Tetraaqua‐1κO,2κ3O‐(μ‐2,4‐dinitrophenolato‐1κ2O1,O2:2κO1)(2,4‐dinitrophenolato‐1κ2O1,O2)dilithium(I): a dinuclear lithium(I) complex

The title complex, [Li₂(C₆H₃N₂O₅)₂(H₂O)₄], contains two kinds of Li atoms, viz. five‐coordinated and four‐coordinated. The five‐coordinated Li ion has a tetragonal–pyramidal geometry, with a water molecule in the apical position and four O atoms from two 2,4‐dinitrophenolate (2,4‐DNP) ligands in the basal plane. The four‐coordinated Li ion has a tetrahedral geometry, with three water molecules and one phenolate O atom of a 2,4‐DNP ligand. The Li ions are bridged by a phenolate O atom, giving the complex a dinuclear structure. The crystal packing is stabilized by O—H...O hydrogen‐bonding interactions involving the water molecules and nitro O atoms.     

A new [(1R,2R)‐1,2‐diaminocyclohexane]platinum(II) complex: formation by nitrate–acetonitrile ligand exchange

The title compound, cis‐diacetonitrile[(1R,2R)‐1,2‐diaminocyclohexane‐κ²N,N′]platinum(II) dinitrate monohydrate, [Pt(C₂H₃N)₂(C₆H₁₄N₂)](NO₃)₂·H₂O, is a molecular salt of the diaminocyclohexane–Pt complex cation. There are two formula units in the asymmetric unit. Apart from the two charge‐balancing nitrate anions, one neutral molecule of water is present. The components interact via N—H...O and O—H...O hydrogen bonds, resulting in supramolecular chains. The title compound crystallizes only from acetonitrile with residual water, with the acetonitrile coordinating to the molecule of cis‐[Pt(NO₃)₂(DACH)] (DACH is 1,2‐diaminocyclohexane) and the water forming a monohydrate.     

Synthesis and structure of tetranuclear copper(Ⅱ) complex containing μ4-oxo bridge

A new dinucleating Schiff base ligand HL(L=C13H17N2O3) has been synthesised and characterized.The single crystal structure of its complex [L2Cu4O(AcO4)]·2H2O has beendetermined by X-ray diffraction methods.The result indicates that every Cu atom has its square pyramidal coordination polyhedron and there is a tetrahedral Cu4O core in the complex molecule.Its active sites where catalytic oxidation of dioxygen occurs have been inferred.     

Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]•0.5bipy•3H2O配合物的合成、晶体结构及荧光性质

在水-乙醇混合体系中, 以2-羰基丙酸水杨酰腙(C₁₀H₁₀N₂O₄)、2,2-联吡啶(C₁₀H₈N₂, 简写bipy)与Eu(NO₃)₃•4H₂O反应, 首次培养出黄色单晶[Eu(C₁₀H₉N₂O₄)(C₁₀H₈N₂O₄)(H₂O)₃]•0.5bipy•3H₂O. 该晶体属三斜晶系, 空间群为P-1, 晶胞参数a＝0.93392(16) nm, b＝1.3100(2) nm, c＝1.3895(2) nm, α＝97.205(3)°, β＝105.411(2)°, γ＝106.364(2)°, V＝15.35(2) nm³, Z＝2, μ＝2.118 mm^－1, D_c＝1.686 Mg/m³, F(000)＝786, R＝0.0116, wR＝0.0507, GOF＝0.995. 晶体测试结果表明, 该单晶结构为铕的9配位配合物, 两个2-羰基丙酸水杨酰腙分别以负一价和负二价酮式和三个水分子同时参与配位; 每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和C＝N中的氮与Eu^3＋配位, 形成两个共边的稳定五元环, 另三个配位原子则分别来自三个水分子中的氧原子, 该配合物在空间呈扭曲的单帽四方反棱柱, 而在不对称单位中还有游离的一个2,2-联吡啶分子和三个水分子, 这些游离分子与配位分子之间存在大量分子内和分子间氢键, 整个分子在空间呈三维网状结构. 发光性能测试表明该配合物具有很好的荧光性质.     

Bis(5‐hydroxy‐2‐hydroxy­methyl‐4‐pyrone‐κ2O4,O5)bis(2‐hydroxy­methyl‐5‐oxido‐4‐pyrone‐κ2O4,O5)­calcium(II) tetrahydrate

In the title compound, [Ca(C₆H₅O₄)₂(C₆H₆O₄)₂]·4H₂O, which is a kojic acid–Ca²⁺ complex, the Ca atom is on a twofold axis and is octacoordinated by O atoms from four pyrone ligand mol­ecules. The hydroxyl and ketone O atoms of each ligand form a five‐membered chelate ring with the Ca atom. The crystal structure is stabilized by partial stacking and O—H?O hydrogen bonds.     

