Band 66, Heft 7

Two new organic hybrid thiogermanates [Ni(dien) 2 ](H 2 dien)Ge 2 S 6 (1, dien = diethylenetriamine) and [Ni(teta) 2 ] 2 Ge4S 10 (2, teta = triethylenetetramine) were synthesized under solvothermal conditions. 1 contains a [Ni(dien) 2 ] 2+ complex cation, a protonated dien molecule and a [Ge 2 S 6 ] 4− dimeric anion, while 2 consists of discrete [Ge 4 S 10 ] 4− adamantane-like cluster anions with [Ni-(teta) 2 ] 2+ complex cations as counter ions. The [Ge 4 S 10 ] 4− anion is composed of four nearly tetrahedral Ge 4+ centers to which are bonded four terminal atoms and six bridging S atoms. Luminescence studies have shown that 2 exhibits an emission at 468 nm. Graphical Abstract Two Organic Hybrid Thiogermanates [Ni(dien) 2 ] 2 (H 2 dien)Ge 2 S 6 and [Ni(teta) 2 ] 2 Ge 4 S 10

The ternary stannides RE 3 Ru 4 Sn 13 (RE = La, Ce, Pr, Nd) were obtained by arc-melting of the elements. The polycrystalline samples were characterized by powder X-ray diffraction. The structures of three compounds were refined from single-crystal diffractometer data: Yb 3 Rh 4 Sn 13 type, Pm3̄n, a = 977.74(3) pm, wR2 = 0.0379, 280 F 2 values for La 3 Ru 4 Sn 13 , a = 971.34(9) pm, wR2 = 0.0333, 274 F 2 values for Ce 3 Ru 4 Sn 13 , a = 970.68(8) pm, wR2 = 0.0262, 272 F 2 values for Nd 3 Ru 4 Sn 13 with 13 variables per refinement. The structures consist of three-dimensional networks of condensed RuSn 6/2 trigonal prisms with the RE (CN 16) and Sn 2 (CN 12) atoms in two different types of cavities of the networks. The two crystallographically independent tin sites have been resolved by 119Sn Mössbauer spectroscopy. Temperature-dependent magnetic susceptibility measurements of Ce 3 Ru 4 Sn 13 gave a reduced magnetic moment of 2.32 μB per Ce atom, indicating intermediate cerium valence. No magnetic ordering was evident down to 3 K. Graphical Abstract Ternary Stannides RE 3 Ru 4 Sn 13 (RE = La, Ce, Pr, Nd) – Structure, Magnetic Properties, and 119 Sn Mössbauer Spectroscopy

The equiatomic rare earth compounds REPtZn (RE = Y, Pr, Nd, Gd-Tm) were synthesized from the elements in sealed tantalum tubes by high-frequency melting at 1500 K followed by annealing at 1120 K and quenching. The samples were characterized by powder X-ray diffraction. The structures of four crystals were refined from single-crystal diffractometer data: TiNiSi type, Pnma, a = 707.1(1), b = 430.0(1), c = 812.4(1) pm, wR2 = 0.066, 602 F 2 , 21 variables for PrPt 1.056 Zn 0.944 ; a = 695.2(1), b = 419.9(1), c = 804.8(1) pm, wR2 = 0.041, 522 F 2 , 21 variables for GdPt 0.941 Zn 1.059 ; a = 688.2(1), b = 408.1(1), c = 812.5(1) pm, wR2 = 0.041, 497 F 2 , 22 variables for HoPt 1.055 Zn 0.945 ; a = 686.9(1), b = 407.8(1), c = 810.4(1) pm, wR2 = 0.061, 779 F 2 , 20 variables for ErPtZn. The single-crystal data indicate small homogeneity ranges REPt 1±x Zn 1±x . The platinum and zinc atoms build up three-dimensional [PtZn] networks (265 - 269 pm Pt-Zn in ErPtZn) in which the erbium atoms fill cages with coordination number 16 (6 Pt + 6 Zn + 4 Er). Bonding of the erbium atoms to the [PtZn] network proceeds via shorter RE-Pt distances, i. e. 288 - 293 pm in ErPtZn. Graphical Abstract Intermetallic REPtZn Compounds with TiNiSi-type Structure

