Volume 64, Issue 7

The macrocyclic hexanuclear manganese(III) 18-metallacrown-6, [Mn 6 (pmshz) 6 (DMF) 4 (C 2 H 5 - OH) 2 ]·4DMF (1), where pmshz 3− is N-propionyl-N'-5-methylsalicylhydrazide, has been synthesized by self-assembly and structurally characterized. The ring is formed by the succession of six structural moieties of the type [Mn(III)-N-N] with hydrazide N-N groups bridging the ring Mn ions. The ligand enforces the metal ions to form the stereochemistry of a configuration with alternate. . .ΔΛΔΛ. . .- type enantiomeric chiral units. The peripheral core ring is ~18.6 in diameter and ~12.4 Å in thickness. The title metallacrown exhibits photoluminescent properties in the solid state and a weak antiferromagnetic exchange interaction. Graphical Abstract An 18-Membered Hexanuclear Manganese (MnN 2 ) 6 Metalladiazamacrocycle

In a Henry-type reaction nitromethane reacts with N-(2-pyridylmethylidene)-methylamine (1) yielding 1-methylamino-1-(2-pyridyl)-2-nitromethane (2) in nearly quantitative yield. This orange compound decomposes slowly in an inert gas atmosphere and fast in contact with air. Therefore 2 has to be stored at −78 ◦C as a methanol solution. Reduction of 2 with hydrogen in the presence of a Pd/C catalyst leads to the formation of 1,4-dinitro-2,3-di(2-pyridyl)butane (3) in the rather poor yield of 12 %. The major product is the meso-isomer, meso-3, whereas only traces of (R,R)- and (S,S)- isomers of 3 are formed. A conversion of the nitro groups into amino functionalities succeeds with hydrazine hydrate in the presence of a Pd/C catalyst yielding meso-1,4-diamino-2,3-di(2-pyridyl)butane (4). Recrystallization from an aqueous solution gives 4・2H 2 O. The zinc(II) chloride complex 5 with the metal atoms in distorted tetrahedral environments can be isolated after addition of two equivalents of ZnCl 2 to 4. The molecular structures of trimeric 1, meso-3, (R,R)/(S,S)-3, meso-4, and 5 have been determined and are discussed. Graphical Abstract Synthesis of 1,4-Diamino-2,3-di(2-pyridyl)butane and its Dinuclear Zinc(II) Chloride Complex

LiBH 4 solutions in diethyl ether or tetrahydrofuran react with N-methylmorpholine, Nmethylimidazole or piperidine not only with the formation of adducts LiBH 4 (L) n (n = 1 or 3) but also with formation of amine boranes BH 3 (L). While LiBH 4 and N-methylimidazole form the 1 : 3 adduct 1, N-methylmorpholine produces the 1 : 1 adduct 2. In both cases the adducts contain hexacoordinated Li atoms. In 1 the Li atom is coordinated to three N atoms and three H atoms. However, in compound 2 the molecules are connected in the solid state with one another to form a two-dimensional polymer built from dimeric units (LiBH 4 )2 that are connected to adjacent dimeric units via the O and N atoms of the N-methylmorpholine ligand. Each of the Li atoms in 2 is connected to four H atoms via Li-H-B hydrogen bridges and an O and an N atom. The reaction of LiBH4 with piperidine leads to the compound (LiBH 4 ) 6 (HNC 5 H1 0 ) 16 , 3, which consists of two independent LiBH 4 (HNC 5 H 10 ) 3 molecules and two others of composition (LiBH 4 ) 2 (HNC 5 H 10 ) 5 containing penta- and hexacoordinated Li atoms. Graphical Abstract Synthesis and Structures of LiBH 4 Complexes with N-Heterocycles [1]