The new three‐dimensional supramolecule bis{μ‐2‐[(4‐hydroxybenzoyl)hydrazonomethyl]phenolato}bis[aquacopper(II)] dinitrate

In the title centrosymmetric binuclear complex, [Cu₂(C₁₄H₁₁N₂O₃)₂(H₂O)₂](NO₃)₂, the two metal centres are bridged by the phenolate O atoms of the ligand, forming a Cu₂O₂ quadrangle. Each Cu atom has a distorted square‐pyramidal geometry, with the basal donor atoms coming from the O,N,O′‐tridentate ligand and a symmetry‐related phenolate O atom. The more weakly bound apical donor O atom is supplied by a coordinated water molecule. When a further weak Cu...O interaction with the 4‐hydroxy O atom of a neighbouring cation is considered, the extended coordination sphere of the Cu atom can be described as distorted octahedral. This interaction leads to two‐dimensional layers, which extend parallel to the (100) direction. The two‐dimensional polymeric structure contrasts with other reported structures involving salicylaldehyde benzoylhydrazone ligands, which are usually discrete mono‐ or dinuclear Cu complexes. The nitrate anions are involved in a three‐dimensional hydrogen‐bonding network, featuring intermolecular N—H...O and O—H...O hydrogen bonds.     

Crystallization experiments with the dinuclear chelate ring complex di‐μ‐chlorido‐bis[(η2‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC1)platinum(II)]

Crystallization experiments with the dinuclear chelate ring complex di‐μ‐chlorido‐bis[(η²‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC¹)platinum(II)], [Pt₂(C₁₅H₁₉O₄)₂Cl₂], containing a derivative of the natural compound eugenol as ligand, have been performed. Using five different sets of crystallization conditions resulted in four different complexes which can be further used as starting compounds for the synthesis of Pt complexes with promising anticancer activities. In the case of vapour diffusion with the binary chloroform–diethyl ether or methylene chloride–diethyl ether systems, no change of the molecular structure was observed. Using evaporation from acetonitrile (at room temperature), dimethylformamide (DMF, at 313 K) or dimethyl sulfoxide (DMSO, at 313 K), however, resulted in the displacement of a chloride ligand by the solvent, giving, respectively, the mononuclear complexes (acetonitrile‐κN)(η²‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC¹)chloridoplatinum(II) monohydrate, [Pt(C₁₅H₁₉O₄)Cl(CH₃CN)]·H₂O, (η²‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC¹)chlorido(dimethylformamide‐κO)platinum(II), [Pt(C₁₅H₁₉O₄)Cl(C₂H₇NO)], and (η²‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC¹)chlorido(dimethyl sulfoxide‐κS)platinum(II), determined as the analogue {η²‐2‐allyl‐4‐methoxy‐5‐[(ethoxycarbonyl)methoxy]phenyl‐κC¹}chlorido(dimethyl sulfoxide‐κS)platinum(II), [Pt(C₁₄H₁₇O₄)Cl(C₂H₆OS)]. The crystal structures confirm that acetonitrile interacts with the Pt^II atom via its N atom, while for DMSO, the S atom is the coordinating atom. For the replacement, the longest of the two Pt—Cl bonds is cleaved, leading to a cis position of the solvent ligand with respect to the allyl group. The crystal packing of the complexes is characterized by dimer formation via C—H…O and C—H…π interactions, but no π–π interactions are observed despite the presence of the aromatic ring.     

Activation of Elemental Sulfur at a Two‐Coordinate Platinum(0) Center

Platinum dichalcogenides have been known to exhibit two‐dimensional layered structures. Herein, we describe the syntheses, isolation, and characterization of air‐stable crystalline cyclic alkyl(amino) carbene (cAAC)‐supported monomeric platinum disulfide three‐membered ring complex [(cAAC)₂Pt(S₂)] ( 2 ). The highly reactive platinum(0) [(cAAC)₂Pt] complex ( 1 ) with two‐coordinate platinum activates elemental sulfur to give 2 . The brown crystals of bis‐carbene platinum(II)monosulfate [(cAAC)₂Pt(SO₄)_x(S₂)_1?x] ( 4 ) have been isolated when the reaction was performed in air. The dioxygen analogue of 2 was formed upon exposing the THF solution of 1 to aerial oxygen (O₂). The binding of oxygen at the Pt⁰ center was found to be reversible. Additionally, DFT study has been performed to elucidate the electronic structure and bonding scenario of 2 , 3 , and 4 . Quantum chemical calculations showed donor–acceptor‐type interaction for the Pt?S bonds in 2 and Pt?O bonds in 3 and 4 .     