Neutral tribromo(2-phenyl-1,8-naphthyridine)gold(III), AuBr 3 (N-N), has been prepared by reaction of KAuBr 4 with the ligand in CHCl 3 /C 2 H 5 OH and was characterized by 1H NMR spectroscopy and X-ray diffraction. The molecular and crystal structure of AuBr 3 (N-N) · 0.5 THF (triclinic, P1̄, a = 11.314(2), b = 12.350(3), c = 14.628(3) A° , α = 107.96(3), β = 98.86(3), γ = 107.29(3)◦, Z = 4, 173 K) shows coordination of the N8 nitrogen atom situated in the unsubstituted pyridine ring to the planar four-coordinate Au III center. Whereas the AuBr 3 N best planes and the coordinated naphthyridine rings are not far from orthogonal (ω ~ 105 ◦ ), the phenyl substituents were found in the crystal with a ca. 22 ◦ dihedral angle relative to the naphthyridine plane. Intermolecular Au· · ·Br distances close to the sum of the van der Waals radii indicate very weak interactions to form a quasi-dimeric arrangement in the crystal. Graphical Abstract Synthesis, Characterization and Structure of Tribromo(2-phenyl- 1,8-naphthyridine)gold(III)

The two-dimensional coordination polymer [Ni(bpdc)(bix) 1.5 ·H 2 O] n (H 2 bpdc = 2,4’-biphenyldicarboxylic acid; bix = 1,4-bis(imidazol-1-ylmethyl)benzene) was hydrothermally synthesized and structurally characterized. In the tile compound, the octahedral coordination environment around the Ni 2+ ion is established by two oxygen atoms from two bpdc 2− anions, one water molecule and three nitrogen atoms from three bix ligands. One bix ligand in the asymmetric unit lies on an inversion center at 1, 0.5, 0.5, and the other bix molecule resides on a general position. Each of the two bix molecules is coordinated to four Ni 2+ ions, forming a 52-membered ring which is further assembled into a one-dimensional tape structure running parallel to the [100] direction. By a combination of the O 2 and O 4 oxygen atoms of one bpdc 2− anion coordinating two Ni 2+ ions, adjacent tapes are joined together, forming a layer structure parallel to the (010) plane. A 22-membered ring is formed by means of two bpdc anions binding to two Ni 2+ ions. Graphical Abstract Characterization and Crystal Structure of a Novel Two-dimensional Coordination Polymer: [Ni(bpdc)(bix) 1.5 ·H 2 O] n

The synthesis and crystal structures of two new salts of chromium(III) with pyridine-2,6-dicarboxylic acid H 2 Pda (and 2,2’-bipyridyl, Bpy, as a co-ligand) are reported, (HPyz)[Cr(Pda) 2 ](H 2 Pda)-(H 2 O) 5 (1) and [Cr(Pda)(Bpy)(H 2 O)][Cr(Pda) 2 ](H 2 O) 2 (2). Both crystal structures contain the octahedral [Cr(Pda) 2 ] − anion with the pincer-type O,N,O-Pda 2− ligand. In 1, the pyrazole additive does not act as a ligand, rather it is included as a mono-protonated cation. In 2, both Pda 2− , the neutral 2,2’-bipyridyl and water are coordinating Cr 3+ in the cation [Cr(Pda)(Bpy)(H 2 O)] + . Graphical Abstract Two New Chromium(III) Complexes with the Pincer-type Pyridine-2,6-dicarboxylate Ligand

Hydrothermal reaction of CoCl 2 ・ 6H 2 O, H6chhc (all-cis-1,2,3,4,5,6-cyclohexanehexacarboxylic acid), phen (1,10-phenanthroline), and NaOH in aqueous solution afforded a new coordination polymer Co(phen)(H 2 O)(H 2 chhc), which crystallizes in the space group P1̄ with the cell constants a = 7.267(2), b = 10.749(2), c = 10.826(2) A° , α = 97.86(3), β = 103.62(3), γ = 95.00(3) ◦ , V = 807.8(3) °A 3 and Z = 2. The [Co(phen)(H 2 O)] 2+ cations in the title complex are interlinked by the di-protonated (H 2 chhc) 4− anions in a η 6 μ 4 bridging mode to form 1 ∞ [Co(phen)(H 2 O)(H 2 chhc) 1/2 ] polymer chains running along the [100] direction. Variable temperature magnetic susceptibility studies revealed the presence of weak, long-range antiferromagnetic ordering and zero-field splitting [J = −0.32(5) cm −1 and D = 11.5(1) cm −1 with g = 2.306(4)]. The IR spectrum and results of thermal and elemental analyses are also presented. Graphical Abstract Synthesis, Crystal Structure and Properties of a Cobalt(II) Coordination Polymer with Cyclohexane-1,2,3,4,5,6-hexacarboxylic Acid

