Synthesis and crystal structure of tetranuclear zinc benzoate

A tetranuclear zinc benzoate Zr4O(C6H5CO2)6 was synthesized and characterized by X-ray single crystal determination. It crystallizes in cubic, space group Ia-3d. Its crystal cell is very large, α=4.10063(18)nm, V=68.953(5)nm^3 and Z=48. The structure is composed of discrete Zr4O(C6H5CO2)6 molecules. In each molecule, four zinc atoms are held together by a central oxygen atom, which results in the formation of a regular tetrahedron. All benzoate ligands coordinate to zinc atoms in a bidentate bridging mode. Each zinc atom is in a slightly distorted tetrahedral geometry, coordinated by three benzoate oxygen atoms and the central oxygen atom. The intermolecular interactions result in the formation of a three-dimensional supramolecular framework, with non-intersecting parallel channels.     

Preparation, crystal structure and quantum chemical investigation of [Li(NTO) (H_2O)_2]

[Li(NTO)(H2O)2] was prepared by mixing the aqueous solution of 3-nitro-1, 2, 4-triazol-5-one (NTO) and lithium hydroxide. The crystal structure of [Li(NTO)(H2O)2] was determined by single crystal diffraction analysis. The crystal is monoclinic, space group P21/n with crystal parameters of a = 0.742 0(2) nm, b = 0.344 9(1) nm, c = 2.490 6(3) nm, β = 94.89(1)° Z = 4, Dc= 1.799 g· cm-3, V = 0.635 nm3,μ = 1.591 cm-1, F(000) =392. The final R is 0.051. The MNDO MO calculation shows that the coordinate bonds of title compound possess certain extent of covalent character. O2 atom of NTO anion is bonded to Li atom; the nitro group will be lost first when NTO is decomposed.     

The ring-substituted phthalocyanines and its metal com-plexes: Crystal structure of 1, 4, 8, 11, 15, 18, 22, 25-octabutoxyphthalocyani-natocopper(Ⅱ)

Crystal structure of 1, 4, 8, 11, 15, 18, 22, 25- octa-butoxyphthalocyaninatocopper (Ⅱ) (1) was determined by X-ray diffraction methods. The crystal system is monoclinic, space group is P21/c, Z = 4, a = 1.3741(1) nm, b = 2.6737(1) nm, c = 1.6690(1) nm, ????101.278(1)°. The steric congestion between the neighbouring butoxyl groups causes the distortion of the ring core of phthalocyanine (Pc) into a saddle shape conformation. In the crystal structure, molecules stack along a axis forming one-dimensional packing structure and there are two molecular overlap types which appear in turn with different distances between molecules, overlap area and angle.     

The ring-substituted phthalo-cyanines and its metal com-plexes: Crystal structure of 1,4, 8,11,15,18,22,25-octa-butoxyphthalocyani-natocopper(Ⅱ)

Crystal structure of 1, 4, 8, 11, 15, 18, 22, 25-octa-butoxyphthalocyaninato- copper (Ⅱ) (1) was determined by X-ray diffraction methods. The crystal system is mono-clinic, space group is P2₁/c, Z = 4, a = 1.3741(1) nm, b = 2.6737(1) nm, c = 1.6690(1) nm, β= 101.278(1)°. The steric congestion between the neighbouring butoxyl groups causes the distortion of the ring core of phthalocyanine (Pc) into a saddle shape conformation. In the crystal structure, molecules stack along a axis forming one-dimensional packing structure and there are two molecular overlap types which appear in turn with different distances between molecules, overlap area and angle.     

Synthesis and structural characterization of lanthanide coordination polymers constructed from a 13-membered macrocycle

The lanthanide coordination polymers bearing a 13-membered macrocycle, [(13-EDTA-pnOH)H2] were synthesized. The products [Ln(13-EDTA-pnOH)(H2O)2·NO3]n (Ln = Eu(1), Tb(2), Dy(3)) have been obtained by MS, IR and element analyses. The solid-state structure of 1 was established by single-crystal X-ray analysis. The coordination geometry around the central metal atom in complex 1 is a nine-coor-dinated, tricapped-trigonal prism having six donor atoms (two amine nitrogen atoms, two amide oxygen atoms and two carboxymethyl oxygen atoms) from one ligand, one oxygen atom from a neighboring ligand, and two more oxygen atoms from two water molecules. The europium atoms are linked by―Eu―O―C―O―Eu―bridges to form an infinite chain.     

Pre-peak on the structure factor of liquid hypoeutectic Al-Fe alloy

Using a θ-θ X ray diffractometer the structure of liquid hypoeutectic Al Fe alloy at 675℃ and its change with different thermal histories are investigated . Liquid Al is used as a reference system. It is found that a pre peak appears on the small angle part of the structure factor of the nonsuperheated hypoeutectic Al Fe alloy, but disappears after superheating whereas the structure factors of liquid Al hardly change with the different thermal histories, and no pre peak can be observed on them. The appearance of a pre peak is a mark of the intermediate range order (IRO). The pre peak is taken as the correlation between Fe atoms on the IRO length scale. Assume that the crystalline structure is the first order approximation of the liquid structure. A model structure is constructed. The basic unit is a cube formed by 8 Al atoms on its corner and one Fe atom occupying its center. The translation of such a unit along its fourbody diagonals by the length of a diagonal can meet the requirement of the Fe_Fe distance and gives a DO 3 like structure. If the vacancy among the units is filled with fcc like Al cells, the composition of the entity is about Al 7Fe, close to that of the metastable phase Al 6Fe from rapid solidification. It is speculated that there are Al 6Fe like clusters in the liquid hypoeutectic Al Fe alloy.     

