Crystallographic report: Bis[bis(N‐methyl‐N‐phenyldithiocarbamato)‐(methylxanthato)bismuth(III)]

The centrosymmetric structure of {Bi[S₂CN(Me)Ph]₂(S₂COMe)}₂ features chelating dithiocarbamate and xanthate ligands, as well as intermolecular Bi·S interactions, so that a distorted pentagonal bipyramidal S₇ coordination geometry results. Copyright © 2004 John Wiley & Sons, Ltd.     

Crystallographic report: Bis[tris(morpholindithiocarbamato)bismuth(III)]

The dimeric and centrosymmetric structure of {Bi[S₂CN(CH₂CH₂)₂O]₃}₂ features chelating dithiocarbamate ligands and intermolecular Bi? S interactions, so that a distorted pentagonal bipyramidal S₇ coordination geometry results. Copyright © 2004 John Wiley & Sons, Ltd.     

Crystallographic report: Bis[(nitro)bis(dithiotetrahydropyrrolocarbamato) bismuth(III)]

The loosely associated centrosymmetric structure of [Bi(S₂CNC₄H₈)₂(NO₃)]₂ features chelating dithiocarbamate and nitrate ligands, as well as weak intermolecular Bi? S interactions, so that a distorted pentagonal bipyramidal S₅O₂ coordination geometry results. Copyright © 2005 John Wiley & Sons, Ltd.     

(Ge4Bi14)4−: A Case of “Element Segregation” on the Molecular Level

Extraction of a solid with the nominal composition “K₂GeBi” with 1,2‐diaminoethane (en) in the presence of 4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane (crypt‐222) afforded the salt [K(crypt‐222)]₄(Ge₄Bi₁₄). The 18‐atom Zintl anion (Ge₄Bi₁₄)⁴⁻ has a heretofore unknown molecular topology, which can be thought of as the formal condensation product of two E₁₁³⁻ cages along a shared Ge₄ waist. In this way, (Ge₄Bi₁₄)⁴⁻ represents the largest and most structurally complex Bi‐containing polyanion. We describe its stepwise formation, its geometric and electronic structure, and comment on relative stabilities of isomers with different distributions of the four Ge atoms on the 18 positions that were investigated using DFT calculations.     

Synthesis,structural characterization,density functional theory calculations and biological evaluation of a new organotin(IV) complex containing N‐isonicotinyl‐N',N″‐diaryl phosphorictriamide as N‐donor ligand

A new diorganotin(IV) complex with the formula SnCl₂(CH₃)₂L₂ ( C_1a ), L = 4‐NC₅H₄CONHPO(NCH₃CH₂C₆H₅)₂, was synthesized and characterized using ¹H NMR, ¹³C NMR, ³¹P NMR, ¹¹⁹Sn NMR and infrared spectroscopies. The molecular structure of C_1a was determined using X‐ray crystallography, revealing that C_1a contains hexa‐coordinated Sn(IV) centres with trans‐configuration of donor atoms around them. Each Sn(IV) atom is positioned in the centre of inversion of an octahedron. C_1a forms one‐dimensional chains via two equal intermolecular P?O…H? N hydrogen bonds. These hydrogen bonds produce centrosymmetric rings as a supramolecular hydrogen‐bonded pattern. In order to compare the relative stability of C_1a (with N‐ligated configuration) and its possible O‐ligated isomer, C_1b , density functional theory calculations were performed, the results showing a preference of C_1a over C_1b from an energy point of view. Also, natural bond orbital analysis was carried out to obtain detailed information on the electronic features of the optimized structures. The theoretical results show that intermolecular hydrogen bonding in the crystal structure has a significant role in the stabilization of C_1a , and Sn(IV) interacts more strongly with the N_py atom than the P?O functional group. Furthermore, the free ligand and its complex were tested against three human cancer cell lines, i.e. human cervical carcinoma (HeLa), human prostate cancer (PC‐3) and human breast adenocarcinoma cancer (MCF‐7). C_1a displays moderate to good cytotoxicity towards all three cancer cell lines. Moreover, antibacterial tests were carried out using the disc‐diffusion method, in which C_1a shows high activity against selected Gram‐negative and Gram‐positive bacteria. Copyright © 2015 John Wiley & Sons, Ltd.     