Two saccharinate complexes: [Mn(phen)2(sac)(H2O)]+·sac– and [Co(bipy)2(sac)(H2O)]+·sac–

The title saccharinate complexes, aqua[1,2‐benzisothiazol‐3(2H)‐onato 1,1‐dioxide‐N]bis(1,10‐phenanthroline‐N,N′)man­ganese(II) 1,2‐benz­isothia­zol‐3(2H)‐onate 1,1‐dioxide,[Mn(C₇H₄NO₃S)(C₁₂H₈N₂)₂(H₂O)](C₇H₄NO₃S), and aqua[1,2‐benz­iso­thiazol‐3(2H)‐onato 1,1‐dioxide‐N]­bis­(2,2′‐bi­pyri­dine‐N,N′)­cobalt(II) 1,2‐benz­iso­thia­zol‐3(2H)‐onate 1,1‐di­oxide, [Co­(C₇H₄NO₃S)­(C₁₀H₈N₂)₂­(H₂O)]­(C₇H₄NO₃S), have been prepared and their crystal structures determined at 150 K. The structure of the manganese complex consists of repeated alternating [Mn(phen)₂(sac)(H₂O)]⁺ cations and non‐coordinated saccharinate anions. The water molecule, bound to manganese as part of a slightly distorted octahedral arrangement, is hydrogen bonded to an O atom of the SO₂ group in the saccharinate counter‐ion. In contrast, the cobalt complex has one pseudo‐octahedral [Co(bipy)₂(sac)(H₂O)]⁺ cation, with the cobalt‐bound water molecule hydrogen bonded to the N atom of the accompanying free saccharinate anion.     

Supramolecular chelate copper(II) complex with 4-[(ethoxyimino)(phenyl)methyl]-5-methyl-2-phenyl-1Hpyrazol-3(2H)-one: Synthesis, crystal structure, and properties

A supramolecular Cu(II) complex, [Cu(L)₂(H₂O)]·C₂H₅OH {HL = 4-[(ethoxyimino)(phenyl)methyl]-5-methyl-2-phenyl-1H-pyrazol-3(2H)-one]} was synthesized and characterized structurally. The structure of the Cu(II) complex consists of one Cu(II) atom, two bidentate L-units, one coordinated H₂O and one crystallization ethanol molecule. The Cu(II) atom of the complex has a slightly distorted tetragonal pyramidal geometry. Moreover, every Cu(II) complex molecule links four other molecules into an infinite 2D-layer supramolecular structure via intermolecular O-H…O, O-H…N, and C-H…O hydrogen bonds.     

Bis[diaquabis(2,2‐bipyridine N,N′‐dioxide‐κ2O,O′)cobalt(II)] ξ‐octamolybdate dihydrate

The title organic–inorganic hybrid compound, [Co(C₁₀H₈N₂O₂)₂(H₂O)₂]₂[Mo₈O₂₆]·2H₂O, consists of [Co(bpdo)₂(H₂O)₂]²⁺ (bpdo is 2,2‐bipyridine N,N′‐dioxide) and ξ‐[Mo₈O₂₆]⁴⁻ groups in a 2:1 ratio, plus two water solvent molecules. The independent Co atom in the cation is coordinated by four O atoms from two bpdo ligands and two water molecules, in a distorted octahedral geometry. The counter‐anions, built up around a symmetry center, are linked by solvent water molecules through O—H...O hydrogen bonds to generate two‐dimensional layers, which are in turn linked by coordinated water molecules from the cationic units through further O—H...O hydrogen bonds, forming a three‐dimensional supramolecular structure.     

Synthesis and magnetic properties of nickel(II) triazamacrocyclic complexes. Crystal structure of [Ni(Me3[12]N3)(O2N)(H2O)]-(ClO4)·2H2O

Summary The synthesis, properties and X-ray crystal structure of [Ni(Me₃[12]N₃)(O₂N)(H₂O)](ClO₄)·2H₂O, in which Me₃[12]N₃ is 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene, are described. The Ni atom is octahedrally coordinated to three N atoms of the macrocycle, two O atoms of the nitrito group and one H₂O molecule. Monomeric units are linked by hydrogen bonds through one of the water of crystallization molecules, forming a chain. Magnetic measurements between 290 and 4 K reveal slight antiferromagnetic behaviour.     

