2‐Ethyl‐1‐[5‐(4‐methylphenyl)pyrazol‐3‐yl]‐3‐(thiophene‐2‐carbonyl)isothiourea: molecular ribbons containing three types of hydrogen‐bonded ring

The title compound, C₁₈H₁₈N₄OS₂, was prepared by reaction of S,S‐diethyl 2‐thenoylimidodithiocarbonate with 5‐amino‐3‐(4‐methylphenyl)‐1H‐pyrazole using microwave irradiation under solvent‐free conditions. In the molecule, the thiophene unit is disordered over two sets of atomic sites, with occupancies of 0.814 (4) and 0.186 (4), and the bonded distances provide evidence for polarization in the acylthiourea fragment and for aromatic type delocalization in the pyrazole ring. An intramolecular N—H...O hydrogen bond is present, forming an S(6) motif, and molecules are linked by N—H...O and N—H...N hydrogen bonds to form a ribbon in which centrosymmetric R₂²(4) rings, built from N—H...O hydrogen bonds and flanked by inversion‐related pairs of S(6) rings, alternate with centrosymmetric R₂²(6) rings built from N—H...N hydrogen bonds.     

Tetracycline hydrochloride: a synchrotron microcrystal study

The title compound, [(4S,4aS,5aS,6S,12aS)‐2‐amino­hydroxy­methyl­ene‐1,2,3,4,4a,5,5a,6,11,12a‐deca­hydro‐6,10,12,12a‐tetra­­hydroxy‐6‐methyl‐1,3,11‐trioxo­naphthacen‐4‐yl]­di­methyl­amm­onium chloride, C₂₂H₂₅N₂O₈⁺·Cl^?, a well known antibiotic, has been structurally characterized from an individual coarse powder grain by use of high‐intensity synchrotron radiation, in conjunction with an exercise in ab initio powder diffraction structure solution. Free refinement of all H atoms establishes the major tautomeric form of the protonated tetracycline mol­ecule without prejudice. The mol­ecule has extensive intramolecular hydrogen bonding involving most of the potential donors and acceptors, and all intermolecular hydrogen bonding uses the chloride anion as acceptor.     

Ba3V2S4O3: A Mott Insulating Frustrated Quasi‐One‐Dimensional S=1 Magnet

Through a solid‐state reaction, a practically phase pure powder of Ba₃V₂S₄O₃ was obtained. The crystal structure was confirmed by X‐ray single‐crystal and synchrotron X‐ray powder diffraction (P6₃, a=10.1620(2), c=5.93212(1) Å). X‐ray absorption spectroscopy, in conjunction with multiplet calculations, clearly describes the vanadium in charge‐disproportionated V^IIIS₆ and V^VSO₃ coordinations. The compound is shown to be a strongly correlated Mott insulator, which contradicts previous predictions. Magnetic and specific heat measurements suggest dominant antiferromagnetic spin interactions concomitant with a weak residual ferromagnetic component, and that intrinsic geometric frustration prevents long‐range order from evolving.     

Two Pseudopolymorphic Star‐Shaped Tetranuclear Co3+ Compounds with Disulfide Anions Exhibiting Two Different Connection Modes and Promising Photocatalytic Properties

The compound [Co₄(C₆H₁₄N₂)₄(μ₄‐S₂)₂(μ₂‐S₂)₄] ( I ) and the pseudo‐polymorph [Co₄(C₆H₁₄N₂)₄(μ₄‐S₂)₂(μ₂‐S₂)₄] ? 4 H₂O ( II ) were obtained under solvothermal conditions (C₆H₁₄N₂=trans‐1,2‐diaminocyclohexane). The structures feature S₂^2? ions exhibiting two different coordination modes. Terminal S₂^2? entities join two Co³⁺ centres in a μ₂ fashion, whereas the central S₂^2? groups connect four Co³⁺ cations in a μ₄‐ coordination mode. Compound II can be transformed into compound I by heat and storage over P₂O₅ and storing compound I in humid air yields in the formation of compound II . The intermolecular interactions investigated through Hirshfeld surface analysis reveal that besides S???H bonding close contacts are associated with relatively weak H???H interactions. A detailed DFT analysis of the bonding situation explains the long S?S bonds in the μ₄‐bridging S₂^2? units and the short bonds for the S₂^2? moieties in the μ₂‐connecting mode. Photocatalytic hydrogen evolution experiments demonstrate the potential of compound II as catalyst.     