Single crystals suitable for X-ray diffraction of ( t Bu 2 P) 3 Ga (monoclinic, space group Cc) were obtained from GaCl 3 and two equivalents of Li[PtBu 2 ] at room temperature in benzene. The phosphanylgallane ( t Bu 2 P) 3 Ga was also produced via a one-pot approach by reaction of GaCl 3 with three or more than three equivalents of Li[PtBu2]. However, treatment of one equivalent of GaCl 3 with one equivalent of Li[PtBu 2 ] and subsequent protolysis yielded [ t Bu 2 PH 2 ][ t Bu 2 P(GaCl 3 ) 2 - Li(Cl 3 Ga) 2 PtBu 2 ]. Single crystals of this phosphonium salt (monoclinic, space group Cc) were obtained from benzene at room temperature. Graphical Abstract Untersuchungen zur Reaktivität des Lithiumphosphanids Li[PtBu 2 ] gegenüber GaCl 3 / Investigations of the Reactivity of the Lithiumphosphanide Li[PtBu 2 ] towards GaCl 3

The reaction of dialkyl acetylenedicarboxylates with 4-hydroxyquinoline in the presence of triphenylphosphine (20 mol-%) produces dialkyl (Z)- and (E)-2-(4-hydroxyquinolin-3-yl)-2-butenedioates in good yields. When the reaction was performed with 2-methyl-4-hydroxyquinoline, similar (E)- and (Z)-isomers were obtained. Graphical Abstract Triphenylphosphine-promoted C-Vinylation of 4-Hydroxyquinolines

Pseudo-ortho- or 4,16-diformyl[2.2]paracyclophane (1) and two polymorphs of pseudo-meta- or 4,13-diformyl[2.2]paracyclophane (2) all display the usual features of [2.2]paracyclophane strain (lengthened C-C bonds and widened C-C(sp 3 )-C angles in the bridges, narrower sp2 ring angles at the bridgehead atoms, and flattened boat conformations of the rings). All bulk samples were racemates. Polymorph 2a crystallizes in space group P2 1 /n with one molecule in a general position, whereas 2b crystallizes in space group C2 with two independent molecules, each with crystallographic twofold symmetry. All three molecules of 2 are different rotamers with respect to the formyl groups; in 2a one is endo and one exo to the neighbouring bridge, whereas in 2b both formyls are exo in one molecule and endo in the other. In all compounds, the packing patterns are preponderantly associated with C-H・ ・ ・O contacts. In 1 the molecules are connected to form tubes parallel to the short a axis. 2a consists of two interconnected layer structures. One is parallel to (100) and involves chains of molecules parallel to [01̄1]; the other is parallel to (001) and involves chains of molecules parallel to the b axis. 2b consists of two hexagonal layers, one for each independent molecule, parallel to (001). One layer contains bifurcated (C-H・ ・ ・ ) 2 O systems, whereas the single H・ ・ ・O interactions in the other are long and markedly bent. Graphical Abstract Isomers of Diformyl[2.2]paracyclophane; X-Ray Structure Determinations of the Pseudo-ortho Isomer and Two Polymorphs of the Pseudo-meta Isomer

By reaction of N-substituted N-phenyl-2-naphthylamimes with the Vilsmeier reagent N-substituted benz[a]acridinium salts are formed in satisfactory yields. Graphical Abstract A Simple Route to Benz[a]acridinium Salts

