Journal of Chemical Crystallography最新文献

A new coordination polymer of coper (II), [tetra-azido)tris(2-pyridyl)amine)dicopper(II)] (1) has been synthesized by the reaction between copper(II) nitrate hexahydrate, sodium azide and tris(2-pyridyl)amine under solvothermal conditions in aqueous methanol. The structure has been characterized by single-crystal X-ray diffraction. An analysis of Hirschfeld surfaces was examined. Single-crystal results reveals that the structure contains two independent copper(II) centers, both having approximately square pyramidal coordination: in one, two of the basal sites are occupied by bidentate tris-(2-pyridyl)amine and two azido ligands, with a third azido ligand at the apical site, while the other center is coordinated only by azido ligands. All azido ligands bind two copper centers, forming a coordination polymer chain with two types of Cu2N2 rings and one type of Cu4N4 ring, and in which all azido ligands form a bridge between two metal centers in mode µ-1,1. The Hirshfeld analysis revealed an azido··· (pyridyl) interaction in the coordination polymer chain, as well as weak C-H···N interactions, one of which links the chains into sheets.

Index Abstract

A new dinuclear copper (II) polymer [tetra-azido(tris(2-pyridyl)amine)dicopper(II)] (1) has been synthesized under solvothermal conditions and been characterized by single-crystal X-ray diffraction and Hirshfeld surface analysis.

The molecular structure of (1)

Reactions of two dialkyl-substituted pyrazine ligands with a triosmium cluster are described. Both 2-ethyl-3-methylpyrazine (C₄H₂N₂MeEt) and 2,5-dimethylpyrazine (C₄H₂N₂Me₂) react with the labile triosmium cluster [Os₃(CO)₁₀(NCMe)₂] at 80 °C to afford [HOs₃(CO)₁₀(µ-C₄HN₂MeEt)] (1) and [HOs₃(CO)₁₀(µ-C₄HN₂Me₂)] (2), respectively. Clusters 1 and 2 are formed via C–H bond activation at the α-carbon of the corresponding pyrazine ligand. Cluster 2 reacts with PPh₃ at room temperature in the presence of Me₃NO‧2H₂O to yield the mono- and diphosphine-substituted clusters [HOs₃(CO)₉(PPh₃)(µ-C₄HN₂Me₂)] (3) and [HOs₃(CO)₈(PPh₃)₂(µ-C₄HN₂Me₂)] (4), respectively, both of which exist in more than one isomeric form in solution. All new clusters have been characterized using spectroscopic methods together with single-crystal X-ray diffraction studies for 1, 2, and 4. The bonding in these clusters have been investigated by electronic structure calculations.

Graphical Abstract

Two new triosmium clusters bearing a metalated pyrazineligand have been synthesized and structurally characterized.The reactivity of one of these newly synthesized clusters towards PPh₃ has also been investigated.

Recrystallization of [Zn(malt)₂(H₂O)_1.5] (malt = maltolato(-1), C₆H₅O₃) from a concentrated aqueous solution acidified with HCl to pH 3.0 yielded colorless crystals of [Zn(Hmalt)₂Cl₂] (Hmalt = neutral maltol, C₆H₆O₃). The Zn(II) site exhibits distorted tetrahedral coordination through bonding to two chloride ligands and to two neutral maltol ligands, each bonding through the ketonic oxygen. [Zn(Hmalt)₂Cl₂] is a unique example of a neutral monodentate coordination by the maltol ligand.

Graphical Abstract

A view of the tetrahedral [Zn(Hmalt)₂Cl₂] (Hmalt = neutral maltol, C₆H₆O₃).

A novel Co(II) complex [Co₄(HL)₂Phen₂(H₂O)₁₀]·20(H₂O) (HL = 5-(Bis-carboxymethyl-amino)-isophthalic acid; Phen = 1,10-Phenanthroline) was synthesized by hydrothermal methods, and its crystal structure was determined by single-crystal X-ray diffraction. The title complex crystallized in the monoclinic space group C2/c as an isolated tetranuclear structure. The strong π···π stacking, hydrogen bonding and van de Waals attractions produce 3D supramolecular structure. A series of properties of the title complex were tested by solid-state photoluminescence, CIE analysis and solid-state diffuse reflectance. The results show that the title complex is blue light emitter, CIE (0.2172, 0.5581) and has an energy bandwidth of 2.33 eV.