Reaction of MoO 2 (S 2 CNMe 2 ) 2 with RuCl 3 ・χH 2 O in acetone at reflux afforded [Ru 2 (S 2 CNMe 2 ) 3 - (μ 3 -S 2 CNMe 2 ) 2 ] 2 [Mo 6 O 19 ]・2CH 3 COCH 3 (1・2CH 3 COCH 3 ) which was characterized by singlecrystal X-ray diffraction to show a dinuclear ruthenium-dithiocarbamate species as cation and hexamolybdate as counter anion. The [Ru 2 (S 2 CNMe 2 )3(μ 3 -S 2 CNMe 2 ) 2 ] + cation may be considered as a combination of [Ru(S 2 CNMe 2 ) 3 ] with a cis-[Ru(S2CNMe 2 ) 2 ] + species, and the Lindqvist anion [Mo 6 O 19 ] 2− is located on an inversion center between two cations. Spectroscopic properties along with the electrochemistry of compound 1・2CH 3 COCH 3 are reported. Graphical Abstract Synthesis, Structure and Electrochemistry of [Ru 2 (S 2 CNMe 2 ) 3 (μ3-S 2 CNMe 2 ) 2 ] 2 [Mo 6 O1 9 ] · 2CH 3 COCH 3

Hydrothermal reactions of Cd(SAr) 2 with 4,4'-trimethylenebipyridine (tmdp) at 145 °C yielded new complexes, [Cd(SAr) 2 (tmdp) 2 ]n (Ar = Ph, 1, C 6 H 4 Me-4, 2), which are one-dimensional wavelike coordination polymers with distorted tetrahedral CdN 2 S 2 coordination environments. The thermal stability of the two complexes was studied by thermal gravimetric (TG) and differential thermal analyses (DTA). Graphical Abstract One-dimensional Coordination Polymers of Cadmium Thiolates with 4,4'-Trimethylenebipyridine Ligands

A new paradodecatungstate-B compound, [{Co(H 2 O) 4 } 4 (H 4 W 12 O 42 )]·10H 2 O (1) of the polyoxometalate series has been synthesized and characterized by elemental analysis, IR and UV spectroscopy, TG analysis, and single-crystal X-ray diffraction. Compound 1 exhibits a unique 8- connected three-dimensional (3D) framework with a (4 2 · 8 20 · 12 6 ) topology. Moreover, 1 displays antiferromagnetic interactions in the 2 - 300 K temperature range, well reproduced by a simulation procedure. Graphical Abstract Highest Connectivity in a Purely Inorganic 3D Compound Based on Paradodecatungstate-B Clusters: Synthesis and Magnetic Properties

The crystal structure of the layered iron arsenide Sr 3 Sc 2 O 5 Fe 2 As 2 was determined between 300 and 10 K. The lattice parameters of the tetragonal cell decrease anisotropically according to Δc/c : Δa/a ≈ 4.2, which results in a slight flattening of the As-Fe-As bond angle within the FeAs layers. No indication of a structural instability could be detected. 57 Fe Mössbauer spectroscopic data show only a single signal at 4.2, 77, and 298 K, subjected to quadrupole splitting. The isomer shift increases from 0.36(1) mms −1 at 298 K to 0.49(1) mms −1 at 4.2 K. No indication for magnetic ordering was found. Graphical Abstract Low-temperature Crystal Structure and 57 Fe Mössbauer Spectroscopy of Sr 3 Sc 2 O 5 Fe 2 As 2