Planarity of benzoylthiocarbazate tuberculostatics. III. Diesters of 3‐(2‐hydroxybenzoyl)dithiocarbazic acid

Searches for new tuberculostatic agents are important considering the occurrence of drug‐resistant strains of Mycobacterium tuberculosis . The structures of three new potentially tuberculostatic compounds, namely isopropyl methyl (2‐hydroxybenzoyl)carbonohydrazonodithioate, C₁₂H₁₆N₂O₂S₂, (Z )‐benzyl methyl (2‐hydroxybenzoyl)carbonohydrazonodithioate, C₁₆H₁₆N₂O₂S₂, and dibenzyl (2‐hydroxybenzoyl)carbonohydrazonodithioate propan‐2‐ol monosolvate, C₂₂H₂₀N₂O₂S₂·C₃H₈O, were determined by X‐ray diffraction. The mutual orientation of the three main fragments of the compounds, namely an aromatic ring, a dithioester group and a hydrazide group, can influence the biological activity of the compounds. In all three of the structures studied, the C(=O)NH group is in the anti conformation. In addition, the presence of the hydroxy group in the ortho position of the aromatic ring in all three structures leads to the formation of an intramolecular hydrogen bond stabilizing the planarity of the molecules.     

Synthesis,structural analysis,spectral investigations,and DFT calculations of 1‐(3‐amino‐4‐thia‐1,2‐diazaspiro[4.11]hexadec‐2‐en‐1‐yl)ethan‐1‐one

1‐(3‐amino‐4‐thia‐1,2‐diazaspiro[4.11]hexadec‐2‐en‐1‐yl)ethan‐1‐one was synthesized and experimentally characterized by using FT‐IR, ¹H NMR, ¹³C NMR, and UV–Vis spectroscopy. The structure of the compound was confirmed by single‐crystal X‐ray diffraction. In the crystal structure, the molecules are linked by pairs of N‐H⋯N hydrogen bonds, forming centrosymmetric dimers with the graph‐set motif. The water molecule also plays an important role in the stabilization of the crystal structure, bridging the dimers to form a two‐dimensional supramolecular network. The molecular geometry, frontier molecular orbitals, vibrational frequencies, electronic properties, and molecular electrostatic potential were calculated using density functional theory (DFT) with the B3LYP/6‐311G(d,p) basis set. Geometric parameters, vibrational assignments, and electronic properties such as calculated energies, excitation energies, and oscillator strengths were compared with the experimental data, and it was seen that the theoretical results support the experimental parameters.     

[Ga6R8]2– (R = SiPh2Me): Eine metalloide Clusterverbindung mit einem unerwarteten Ga6‐Gerüst

[Ga₆R₈]^2– (R = SiPh₂Me): A Metalloid Cluster Compound with an Unexpected Ga₆‐Frame The reaction of a metastable solution of GaBr with a solution of LiSiPh₂Me in a toluene/THF mixture results in orange coloured crystals of [Ga₆(SiPh₂Me)₈]^2– · 2 [Li(THF)₄]⁺ ( 1 ). The unexpected structure of the planar Ga₆ frame (C_2h) could also be realized with the help of DFT calculation. DFT calculations furthermore show that 1 is energetically favoured against an octahedral Ga₆R₆^2– species and R₂. In contrast calculations for the similar Al and B species show that in these cases the octahedral entities are favoured. These results demonstrate that even for similar compounds of B, Al, and Ga Wade rules are too general and that they cannot predict the correct structure. Moreover the atomic arrangement within 1 shows that a structure is preferred which is also present in allotropic β‐Ga and that therefore clusters of this type should be called metalloid or more general elementoid.     