Graphical Abstract

A novel monoclinic space group C2/c complex of [Co₄(L)₂Phen₂(H₂O)₁₀]·20(H₂O) (HL = 5-(Bis-carboxymethyl-amino)-isophthalic acid; Phen = 1,10-Phenanthroline) was synthesized by hydrothermal methods, and a series of properties of the complex were tested by solid-state photoluminescence, CIE analysis and solid-state diffuse reflectance, which results show that the title complex is blue light emitter, CIE (0.2172, 0.5581) and has an energy bandwidth of 2.33 eV.

One quaternary selenidoantimonate of [Mn(en)₃]CdSb₂Se₅ (1) (en = ethylenediamine) was prepared under 1,2-propanediamine condition by mild solvothermal method. Single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in the monoclinic space group C2/c. Its structure consists of infinite 1D [CdSb₂Se₅]_n²ⁿ⁻ anionic chains and [Mn(en)₃]²⁺ cations. Meanwhile, “Z” shaped eight-membered [Cd₂Sb₂Se₄] and six-membered [CdSb₂Se₃] rings are alternately found. As estimated from UV–Vis absorption spectrum, the band gap of 1 is 2.58 eV. Compound 1 also showed rapid response and excellent reproducibility based on photoelectric test. In addition, the magnetic and other properties of 1 were studied.

Graphical Abstract

The manuscript describes the synthesis, crystal structure, single-crystal X-ray diffraction, elemental analysis, photoelectric response, thermogravimetric analysis, magnetic properties, infrared spectroscopy and UV-Vis diffuse reflectance spectroscopy of [Mn(en)₃]CdSb₂Se₅. The photoelectric response of compound 1 was explored, and a highly repetitive and stable photocurrent curve was found, indicating that 1 is a typical p-type semiconductor. In addition, the magnetism of compound 1 was also studied, which showed that 1 had antiferromagnetic behavior.

The crystal structures of C₂₃H₃₀O₆·C₂H₅OH and C₂₃H₃₀O₆·C₃H₇OH were determined by X-ray diffraction analysis at temperatures 100 K (space group P2₁, Z = 2): a = 9.6973(4), b = 7.4950(3), c = 16.1828(7) Å, β = 93.559(4)°, R = 0.0698 (C₂₃H₃₀O₆·C₂H₅OH); a = 9.8941(3), b = 7.3833(2), c = 16.5816(5) Å, β = 90.110(3)°, R = 0.0318 (C₂₃H₃₀O₆·C₃H₇OH). The method molecular Voronoi–Dirichlet polyhedra were also used to analyze non-bonded interactions in the structures of solvate crystals. The analysis showed that the studied solvates are isostructural. There is a slight increase in the fraction of intermolecular H/H contacts for isopropanol solvate.

Graphical Abstract

The crystal structures of C₂₃H₃₀O₆·C₂H₅OH and C₂₃H₃₀O₆·C₃H₇OH were determined by X-ray diffraction analysis at temperatures 100 K and the method molecular Voronoi–Dirichlet polyhedra were also used to analyze non-bonded interactions in the structures.

Arrangement of molecules in the unit cell of solvates of cortisone acetate (a—ethanol solvate; b—isopropanol solvate).

One Ni(II)-Na(I) complex namely {[Ni^II-L-Na^I(dca)]₂}_n [H₂L = 1,2-ethanediylbis(2-iminomethylene-6-methoxy-phenol)] was synthesized under mild conditions at room temperature and characterized by elemental analysis, infrared spectroscopy, X-ray diffraction and thermogravimetric analysis. Single crystal X-ray diffraction analyses show that Ni(II) centers are in four-coordinate D_4h geometry and Na(I) centers are in a six-coordinate slightly distorted pentagonal pyramidal C_5v geometry in the complex. The basic structural components of the complex are the [Ni^II-L-Na^I] units, which are further connected by the dicyanamide through μ_1,5 mode between the Na centers to form 1D chain structures. Thermogravimetric analysis indicate that complex 1 shows good thermal stability.

Graphical Abstract