Metabolism of Deuterated threo‐Dihydroxy Fatty Acids in Saccharomyces cerevisiae: Enantioselective Formation and Characterization of Hydroxylactones and γ‐Lactones

Biotransformation of (±)‐threo‐7,8‐dihydroxy(7,8‐²H₂)tetradecanoic acids (threo‐(7,8‐²H₂)‐ 3 ) in Saccharomyces cerevisiae afforded 5,6‐dihydroxy(5,6‐²H₂)dodecanoic acids (threo‐(5,6‐²H₂)‐ 4 ), which were converted to (5S,6S)‐6‐hydroxy(5,6‐²H₂)dodecano‐5‐lactone ((5S,6S)‐(5,6‐²H₂)‐ 7 ) with 80% e.e. and (5S,6S)‐5‐hydroxy(5,6‐²H₂)dodecano‐6‐lactone ((5S,6S)‐5,6‐²H₂)‐ 8 ). Further β‐oxidation of threo‐(5,6‐²H₂)‐ 4 yielded 3,4‐dihydroxy(3,4‐²H₂)decanoic acids (threo‐(3,4‐²H₂)‐ 5 ), which were converted to (3R,4R)‐3‐hydroxy(3,4‐²H₂)decano‐4‐lactone ((3R,4R)‐ 9 ) with 44% e.e. and converted to ²H‐labeled decano‐4‐lactones ((4R)‐(3‐²H₁)‐ and (4R)‐(2,3‐²H₂)‐ 6 ) with 96% e.e. These results were confirmed by experiments in which (±)‐threo‐3,4‐dihydroxy(3,4‐²H₂)decanoic acids (threo‐(3,4‐²H₂)‐ 5 ) were incubated with yeast. From incubations of methyl (5S,6S)‐ and (5R,6R)‐5,6‐dihydroxy(5,6‐²H₂)dodecanoates ((5S,6S)‐ and (5R,6R)‐(5,6‐²H₂)‐ 4a ), the (5S,6S)‐enantiomer was identified as the precursor of (4R)‐(3‐²H₁)‐ and (2,3‐²H₂)‐ 6 ). Therefore, (4R)‐ 6 is synthesized from (3S,4S)‐ 5 by an oxidation/keto acid reduction pathway involving hydrogen transfer from C(4) to C(2). In an analogous experiment, methyl (9S,10S)‐9,10‐dihydroxyoctadecanoate ((9S,10S)‐ 10a ) was metabolized to (3S,4S)‐3,4‐dihydroxydodecanoic acid ((3S,4S)‐ 15 ) and converted to (4R)‐dodecano‐4‐lactone ((4R)‐ 18 ).     

1‐Aminoindan‐2‐ol,a Suitable Ligand for the Synthesis of Chiral,Intramolecularly Stabilized Compounds of Aluminum,Gallium, and Indium

The reactions of enantiomerically pure (1R, 2S)‐(+)‐cis‐1‐aminoindan‐2‐ol, (1S, 2R)‐(‐)‐cis‐1‐aminoindan‐2‐ol, and racemic trans‐1‐aminoindan‐2‐ol with trimethylaluminum, ‐gallium, and ‐indium produce the intramolecularly stabilized, enantiomerically pure dimethylmetal‐1‐amino‐2‐indanolates (1R, 2S)‐(+)‐cis‐Me₂AlO‐2‐C*HC₇H₆‐1‐C*HNH₂ ( 1 ), (1S, 2R)‐(‐)‐cis‐Me₂AlO‐2C*HC₇H₆‐1‐C*HNH₂ ( 2 ), (1R, 2S)‐(+)‐cis‐Me₂GaO‐2‐C*HC₇H₆‐1‐C*HNH₂ ( 3 ), (1R, 2S)‐(+)‐cis‐Me₂InO‐2‐C*HC₇H₆‐1‐C*HNH₂ ( 4 ), (1S, 2R)‐(‐)‐cis‐Me₂InO‐2‐C*HC₇H₆‐1‐C*HNH₂ ( 5 ), and racemic (+/‐)‐trans‐Me₂InO‐2‐C*HC₇H₆‐1‐C*HNH₂ ( 6 ). The compounds were characterized by ¹H NMR, ¹³C NMR, ²⁷Al NMR and mass spectra as well as 1 and 3 to 6 by determination of their crystal and molecular structures. The dynamic dissociation/association behavior of the coordinative metal‐nitrogen bond was studied by low temperature ¹H NMR spectroscopy.     