1‐Carboxymethyl‐3‐methyl‐1H‐imidazol‐3‐ium chloride 2‐(3‐methyl‐1H‐imidazol‐3‐ium‐1‐yl)acetate monohydrate: a crystal stabilized by imidazolium zwitterions

The title compound, C₆H₉N₂O₂⁺·Cl⁻·C₆H₈N₂O₂·H₂O, contains one 2‐(3‐methyl‐1H‐imidazol‐3‐ium‐1‐yl)acetate inner salt molecule, one 1‐carboxymethyl‐3‐methyl‐1H‐imidazol‐3‐ium cation, one chloride ion and one water molecule. In the extended structure, chloride anions and water molecules are linked via O—H...Cl hydrogen bonds, forming an infinite one‐dimensional chain. The chloride anions are also linked by two weak C—H...Cl interactions to neighbouring methylene groups and imidazole rings. Two imidazolium moieties form a homoconjugated cation through a strong and asymmetric O—H...O hydrogen bond of 2.472 (2) Å. The IR spectrum shows a continuous D‐type absorption in the region below 1300 cm⁻¹ and is different to that of 1‐carboxymethyl‐3‐methylimidazolium chloride [Xuan, Wang & Xue (2012). Spectrochim. Acta Part A, 96 , 436–443].     

X‐ray structures,spectroscopic, electrochemical,thermal, antibacterial,and DFT studies of two nickel(II) and cobalt(III) complexes constructed from a new quinazoline‐type ligand

Two two‐dimensional supramolecular Nickel(II) and Cobalt(III) complexes, [Ni( L ² )₂]·2CH₃OH ( 1 ) and [2Co( L ² )₂] ( 2 ) ( HL ²  = 1‐(2‐{[(E)‐3‐bromo‐5‐chloro‐2‐hydroxybenzylidene]amino}phenyl)ethanone oxime), were synthesized via complexation of salts acetate with HL ¹ (2‐(3‐bromo‐5‐chloro‐2‐hydroxyphenyl)‐4‐methyl‐1,2‐dihydroquinazoline 3‐oxide, H is the deprotonatable hydrogen). During the reaction, the C–N bond in HL ¹ is converted into the C=N–OH group in HL ² . The spectroscopic data of both complexes were compared with the ligand HL ¹ . HL ¹ and both complexes were determined by single‐crystal X‐ray crystallography. The differently geometric features of the obtained complexes 1 and 2 are observed. In the crystal structure, 1 and 2 form an infinite 1‐D chain‐like and 2‐D supramolecular frameworks. EPR spectroscopy of 2 was investigated. Moreover, electrochemical properties and antimicrobial activities of both complexes were also studied. In addition, the calculated HOMO and LUMO energies show the character of HL ¹ , complexes 1 and 2 . The electronic transitions and spectral features of HL ¹ and both complexes were discussed by TD‐DFT calculations.     

2,2′‐[(Disulfanediyl)bis{5‐[(1E)‐(2‐hydroxybenzylidene)amino]‐1,3‐thiazole‐4,2‐diyl}]diphenol: synthesis,crystal structure and calculation of molecular hyperpolarizability

The title Schiff base compound {systematic name: 2‐[5‐[(E )‐(2‐hydroxybenzylidene)amino]‐4‐(2‐{5‐[(E )‐(2‐hydroxybenzylidene)amino]‐2‐(2‐hydroxyphenyl)‐1,3‐thiazol‐4‐yl}disulfanyl)‐1,3‐thiazol‐2‐yl]phenol}, C₃₂H₂₂N₄O₄S₄, incorporating a disulfanediyl (dithio) linkage, was obtained from the condensation reaction between two equivalents of salicylaldehyde and one equivalent of dithiooxamide in dimethylformamide, and was characterized by elemental analysis, IR spectroscopic analysis and single‐crystal X‐ray diffraction. A one‐dimensional chain is formed along the b axis via double intermolecular C—H…S hydrogen bonds. The HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energies and some related molecular parameters were calculated at the B3LYP/6‐311G(d,p) level of theory. The molecular hyperpolarizability was also calculated.     