A series of 3-(alkylthio)-6-chlorothieno[2,3-e][1,4,2]dithiazine 1,1-dioxides (7a - e) were prepared via interaction of deprotonated 2,5-dichlorothiophene-3-sulfonamide with carbon disulfide under reflux, followed by alkylation with alkyl halides. Employment of dimethyl sulfate afforded the isomeric 2-methyl-3-thione derivative 8 together with the expected 3-(methylthio) derivative 7a in a molar ratio of 1 : 4. Treatment of 7a or 10 with ethylamine, aniline or p-chloroaniline produced the corresponding N-ethyl- (or N-phenyl)-6-chlorothieno[2,3-e][1,4,2]dithiazine-3-amine 1,1-dioxides 3a - c. Likewise, interaction of 7a with methylhydrazine (or phenylhydrazine) gave the respective 3-(1-methylhydrazinyl or 2-phenylhydrazinyl) 1,1-dioxides 9a, b. Desulfonation of 6-chloro-3-(methylthio)thieno[ 2,3-e][1,4,2]dithiazine 1,1-dioxide (7a) with sulfuryl chloride produced 3,6-dichlorothieno[2,3- e][1,4,2]dithiazine 1,1-dioxide (10). The latter compound was used as a substrate for the preparation of N-alkyl- (or aryl)-6-chlorothieno[2,3-e][1,4,2]dithiazin-3-amine 1,1-dioxides 3a - c representing a new approach for the synthesis of similar derivatives. Compounds 7a - e showed modest to low antibacterial activity against E. coli and S. aureus. Graphical Abstract Concise Synthesis and Displacement Reactions of Model 3-(Alkylthio)- 6-chloro- and 2,6-Dichlorothieno[2,3-e][1,4,2]dithiazine 1,1-Dioxides

The preparation and characterization of tris-pyridyl bispidine (3,7-diazabicyclo[3.3.1]nonane) derivatives with benzimidazole and imidazole donor groups at the N-3 position of the bispidine skeleton and their copper(II) complexes are reported. The impact of the hetaryl substituents on the configurational isomerism of piperidones and their corresponding bispidones has been studied by NMR spectroscopy, revealing the exclusive appearance in the enol form for the piperidones in solution and the trans-configuration regarding the two pyridyl substituents, as well as the sole formation of the unsymmetric exo-endo isomers for the corresponding bispidones. Thus, the bispidones are preorganized ligands for building pentacoordinated complexes, confirmed by the preparation and characterization of the corresponding Cu(II) complexes. Of the di-pyridyl piperidones with benzimidazole and imidazole substituents, and of the Cu(II) complex of the benzimidazole-containing bispidone, crystals have become available for the analysis by X-ray diffraction, showing that the piperidones form the enol tautomers also in the solid state. Graphical Abstract Imidazole-containing Bispidine Ligands: Synthesis, Structure and Cu(II) Complexation

Two new sesquiterpene lactones (guaianolides), 15-hydroxytaraxacin (1) and 6,8,11-epi-desacetylmatricarin (2), along with three known compounds, desacetylmatricarin (3), 11β ,13-dihydrolactucin (4), and 11β ,13-dihydrolactucopicrin (5), were isolated from the aerial parts of Cichorium intybus L. Graphical Abstract Sesquiterpene Lactones from Cichorium intybus

Seven new compounds, including three benzoic acid allopyranosides keteleeroside A (1), keteleeroside B (2) and keteleeroside C (3), and four lignan glycosides 3’-demethylicariside E 3 (4), isocupressoside B (5), 3-methoxyisocupressoside B (6), and isomassonianoside B (7), along with five known compounds (8 - 12), were isolated from the n-butanol part of the methanolic extract of the twigs of Keteleeria evelyniana. The structures of these compounds were elucidated mainly by the analysis of their NMR and MS data. All compounds were isolated from this genus for the first time. The skeleton of lignan glycoside 4 was isolated from the Pinaceae family for the first time. All compounds were evaluated for antimicrobial activity against Candida albicans and Staphylococcus aureus, and their cytotoxic activity against K562, HT-29, B16, BGC-823, BEL-7402, SGC-7901, U251, and A549 cancer cell lines was studied. Results indicated that none of the compounds showed antimicrobial or cytotoxic activity. Graphical Abstract Benzoic Acid Allopyranosides and Lignan Glycosides from the Twigs of Keteleeria evelyniana