Quaternary Sulfide Ba6Zn6ZrS14: Synthesis,Crystal Structure,Band Structure,and Multiband Physical Properties

Ba₆Zn₆ZrS₁₄ was synthesized by a traditional salt‐melt method with KI as flux. The pale yellow crystals of Ba₆Zn₆ZrS₁₄ crystallize in the tetragonal space group I4/mcm with a=16.3481 (4) Å and c=9.7221(6) Å. The structure features unique one‐dimensional parallel [Zn₆S₉]^6? and [ZrS₅]^6? straight chains. The D_2h‐symmetric [Zn₆S₉]^6? cluster serves as the building block of the [Zn₆S₉]^6? chains. A powder sample was investigated by X‐ray diffraction, optical absorption, and photoluminescence measurements. The compound shows multiple‐absorption character with three optical absorption edges around 1.78, 2.50, and 2.65 eV, respectively, which are perfectly consistent with the results of first‐principles calculations. Analysis of the density of states further revealed that the three optical absorption bands are attributable to the three S(3p⁶)→Zr(4d⁰) transitions due to the splitting of the Zr 4d orbitals in the D_4h crystal field. The multiband nature of Ba₆Zn₆ZrS₁₄ also results in photocatalytic activity under visible‐light irradiation and three band‐edge emissions.     

Pentanuclear Gold(I) Cluster with an Axially Chiral Biaryl Center: Synthesis and Chiral Transformation

We synthesized and structurally characterized a novel pentanuclear gold(I) cluster by a Ag(I)‐mediated organometallic transformation. The racemic mixture of this pentanuclear gold cluster has been successfully transformed into an enantio‐rich hexanuclear cluster compound by adding adscititious chiral species [Au₂(S‐BINAP)₂]²⁺ (S‐BINAP = (S)‐2,2’‐bis(diphenylphosphino)‐1,1’‐binaphthyl). In this process, a [AuPPh₃]⁺ species in the pentanuclear cluster is replaced by [Au₂(S‐BINAP)₂]²⁺. This strategy represents a new method for the designed construction of chiral metal clusters.     

Synthesis and Characterization of Copper Hexathiometadiphosphate Cu2P2S6

Copper hexathiometadiphosphate, Cu₂P₂S₆, was synthesized and characterized. Brick‐red copper hexathiometadiphosphate Cu₂P₂S₆ crystallizes in the tetragonal space group P4₂/mnm (no. 136) with a = b = 5.2565(7), c = 15.066(3) Å and V = 416.3(1) ų in a novel structure type. This is the first hexathiometadiphosphate, whose crystal structure is based on a slightly distorted cubic closest packing of sulfur atoms. 1/3 of the tetrahedral voids are occupied by Cu and P in an ordered fashion, thus resulting in a layered structure. The structural motif of layers composed of corner‐sharing CuS₄ tetrahedra (comparable to red HgI₂) that are separated by [P₂S₆]^2– anions orientated perpendicular to these layers, is rarely found in solid state chemistry. The compound is diamagnetic and shows negligible electronic conductivity. Electronic structure calculations and UV/Vis measurements point to a bandgap in the visible range and explain the red color of the compound. Additionally, the oxidation state +1 for Cu was confirmed by the electronic structure calculations. The thermal properties of Cu₂P₂S₆ were investigated by DTA.     