Geometrical and Ground State Electronic Structures of Nitrosylcobalt Complexes [(RNCHCHNR)Co(NO)(CO)] (R = Isopropyl, 2,6‐Diisopropylphenyl or p‐Tolyl) from Experiment and DFT‐Calculations

The new complexes (RN=CH‐CH=NR)Co(NO)(CO), R = isopropyl ( 1 ), 2,6‐diisopropylphenyl ( 2 ) and p‐tolyl ( 3 ), were synthesized and spectroscopically characterized. Compounds 1 and 2 could be crystallized for X‐ray structure analysis, CO/NO disorder was observed for 1 . The results indicate a negligible amount of charge transfer from the Co(NO)(CO) moiety to the 1, 4‐diazabutadiene acceptor ligands in the ground state, in agreement with DFT calculations on 1 and as similarly reported for related 1, 4‐diaza‐1, 3‐butadiene complexes of Ni(CO)₂ and Fe(NO)₂.     

209Bi NQR study of bismuth(III) complexes

Potassium pentafluorobismuthate(III), nitrate-chloride Bi^III complexes MBiCl₃NO₃ (M=K, (NH₂)₂CNH₂), sulfate-chloride Bi^III complexes MBiCl₂SO₄ (M=K, Rb, NH₄, (NH₂(₂CNH₂), and Bi^III complexonates with the anions of ethylenediaminetetraacetic acid M[Bi(edta)]₂·nH₂O (M=Mg, Ca, Ni, Cd) and nitrilotriacetic acid Bi(nta)·2H₂O, and Bi(nta)·3thio·H₂O (thio is thiourea) were studied by²⁰⁹Bi NQR spectroscopy. A second-order phase transition was observed in K₂BiF₅ at 100 K. The compounds Bi(nta)·2H₂O, (NH₂)₂CNH₂BiCl₃NO₃, and MBiCl₂SO₄ (M=K, NH₄) are piezoelectrics. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2237–2240, November, 1998.     

(Hexafluorosilicato‐κ2F,F′)bis(1,10‐phenanthroline‐κ2N,N′)zinc(II) methanol monosolvate

The title compound, [Zn(SiF₆)(C₁₂H₈N₂)₂]·CH₃OH, contains a neutral heteroleptic tris‐chelate Zn^II complex, viz. [Zn(SiF₆)(phen)₂] (phen is 1,10‐phenanthroline), exhibiting approximate molecular C₂ point‐group symmetry. The Zn^II cation adopts a severely distorted octahedral coordination. As far as can be ascertained, the title complex represents the first structurally characterized example of a Zn^II complex bearing a bidentate‐bound hexafluorosilicate ligand. A density functional theory study of the isolated [Zn(SiF₆)(phen)₂] complex was undertaken to reveal the influence of crystal packing on the molecular structure of the complex. In the crystal structure, the methanol solvent molecule forms a hydrogen bond to one F atom of the hexafluorosilicate ligand. The hydrogen‐bonded assemblies so formed are tightly packed in the crystal, as indicated by a high packing coefficient (74.1%).     

Crystallographic report: Bi(S2CNC5H10)2(NO3)(1,10‐phenanthroline)

The structure of Bi(S₂CNC₅H₁₀)₂(NO₃)(1,10‐Phen) features an eight‐coordinated distorted square antiprismatic geometry around bismuth, defined by an N₂O₂S₄ donor set, with Bi? S distances ranging from 2.641(2) to 2.824(2) Å. Copyright © 2004 John Wiley & Sons, Ltd.     