Two new gingerol derivatives, [8]-gingesulfonic acid (1) and [10]-gingesulfonic acid (2), were isolated from the rhizomes of Zingiber officinale, along with nine known gingerol derivatives, [6]- gingesulfonic acid (3), 1-dehydro-[6]-gingerdione (4), 1-dehydro-[8]-gingerdione (5), 1-dehydro- [10]-gingerdione (6), [6]-gingerdione (7), [10]-gingerdione (8), [6]-gingerol (9), methyl [6]-gingerdiol (10), and 6-hydroxyl-[6]-shogaol (11). Their structures were elucidated on the basis of spectral evidence and comparisons with literature data. Graphical Abstract Gingerol Derivatives from the Rhizomes of Zingiber Officinale

For the first time, the macrocyclic monomeric 3-alkyl pyridinium alkaloid with an alkyl chain of 13 methylene groups, haliclocyclin C (1), could be identified from a natural source in the crude extract of the Arctic sponge Haliclona viscosa. Structure elucidation was carried out by comparison of the natural product with the corresponding synthetic compound. Graphical Abstract Haliclocyclin C, a New Monomeric 3-Alkyl Pyridinium Alkaloid from the Arctic Marine Sponge Haliclona viscosa

The new secoiridoids Enicostemins A (1) and B (2) were isolated from the n-butanol-soluble fraction of Enicostemma verticillatum along with gentiocrucine (3) and rutin (4), which were isolated for the first time from the genus Verticillatum. Their structures were assigned based on spectroscopic studies. Graphical Abstract Enicostemins A and B, New Secoiridoids from Enicostemma verticillatum

The crystal and molecular structure of the [VO(DLmeth)( NH 2 O) 2 ]・H 2 O complex has been determined by X-ray diffraction methods (monoclinic, P2 1 /c with a = 5.8138(2), b = 27.3496(8), c = 7.5663(2) A° , β = 103.059(3)◦, and Z = 4). The vanadium(V) cation is in a pentagonal bipyramidal environment axially coordinated to the oxo group and equatorially to two hydroxylamido groups in a side-on fashion. The fifth equatorial binding site and the other apical position are occupied by an N and an O atom, respectively, from the methioninate anion acting as a bidentate ligand. Graphical Abstract Crystal and Molecular Structure of a New Hydroxylamido/Amino Acid Oxovanadium(V) Complex, [VO(NH 2 O) 2 (DL-methioninato)]·H 2 O

N,N´-Dipropyl-N,N,N´ ,N´-tetramethyl-1,2-ethylenediammonium dichloride (1) and dibromide (2) were prepared by the reaction of N,N,N´,N´-tetramethyl-1,2-ethylenediamine and the corresponding 1-halopropane. The structures of the compounds were characterized by single-crystal X-ray diffraction. 1 · 2H 2 O crystallizes in the triclinic crystal system, space group P1, with Z = 1, and 2 in the monoclinic crystal system, space group P2 1 /c, with Z = 2. The crystal structures of the salts consist of discrete dications and halide anions. The packing in 1 · 2H 2 O consists of layers of cations with the chloride anions and water molecules forming hydrogen-bonded chains between the cation layers. In 2, the strongest H· · ·Br hydrogen bonds of 2.8138(6) and 2.8187(7) °A link the cations and anions into doublestranded chains. In both salts, cations and anions are also linked together by a further weak C-H· · ·Cl/Br hydrogen bonding network. Graphical Abstract Synthesis and Structural Characterization of N,N´- Dipropyl-N,N,N´,N´-tetramethyl-1,2- ethylenediammonium Dichloride and Dibromide

Sinenxan H [2α,14β -diacetoxytaxa-4(20),11-diene-5α, 10β -diol, 1] was isolated from the heartwood of Taxus cuspidata, for the first time from natural sources. Compound 1 was found to be readily converted into 2α-acetoxytaxa-4(20),10,12(18),13-tetraen-5α-ol (2), the first example of a taxane with 10,11- and/or 13,14-double bond(s) and a conjugated triene system, in CDCl 3 . Graphical Abstract A Novel Taxatetraene Framework Formed From a New Natural Taxane from Taxus cuspidata