The sandwich-type complex Na(H 2 O) 6 (C 6 H 16 O 3 N) 2 [Na 2 (H 2 O) 7 (C 6 H 16 O 3 N)] 2 [(Na(H 2 O) 2 ) 3- (Cu(H 2 O)) 3 (BiW 9 O 33 ) 2 ]・14H 2 O (1) (C 6 H 16 O 3 N + = protonated triethanolamine) has been synthesized and structurally characterized by single-crystal X-ray diffraction, IR spectroscopy and TG analysis. The basic framework of 1 is built from a sandwich-type [(Na(H 2 O) 2)3- (Cu(H 2 O)) 3 (BiW 9 O 33 ) 2 ] 9− anion, two [Na 2 (H 2 O) 7 (C 6 H 16 O 3 N)] 3+ cations, a free Na(H 2 O) 6 + cation, and two free C 6 H 16 O 3 N + units. In compound 1, the [(Na(H 2 O) 2 ) 3 (Cu(H 2 O)) 3- (BiW 9 O 33 ) 2 ] 9− anion links two bi-nuclear units [Na2(H2O)7(C6H16O3N)] 3+ to form a [Na 2 - (H 2 O) 7 (C 6 H 16 O 3 N)] 2 [(Na(H 2 O) 2 ) 3 (Cu(H 2 O)) 3 (BiW 9 O33)2] 3− cluster, and a new 3D supramolecular structure is further constructed by hydrogen bonding interactions among this cluster, the free Na(H 2 O) 6 + cation, and the free C 6 H 16 O 3 N + cations. Crystal data: Cu 3 Na 8 Bi 2 W 18 C 24 H 150 O 121 N 4 , monoclinic, C2/c, a = 14.5668(13), b = 23.0405(13), c = 37.412(2) Å , β = 91.569(10)° , Z = 4. Graphical Abstract Synthesis and Crystal Structure of a Sandwich-type Transition Metal Complex with Tungstobismutate and Triethanolamine

We report herein on the utility of the Pfitzinger reaction in a facile two-step synthesis of the new heterocyclic ring system 6-arylbenzo[4,5]imidazolo[2,1-b]quino[4,3-e]-1,3-thiazin-14-one using microwave irradiation (MWI) and/or conventional heating. Microwave irradiation was used for a rapid and efficient synthesis of quinoline-4-carboxylic acids 6a - d from the reaction of isatin with 2-(1Hbenzimidazol- 2-ylthio)-1-arylethanones 3a - d. Cyclization of cinchoninic acids 6a - d afforded the fused title compounds 7a - d. Graphical Abstract A New Aspect of the Pfitzinger Reaction: Microwave-assisted Synthesis of the New Heterocyclic Ring System 6-Arylbenzo[4,5]imidazolo[2,1-b]quino[4,3-e]-1,3-thiazin-14-one

The title compound has been isolated as single crystals from the synthesis of propylene carbonate from racemic 1,2-propanediol and carbon dioxide using n-Bu 2 SnO as a catalyst precursor. The X-ray crystallographic structure analysis revealed the self-assembly of di-n-butyltin(IV) 1,2-propanediolate units, linked together through long-distance Sn-O interactions leading to a one-dimensional polymeric architecture organized in a syndiotactic arrangement. The coordination geometry around the tin atoms can be described as an unusual faced-capped trigonal bipyramidal environment. Graphical Abstract Structural Characterization of 2,2-Di-n-butyl-4-methyl-1,3,2- dioxastannolane Isolated from Supercritical CO 2 Conditions

1,3-Diisopropyl-4,5-dimethylimidazolium phenolate (4a), pentafluorophenolate (4b), and pentachlorophenolate (4c) are obtained from 2,3-dihydro-1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (2) and the corresponding phenols 3 as stable crystals in excellent yields. The crystal structure analyses of compounds 4 reveal the presence of ion pairs linked by almost linear C-H・・・O hydrogen bonds. With 4-hydroxypyridine (5), the carbene 2 gives 1,3-diisopropyl-4,5-dimethylimidazolium 4- pyridinolate (6) whose crystal structure analysis indicates the ions to be connected by a C-H・・・N bond. Graphical Abstract Imidazolium Phenolates

N1-Substituted-5-amino-4-cyanopyrazoles were cyanoacetylated with a mixture of cyanoacetic acid and acetic anhydride. Cyclization with POCl 3 gave 4-chloro-pyrazolo[3,4-d]pyrimidine derivatives. From the reaction with hydrazine and arylhydrazines, the hydrazinyls and their oxidized forms, the azo products, were obtained. The structure of the compounds obtained has been confirmed by 1 H and 13 C NMR spectroscopy. Graphical Abstract Cyanoacetylation of 5-Aminopyrazole: Synthesis of 2-(1-Aryl-4- substituted pyrazolo[3,4-d]pyrimidin-6-yl)acetonitrile Derivatives