Interaction of dioxygen with the platinum Pt19/SnO2/H2 cluster: DFT calculation

The adsorption of the O₂ molecule onto the surface of the Pt₁₉ platinum cluster deposited onto the tin dioxide crystal surface in the presence of dissociated hydrogen molecule has been calculated by the density functional theory method within the generalized gradient approximation (GGA-PBE) with periodic boundary conditions and a projector-augmented plane-wave (PAW) basis set. It has been demonstrated that the oxygen molecule can be adsorbed without a barrier onto the free surface of the Pt₁₉/SnO₂/H₂ cluster to form a superoxy isomer with one Pt-O bond (the energy of elimination of the oxygen molecule is 0.75 eV), which converts almost without a barrier to more stable peroxide isomers with two Pt-O bonds (the energy of elimination of the O₂ molecule is 1.2?1.7 eV). The energy of elimination of the oxygen molecule from the isomers with two-coordinated oxygen positions at the cluster edges is 2.10?2.53 eV. The isomers with mono- and tricoordinated oxygen positions are less energetically favorable than the isomers with two-coordinated oxygen positions. The process of addition of the oxygen molecule to the platinum cluster and elimination of the water molecule formed in the reaction Pt₁₉/SnO₂/H₂ + O₂ → Pt₁₉/SnO₂/O + H₂O is energetically favorable by 1.6 eV.     

A one‐dimensional coordination polymer based on Cd2O2 clusters: poly[aqua(μ3‐4,4′‐sulfonyldibenzoato)(3,4,7,8‐tetramethyl‐1,10‐phenanthroline‐κ2N,N′)cadmium(II)]

In the title mixed‐ligand metal–organic polymeric complex [Cd(C₁₄H₈O₆S)(C₁₆H₁₆N₂)(H₂O)]_n, the asymmetric unit contains a crystallographically unique Cd^II atom, one doubly deprotonated 4,4′‐sulfonyldibenzoic acid ligand (H₂SDBA), one 3,4,7,8‐tetramethyl‐1,10‐phenanthroline (TMPHEN) molecule and one water molecule. Each Cd^II centre is coordinated by two N atoms from the chelating TMPHEN ligand, three O atoms from monodentate carboxylate groups of three different SDBA²⁻ ligands and one O atom from a coordinated water molecule, giving a distorted CdN₂O₄ octahedral geometry. Single‐crystal X‐ray diffraction analysis reveals that the compound is a one‐dimensional double‐chain polymer containing 28‐membered rings based on Cd₂O₂ clusters, with a Cd...Cd separation of 3.6889 (4) Å. These chains are linked by O—H...O and C—H...O hydrogen bonds to form a three‐dimensional supramolecular framework. The framework is reinforced by π–π and C—O...π interactions.     

Methyl 2‐O‐β‐l‐fucopyranosyl α‐d‐glucopyranoside monohydrate: a synchrotron study

The structure of the title compound, C₁₃H₂₄O₁₀·H₂O, is stabilized by hydrogen bonds situated adjacent to the glycoside linkage. A direct intramolecular hydrogen bond is present between the fucopyranosyl ring O atom and a glucopyranoside OH group, and a bridging water molecule mediates a hydrogen‐bond‐based interaction from a fucopyranosyl OH group to the methoxy O atom. The conformation of the disaccharide is described by the glycosidic torsion angles ϕ_H = −41° and ψ_H = −2°.     

X-ray photoelectron study of the interaction of H<Subscript>2</Subscript> and H<Subscript>2</Subscript>+O<Subscript>2</Subscript> mixtures on the Pt/MoO<Subscript>3</Subscript> model catalyst

The effects of H₂ and H₂ + O₂ gas mixtures of varying composition on the state of the surface of the Pt/MoO₃ model catalyst prepared by vacuum deposition of platinum on oxidized molybdenum foil were investigated by X-ray photoelectron spectroscopy (XPS) at room temperature and a pressure of 5–150 Torr. For samples with a large Pt/Mo ratio, the XP spectrum of large platinum particles showed that the effect of hydrogen-containing mixtures on the catalyst was accompanied by the reduction of molybdenum oxide. This effect results from the activation of molecular hydrogen due to the dissociation on platinum particles and subsequent spill-over of hydrogen atoms on the support. The effect was not observed at low platinum contents in the model catalyst (i.e., for small Pt particles). It is assumed for the catalyst that the loss of its hydrogen-activating ability is a consequence of the formation of platinum hydride. Possible participation of platinum hydride as intermediate in hydrogen oxidation to H₂O₂ is discussed.     