The conformations of two copper(I) complexes of 1H‐benzimidazole‐2(3H)‐thione and thiosaccharinate

(Acetonitrile‐1κN)[μ‐1H‐benzimidazole‐2(3H)‐thione‐1:2κ²S:S][1H‐benzimidazole‐2(3H)‐thione‐2κS]bis(μ‐1,1‐dioxo‐1λ⁶,2‐benzothiazole‐3‐thiolato)‐1:2κ²S³:N;1:2κ²S³:S³‐dicopper(I)(Cu—Cu), [Cu₂(C₇H₄NO₂S₂)₂(C₇H₆N₂S)₂(CH₃CN)] or [Cu₂(tsac)₂(Sbim)₂(CH₃CN)] [tsac is thiosaccharinate and Sbim is 1H‐benzimidazole‐2(3H)‐thione], (I), is a new copper(I) compound that consists of a triply bridged dinuclear Cu—Cu unit. In the complex molecule, two tsac anions and one neutral Sbim ligand bind the metals. One anion bridges via the endocyclic N and exocyclic S atoms (μ‐S:N). The other anion and one of the mercaptobenzimidazole molecules bridge the metals through their exocyclic S atoms (μ‐S:S). The second Sbim ligand coordinates in a monodentate fashion (κS) to one Cu atom, while an acetonitrile molecule coordinates to the other Cu atom. The Cu^I—Cu^I distance [2.6286 (6) Å] can be considered a strong `cuprophilic' interaction. In the case of [μ‐1H‐benzimidazole‐2(3H)‐thione‐1:2κ²S:S]bis[1H‐benzimidazole‐2(3H)‐thione]‐1κS;2κS‐bis(μ‐1,1‐dioxo‐1λ⁶,2‐benzothiazole‐3‐thiolato)‐1:2κ²S³:N;1:2κ²S³:S³‐dicopper(I)(Cu—Cu), [Cu₂(C₇H₄NO₂S₂)₂(C₇H₆N₂S)₃] or [Cu₂(tsac)₂(Sbim)₃], (II), the acetonitrile molecule is substituted by an additional Sbim ligand, which binds one Cu atom via the exocylic S atom. In this case, the Cu^I—Cu^I distance is 2.6068 (11) Å.     

Aqua­bis(3‐meth­oxy‐2‐pyridonato)­(2,2′:6′,2′′‐terpyridine)ruthenium(II)–acetonitrile–water (1/1/1)

The title compound, [Ru(C₆H₆NO₂)₂(C₁₅H₁₁N₃)(H₂O)]·CH₃CN·H₂O, is a transfer hydrogenation catalyst supported by nitro­gen‐donor ligands. This octa­hedral Ru^II complex features rare monodentate coordination of 3‐meth­oxy‐2‐pyridonate ligands and inter­ligand S(6)S(6) hydrogen bonding. Comparison of the title complex with a structural analog with unsubstituted 2‐pyridonate ligands reveals subtle differences in the orientation of the ligand planes.     

Synthesis,Structural Characterization,and Physical Properties of Cs2Ga2S5, and Redetermination of the Crystal Structure of Cs2S6

The reaction of CsN₃ with GaS and S at elevated temperatures results in Cs₂Ga₂S₅. Its crystal structure was determined from single‐crystal X‐ray diffraction data. The colorless solid crystallizes in space group C2/c (no. 15) with V=1073.3(4) ų and Z=4. Cs₂Ga₂S₅ is the first compound that features one‐dimensional chains ${{{\hfill 1\atop \hfill \infty }}}$ [Ga₂S₃(S₂)^2?] of edge‐ and corner‐sharing GaS₄ tetrahedra. The vibrational band of the S₂^2? units at 493 cm^?1 was revealed by Raman spectroscopy. Cs₂Ga₂S₅ has a wide bandgap of about 3.26 eV. The thermal decomposition of CsN₃ yields elemental Cs, which reacts with sulfur to provide Cs₂S₆ as an intermediate product. The crystal structure of Cs₂S₆ was redetermined from selected single crystals. The red compound crystallizes in space group ${P\bar 1}$ with V=488.99(8) ų and Z=2. Cs₂S₆ consists of S₆^2? polysulfide chains and two Cs positions with coordination numbers of 10 and 11, respectively. Results of DFT calculations on Cs₂Ga₂S₅ are in good agreement with the experimental crystal structure and Raman data. The analysis of the chemical bonding behavior revealed completely ionic bonds for Cs, whereas Ga?S and S?S form polarized and fully covalent bonds, respectively. HOMO and LUMO are centered at the S₂ units.     