Hydroxycycloalkanones 1 of medium ring size (8 -10) exist in a transannular tautomeric equilibrium with the corresponding oxabicycloalkan-1-ols 2, which represent hemiacetals. Normally, the bicyclic structures 2 predominate in solution although their portion decreases with increasing solvent polarity. A correlation of the Gibbs reaction enthalpies ΔG (1→2) with the solvent parameters E T (30) is presented. Graphical Abstract Equilibrium between Hydroxycycloalkanones and Oxabicycloalkanols

4-Chloro-2-methylquinolines 1a-d on reaction with p-toluidine afforded 2,4’-dimethyl-4-(N-phenylamino) quinolines 2a-d which on reaction with aliphatic and aromatic carboxylic acids yielded the respective 7-substituted dibenzonaphthyridines 3a-d and 4a- d whereas a heterocyclic acid afforded 5a-c and 6a-c. Graphical Abstract Synthesis of Novel Substituted Dibenzonaphthyridines

4-Arylaminoquinazoline-2-carbonitriles 5a - i were obtained by a one-step synthesis in moderate to good yield by reacting 2-aminoarylbenzimidamides 3a - i with tetracyanoethylene (TCNE, 4) in ethyl acetate at r. t. for 4 - 6 h. The structure of the selected benzimidamide 3c was determined by single crystal X-ray diffraction. Graphical Abstract A General Synthesis of 4-Arylaminoquinazoline-2-carbonitriles

Diphenethylamine forms two adducts (1 : 1, 1a and 2 : 1, 1b) with terephthalic acid (H 2 TPA). The former is bis(diphenethylammonium)H 2 TPA・TPA 2− and the latter is bis(diphenethylammonium) ・TPA 2− . The amine cis-2,6-dimethylpiperidine forms a hydrated 2 : 1 adduct, bis(2,6-dimethylpiperidinium) ・TPA 2− ・H 2 O (2). The crystal structures of all three compounds were determined. All H 2 TPA and TPA 2− residues display inversion symmetry, while the water oxygen atom of 2 lies on a twofold axis. Packing analyses have identified some supramolecular synthons known from related structures. Graphical Abstract Three Crystal Structures of Terephthalic Acid Salts of Simple Amines

Two new aporphine-type isoquinoline alkaloids, (+)-N-(methoxy-carbonyl)-N-norlauroscholtzine (1) and (+)-N-(methoxy-carbonyl)-N-norglaucine (2), were isolated from Litsea cubeba and identified by spectroscopic techniques (NMR, MS, UV, and IR). Their structures contain an N-(methoxycarbonyl) moiety, which has seldomly been found in the natural products of these analogs. Both compounds 1 and 2 showed no antibacterial activity against Staphylococcus aureus. Graphical Abstract Two New Isoquinoline Alkaloids from Litsea cubeba

The new compound AgMnPO 4 has been synthesized by a solid-state reaction route. Its crystal structure was determined from single-crystal X-ray diffraction data. AgMnPO 4 crystallizes with triclinic symmetry, space group P1̄, a = 9.6710(6), b = 5.695(2), c = 6.629(3) Å , α = 102.55(3), β = 105.85(2), γ = 80.70(2)◦, and Z = 4. Its structure is built up from MnO 6 , MnO 5 and PO 4 polyhedra forming tunnels filled with silver atoms. Graphical Abstract Crystal Structure of the New Phosphate AgMnPO 4

The first total synthesis of racemic hydroxymoloka’iamine, a new brominated metabolite isolated from Red Sea sponge Pseudoceratna arabica, was achieved in a high-yield reaction sequence. Graphical Abstract The First Total Synthesis of Racemic Hydroxymoloka’iamine