 5, respectively. Reaction of 5 with primary amines furnished the urea derivatives 6 in good yield. The biological activity of 6a - o against HIV-1 was determined. Graphical Abstract Facile Synthesis of Non-nucleoside Compounds Starting from α-Chlorocarbenium Ions and Isocyanates as Potential HIV-1 Reverse Transcriptase Inhibitors

Mixed diamidophosphoric acid esters [(CH 3 ) 2 N][p-H 3 C-C 6 H 4 -O]P(O)X, where X = NH(CH 3 ) (1), NHCH(CH 3 ) 2 (2), NHC(CH 3 ) 3 (3) and p-H 3 C-C 6 H 4 -NH (4) were synthesized and characterized by 31 P, 31 P{ 1 H}, 13 C, 1 H NMR, and IR spectroscopy and mass spectrometry, and single crystal X-ray diffraction analysis for the compounds 3 and 4. Compound 3 crystallizes in the monoclinic, space group P2 1 /c with unit cell parameters a = 9.006(3), b = 16.286(5), c = 10.319(3) A° , β = 99.633(6)◦, V = 1492.2(8) °A 3 , Z = 4. The final R value is 0.0622 for 2074 reflections [I ≥ 2σ (I)]. Compound 4 crystallizes in the orthorhombic, space group Pna2 1 with unit cell parameters a = 7.0459(14), b = 20.934(4), c = 10.436(2) ° A, V = 1539.3(5) °A 3 , Z = 4. The final R value is 0.0530 for 3025 reflections [I ≥ 2σ (I)]. Graphical Abstract Synthesis and Spectroscopic Characterization of Mixed Diamidophosphoric Acid Esters: X-Ray Crystal Structure of [(CH 3 ) 2 N]-[p-H 3 C-C 6 H 4 -O]P(O)X (X = NHC(CH 3 ) 3 and p-H 3 C-C 6 H 4 -NH)

The chromatographic behavior of new derivatives of 1,2,4-triazol-5-one and semicarbazide was determined. The lipophilicity was confirmed by the use of a RP-TLC method. The partition coefficients were calculated by use of theoretical procedures. The correlation between theoretical and experimental lipophilicity was determined. All obtained compounds were tested for their antimicrobial activity. Graphical Abstract Determination of the Lipophilicity of Some New Derivatives of Semicarbazide and 1,2,4-Triazol-5-one with Potential Antibacterial Activity

The chloroapatite Eu 5 (PO 4 ) 3 Cl has been synthesized by a solid-state reaction route using a salt flux. Its structure has been solved and refined from single crystal X-ray data: apatite type, P6 3 /m, a = 988.36(4), c = 720.32(3) pm, Z = 2, R(F) = 0.021 and wR(F 2 ) = 0.063 for 748 unique reflections and 40 variables. The Eu 5 (PO 4 ) 3 Cl structure contains isolated (PO 4 ) 3− tetrahedra and two crystallographically independent divalent europium sites. The Eu1 2+ ion at the 4 f position is located in a distorted tri-capped trigonal prism whereas the Eu2 2+ ion at the 6h position is located in a strongly distorted square anti-prism. The chloride ions have octahedral europium coordination (307 pm Eu-Cl). Graphical Abstract Single Crystal Structure of the Divalent Europium Chloroapatite Eu 5 (PO 4 ) 3 Cl

The tetra(tert-butyl)-tetraazido-borazocine, 1, has the expected tub shape as determined for (SCNB=NtBu) 4 . However, it crystallizes in the triclinic system and shows no symmetry element in contrast to the isothiocyanato derivate which has C 2 symmetry. There are two kinds of BN bonds which alter from long to short (average 1.491 and 1.388 A° ). The BN bond lengths to the azido groups are, on average, 1.486 °A. All B and N atoms of the ring reside in a trigonal planar environment. The B-N-N bond angles are close to 120◦ showing that the central nitrogen atom can be considered as sp 2 -hybridized. The N-N-N bond angles are on average 173.6◦. The two sets of the opposite B 2 N 2 planes include an angle of 114.8◦. The atoms of the azido groups are almost coplanar with the respective NBN planes. This together with the short BN(N 2 ) bond lengths indicates that these azido groups are π-bonded to their corresponding boron atom. Graphical Abstract The Molecular Structure of 1,3,5,7- Tetra(tert-butyl)-2,4,6,8-tetraazidoborazocine [1]