Preparation,Spectroscopic Properties,and Crystal Structures of Fe2(CO)6(μ‐CO)(μ‐CF2)2, Fe2(CO)6(μ‐CO)2(μ‐CF2), and Fe2(CO)6(μ‐CF2)(PPh3)2 – Theoretical Studies of Methylenic vs. Carbonyl Bridges in Diiron Complexes

The reaction of Na₂[Fe(CO)₄] with Br₂CF₂ in n‐pentane generates a mixture of the compounds (CO)₃Fe(μ‐CO)_3–n(μ‐CF₂)_nFe(CO)₃ ( 2 , n = 2; 3 , n = 1) in low yields with 3 as the main product. 3 is obtained free from 2 by reacting Br₂CF₂ with Na₂[Fe₂(CO)₈]. The non‐isolable monomeric complex (CO)₄Fe=CF₂ ( 1 ) can probably considered as the precursor for 2 . 3 reacts with PPh₃ with replacement of two CO ligands to form Fe₂(CO)₆(μ‐CF₂)(PPh₃)₂ ( 4 ). The complexes 2 – 4 were characterized by single crystal X‐ray diffraction. While the structure of 2 is strictly similar to that of Fe₂(CO)₉, the structure of 3 can better be described as a resulting from superposition of the two enantiomers 3 a and 3 b with two semibridging CO groups. Quantum chemical DFT calculations for the series (CO)₃Fe(μCO)_3–n(μ‐CF₂)_nFe(CO)₃ (n = 0, 1, 2, 3) as well as for the corresponding (μ‐CH₂) derivatives indicate that the progressively larger σ donor and π acceptor properties for the bridging ligands, in the order CO < CF₂ < CH₂, favor a stronger Fe–Fe bond.     

Crystallographic report: [N,N′‐Bis‐(6‐methylpyrid‐2‐ylium)‐(1R,2R)‐1,2‐diaminocyclohexane] bis‐[(p‐cymene)‐ trichlororuthenate(II)]

The chiral compound (H₂cydiampy)[RuCl₃(p‐cymene)]₂ has been obtained in high yield by treating [RuCl₂(p‐cymene)]₂ with an excess of hydrochloric acid in the presence of one equivalent of N,N′‐bis‐(6‐methylpyrid‐2‐yl)‐(1R,2R)‐1,2‐diaminocyclohexane (cydiampy). It crystallizes in the chiral tetragonal space group P4₃2₁2, with half of the atoms of the dication related to the other half by a crystallographic C₂ axis that also makes equivalent the two anionic metal moieties. Copyright © 2005 John Wiley & Sons, Ltd.     

Crystallographic report: (η5‐Fluorenyl)‐tris‐pyridine‐di‐iodo‐lanthanum(III) and ‐neodymium(III)

The structures of the title compounds are mononuclear with each lanthanide bound by a single η⁵‐fluorenyl ligand, two trans‐disposed iodides and three meridionally oriented pyridine molecules. Copyright © 2005 John Wiley & Sons, Ltd.     

Bis(triphenylphosphin)iminium-bis(methoxo)phthalocyaninato(2–)ferrat(III) – Synthese und Kristallstruktur

Bis(triphenylphosphine)iminium Bis(methoxo)phthalocyaninato(2–)ferrate(III) – Synthesis and Crystal Structure Chlorophthalocyaninato(2–)ferrate(III) reacts with bis(triphenylphosphine)iminium hydroxide in methanol/acetone solution to yield blue crystals of bis(triphenylphosphine)iminium bis(methoxo)phthalocyaninato(2–)ferrate(III). The complex salt crystallizes as an acetone/methanol solvate (^bPNP)[Fe(OCH₃)₂pc^2–] · (CH₃)₂CO · 1.5 CH₃OH in the triclinic space group P 1 (no. 2) with the cell parameters a = 13.160(5) Å, b = 15.480(5) Å, c = 17.140(5) Å, α = 97.54(5)°, β = 91.79(5)°, γ = 95.44(5)°. The Fe atom is located in the centre of the pc^2– ligand coordinating four isoindole N atoms (N_iso) of the pc^2– ligand and two O atoms of the methoxo ligands in a mutual trans arrangement. The average Fe–O and Fe–N_iso distances are 1.887 and 1.943 Å, respectively. The cation adopts the bent conformation (< P–N–P = 140.4(2)°) with P–N distances of 1.579(3) and 1.575(3) Å.