Tetraaquabis[5‐(3‐pyridyl‐κN)pyrimidine]zinc(II) bis(trifluoromethanesulfonate): a novel cationic complex and three‐dimensional hydrogen‐bonded network

The title compound, [Zn(C₉H₇N₃)₂(H₂O)₄](CF₃O₃S)₂, contains an octahedral [ZnL₂(H₂O)₄]²⁺ cationic complex with trans geometry (Zn site symmetry ), and each 5‐(3‐pyridyl)pyrimidine (L) ligand is coordinated in a monodentate fashion through the pyridine N atom. In the extended structure, these complexes, with both hydrogen‐bond acceptor (pyrimidine) and donor (H₂O) functions, are linked to each other by intermolecular water–pyrimidine O—H...N hydrogen‐bonding interactions, resulting in a double chain along the crystallographic a axis. The trifluoromethanesulfonate anions are integrated into the chains via O—H...O hydrogen bonds between the coordinated water and sulfonate O atoms. These double chains are associated into a novel three‐dimensional network through interchain water–pyrimidine O—H...N hydrogen bonds. The asymmetric ligand plays an important role in constructing this unusual supramolecular structure.     

Bis{μ‐(E)‐2‐[(2‐pyridylamino)(2‐pyridylimino)methyl]benzato}bis[acetatozinc(II)] tetrahydrate

In the C₂‐symmetric dinuclear title complex, [Zn₂(C₁₈H₁₃N₄O₂)₂(C₂H₃O₂)₂]·4H₂O, each Zn^II ion is five‐coordinated in a distorted trigonal bipyramidal fashion by one carboxylate O atom from one benzoate ligand, one imine N atom and two pyridyl N atoms from a second benzoate ligand, and one O atom from an acetate anion. The two Zn atoms are bridged by the two benzoate ligands, forming a dinuclear structure with a 14‐membered macrocycle. Adjacent dinuclear units are further connected by extensive hydrogen bonds involving the solvent water molecules, giving a three‐dimensional hydrogen‐bonded framework. The framework can be regarded as an example of the four‐connected node network of the PtS topology.     

A novel amido–pyrophosphate MnII chelate complex with the synthetic ligand O{P(O)[NHC(CH3)3]2}2 (L): [Mn(L)2{OC(H)N(CH3)2}2]Cl2·2H2O

The title complex, trans‐bis(dimethylformamide‐κO)bis{N,N′‐N′′,N′′′‐tetra‐tert‐butyl[oxybis(phosphonic diamide‐κO)]}manganese(II) dichloride dihydrate, [Mn(C₁₆H₄₀N₄O₃P₂)₂(C₃H₇NO)₂]Cl₂·2H₂O, is the first example of a bis‐chelate amido–pyrophosphate (pyrophosphoramide) complex containing an O[P(O)(NH)₂]₂ fragment. Its asymmetric unit contains half of the complex dication, one chloride anion and one water molecule. The Mn^II atom, located on an inversion centre, is octahedrally coordinated, with a slight elongation towards the monodentate dimethylformamide ligand. Structural features of the title complex, such as the P=O bond lengths and the planarity of the chelate ring, are compared with those of previously reported complexes with six‐membered chelates involving the fragments C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)₂ and P(O)] and O[P(O)(N)₂]₂. This analysis shows that the six‐membered chelate rings are less puckered in pyrophosphoramide complexes containing a P(O)OP(O) skeleton, such as the title compound. The extended structure of the title complex involves a linear aggregate mediated by N—H...O and N—H...Cl hydrogen bonds, in which the chloride anion is an acceptor in two additional O—H...Cl hydrogen bonds.     

Tetranuclear Pt<Subscript>2</Subscript>Cu<Subscript>2</Subscript> Complex with a Staircase-Shaped Chain Aggregate in the Solid State

The reaction of the tetranuclear cyanide aquo complex [{Pt(CN)₄Cu(bipy)(H₂O)}₂]· 2H₂O with aqueous ammonia produces the new tetranuclear ammino-containing product [{Pt(CN)₄Cu(bipy)(NH₃)}₂] (1), with terminal cyanide groups and with NH₃ coordinated to the Cu atom. The distorted trigonal bipyramidal coordination about copper in 1 differs from the square-pyramidal coordination present in the starting material. The bipyridine ligand in 1 is nearly perpendicular to the tetranuclear core of the molecule, as opposed to its coplanar disposition in the aquo complex. The two platinum atoms of the tetranuclear core in 1 form Pt···Pt interactions of 3. 2390(8) Å with platinum atoms of neighboring molecules, producing an echelon-shaped supramolecular chain held together by staggered (CN)₄Pt···Pt(CN)₄ linkages, an aggregate structure which does not have a precedent in chemistry derived from the Pt(CN)₄ building block.