Synthesis and Crystal Structure of a New Salt of the Water‐Stable Hexathiohypodiphosphate Anion: [py2Li]4[P2S6] ·2 py

A new rare example of a synthetic route in solution to the hexathiohypodiphosphate anion P₂S₆⁴⁻ is presented. Starting from P₄S₃, Li₂S, and elemental sulfur in pyridine, this reaction yields yellow block‐shaped crystals of [py₂Li]₄[P₂S₆] · 2 py ( 1 ). The molecular structure of this hitherto unknown compound was determined by single crystal X‐ray diffraction and reveals a heteronorbornane skeleton within the Li₄P₂S₆ entity.     

An ethanol‐solvated centrosymmetric dimer of bismuth(III) and thiosaccharinate resulting from `semicoordination' contacts

In the title compound, bis(μ‐1,1‐dioxo‐1,2‐benzothiazole‐3‐thiolato)‐κ³N,S:S;κ³S:N,S‐bis[(1,1‐dioxo‐1,2‐benzothiazole‐3‐thiolato‐κ²N,S)(ethanol‐κO)bismuth(III)] ethanol hemisolvate, [Bi₂(C₇H₄NO₂S₂)₆(C₂H₅OH)₂]·0.5C₂H₅OH, three independent thiosaccharinate (tsac) anions chelate the metal centre through the endocyclic N and exocyclic S atoms. The complex also presnts two `semicoordination' contacts, one from a pendant ethanol solvent molecule and a second one from an S atom of a centrosymmetrically related molecule. This latter interaction complements two π–π interactions between tsac rings to form a dimeric entity which is the elemental unit that builds up the crystal structure. These dinuclear units are connected to each other via a second type of π–π interaction, generating chains along [11]. Two ethanol molecules, one of them of full occupancy at a general position and semicoordinated to the central cation, and a second one depleted and disordered around a symmetry centre, stabilize the structure. The complex was studied theoretically and the vibrational assignations were confirmed by employing theoretical density functional theory (DFT) methods.     

A Series of Novel Organically Templated Germanium Antimony Sulfides

A series of novel organically templated germanium antimony sulfides have been solvothermally synthesized and structurally, thermally, and optically characterized. The compound [Me₂NH₂]₆[(Ge₂Sb₂S₇)(Ge₄S₁₀)] ( 1 ) features two distinct tetranuclear [Ge₂Sb₂S₇]^2? and [Ge₄S₁₀]^4? isolated clusters. The compound [(Me)₂NH₂][DabcoH]₂[Ge₂Sb₃S₁₀] ( 2 ) (Dabco=triethylenediamine) features a 1D‐[Ge₂Sb₃S₁₀]_n^3n? ribbon constructed with two [GeSbS₅]_n^3n? chains bridged by Sb³⁺ ion in ψ‐SbS₄ configuration. Compounds [M(en)₃][GeSb₂S₆] (M=Ni ( 3 ), Co ( 4 ) en=ethylenediamine) feature the unique 2D grid layer structures of [GeSb₂S₆]_n^2n?. The compound [(Me)₂NH₂]₂[GeSb₂S₆] ( 5 ) previously reported by us features a 3D chiral microporous structure with the chiral channels. The optical absorption spectra indicate that all the compounds are wide bandgap semiconductors. Thermal stabilities of these compounds have been investigated by thermogravimetric analyses (TGA).     

A three‐dimensional homochiral metal–organic framework constructed from manganese(II) with S‐carboxymethyl‐N‐(p‐tosyl)‐l‐cysteine and 4,4′‐bipyridine

In the chiral polymeric title compound, poly[aqua(4,4′‐bipyridine)[μ₃‐S‐carboxylatomethyl‐N‐(p‐tosyl)‐l ‐cysteinato]manganese(II)], [Mn(C₁₂H₁₃NO₆S₂)(C₁₀H₈N₂)(H₂O)]_n, the Mn^II ion is coordinated in a distorted octahedral geometry by one water molecule, three carboxylate O atoms from three S‐carboxyatomethyl‐N‐(p‐tosyl)‐l ‐cysteinate (Ts‐cmc) ligands and two N atoms from two 4,4′‐bipyridine molecules. Each Ts‐cmc ligand behaves as a chiral μ₃‐linker connecting three Mn^II ions. The two‐dimensional frameworks thus formed are further connected by 4,4′‐bipyridine ligands into a three‐dimensional homochiral metal–organic framework. This is a rare case of a homochiral metal–organic framework with a flexible chiral ligand as linker, and this result demonstrates the important role of noncovalent interactions in stabilizing such assemblies.     

[2,6‐Bis(isopropylthiomethyl)phenyl‐κ3S,C1,S′]bromopalladium(II)

The title compound, [PdBr(C₁₄H₂₁S₂)] or [PdBr{C₆H₃(CH₂SⁱPr)₂‐2,6}], exhibits square‐planar geometry at the Pd centre, with three atoms of the square plane provided by the rigid thio­pincer ligand, i.e. 1,3‐bis­(thio­methyl)­benzene.     

Phenanthroline complexes of zinc and calcium carbamates

Bis(N,N‐di‐n‐butyl­di­thio­carbamato‐κ²S,S′)(1,10‐phenanthroline‐κ²N,N′)­zinc(II) ethanol hemisolvate, [Zn(C₉H₁₈NS₂)₂(C₁₂H₈N₂)]·0.5C₂H₆O, (I), and bis(N,N‐di‐n‐hexyldithiocarbamato‐κ²S,S′)­bis(1,10‐phenanthroline‐κ²N,N′)calcium(II), [Ca(C₁₃H₂₆NS₂)₂(C₁₂H₈N₂)₂], (II), are mixed‐ligand com­plexes. In the first compound, the Zn atom has a distorted octahedral coordination, while in the second compound, the Ca atom is eight‐coordinate, with four S and four N atoms forming a highly distorted cube.     

γ‐Modification of poly[(N,N‐diethyl­dithio­carbamato)silver(I)]

In the title compound, catena‐poly[[tri­silver(I)‐tri‐μ₃‐N,N‐diethyl­dithio­carbamato‐3′κS:1κS′:2κS;1κS:2κS′:3κS;2κS:3κ²S,S′:1′κS′], [Ag₃(C₅H₁₀NS₂)₃]_n, the trigonally and tetra­hedrally coordinated Ag atoms are μ₃‐bridged by κ³‐ and κ⁴‐S₂CNEt₂ ligands to form a ribbon structure along the c axis. There is a twofold axis parallel to the b axis and passing through the tetra­hedrally coordinated Ag atom. The S₂CNEt₂ ligands coordinate the Ag atoms in η¹,η²‐ and η²,η²‐fashions, depending on the bridging S atoms. The distances between the trigonal Ag and S atoms are 2.4915 (11)–2.6205 (11) Å, while those between the tetra­hedral Ag and S atoms are 2.5457 (11) and 2.7145 (10) Å. The shortest Ag⋯Ag distance between trigonal Ag atoms is 2.8336 (7) Å, which indicates a weak Ag⋯Ag inter­action, whereas the shortest distance between trigonal and tetra­hedral Ag atoms is 3.463 (6) Å, which is considered as non‐bonding.     

Nonmerohedrally twinned 6‐amino‐3‐methyluracil‐5‐carbaldehyde: a hydrogen‐bonded ribbon containing four types of ring

In the title compound [systematic name: 6‐amino‐5‐formyl‐3‐methylpyrimidine‐2,4(1H,3H)‐dione], C₆H₇N₃O₃, the intramolecular dimensions provide evidence for some polarization of the electronic structure. There is an intramolecular N—H...O hydrogen bond; this and a combination of three intermolecular N—H...O hydrogen bonds generate an almost planar ribbon containing S(6), R₂²(4), R₂¹(6) and R₄⁴(16) rings. These ribbons are linked into sheets by a dipolar carbonyl–carbonyl interaction. The structure was refined as a nonmerohedral twin, with twin fractions 0.7924 (1) and 0.2076 (10).