Reactivity and structural characterization of divalent samarium aryloxide with diethylaluminum chloride

Reaction of (ArO)2Sm(THF)4 (ArO=2,6-ditert-butyl-4-methylphenolate) with Et2AICI in THF gives SmCI2 (1) and (ArO)AIEt2(THF) (2) via ligand exchange.Complex 1 reacts with cyclooctatetraene (C8H8) to give [(C8H8)SmCI(THF)2]2 (3). Crystal structural determinations show that complex 2 has a monomeric structure, the aluminum atom is coordinated by two carbon atoms and two oxygen atoms, to form a distorted tetrahedron. Complex 3 has a dimeric structure, the samarium atom is coordinated by a cyclooctatetraenyl ring, two chorine atoms and two oxygen atoms, the coordination number of the central metal is 9.     

Synthesis and structure of Cu5(BTA)6(TTA)4 · 5DMF, a copper-nitrogen cluster containing η Π3-benzotriazolate

The title cluster compound—Cu₅(BTA)₆(TTA)₄·5DMF was prepared using thenyltrifluoroacetone and benzotriazolate ligands. The crystal structure indicates that a tetrahedral array of Cu(1), Cu(2), Cu(3) and Cu(4) ions surrounding a central Cu(5) ion are held together by bridging tridentate BTA^- and terminated by TTA^- bond cap. The three nitrogen atoms of a BTA^- bond three different copper ions to form a η³-benzotriazolate. The central Cu ion has a distorted octahedral structure and the surrounding Cu ions are 5 coordinated forming distorted tetragonal structures. The distances between the surrounding Cu(Ⅱ) ions and the central Cu(Ⅱ) ion are in the range of 0.3561—0.3755 nm and those between the surrounding Cu(Ⅱ) ions are in the range of 0.5785—0.6301 nm.     

Liquid structure of pure iron by X-ray diffraction

The liquid structure of pure iron at 1540, 1560 and 1580℃ was studied by X-ray diffraction. The results show that near the melting point there is a medium-range order structure that fades away with the increasing temperature. The average nearest distance of atoms is almost independent of the melts temperature, but the average coordination number, the atom cluster size and the atom number in an atom cluster all decrease with the increasing temperature of the melt. Near the melting point there area lot of atom clusters in the pure iron melt. The atom cluster of pure iron has the body-centered cubic lattices, which are kept from the solid state. And the body-centered cubic lattices connect into network by occupying a same edge. The atoms in the surrounding of the atom clusters are arranged disorderly.     

Structure and second-order NLO property of the molecules bridged through n-vertex bis-substituted carborane （n=5, 6, 7）

Density functional theory (DFT) B3LYP at 6-31G* level is employed to optimize the structures of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) and combined with finite field (FF) formalism to calculate the second-order NLO properties. The results indicate that the structures of n-vertex bis-substituted carborane (n=5, 6, 7) are changed due to bridged donor and acceptor moieties. The distances between two C atoms are becoming longer. And the stability and dipole moment are in- fluenced by changing substituted positions of C atoms. The isomers with the substituents connecting with C atoms of lower coordination number have better stability and larger values of polarizability. One-dimensional structure of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) is in favor of intramolecular charge-transfer. Meanwhile, the isomer with a larger change of dipole moment has larger value of second-order NLO properties during the charge-transfer process.     

First-principles Study of the Au surfactant on the growth of Zn vacancies in ZnO nanostructures

Influence of Au surfactant on the growth of Zn atom vacancies in ZnO nanostructures has been investigated by using first-principles slab calculations based on density functional theory.The adsorption of Au atoms on the Zn-terminated (0001)polar surface with a (2×2)surface unit cell is studied by using a standard supercell model.It is found that (1)the binding energies of Au atoms on (0001)-Zn increase and the most stable position of the Au atom is invariable; (2)on the (0001)surface,the preferred sites for Zn atom vacancy are on the first layer of Zn atoms; (3)Under the Au surfactant,the Zn atom vacancies become more difficult to form.     

Origin of the pre-peak in the structure factor of liquid Fe-4.30C-0.21Ce alloy

The liquid structure of Fe-4.30C and Fe-4.30C-0.21Ce alloys was studied by high temperature X-ray diffractometer. The results show that for Fe-C alloy the nearest neighbor distance of the eutectic alloy is 0.259-0.260 nm at the temperature range of 1200-1400℃, which increases to 0.269-0.271 nm with the addition of 0.21% (mass fraction) Ce in the Fe-C alloy at the same temperature range. There is a pre-peak at Q = 15.5 nm-1 on the original intensity curve and structure factor S(Q) of the liquid Fe-4.30C-0.21Ce alloy, which was caused by the Ce atoms in the C-Ce clusters. Combined with the shared face, the tetragonal structure can meet the requirement for the distance of Ce-Ce atoms. It also shows that the cluster size in the liquid Fe-4.30C-0.21Ce alloy in-creases with the decreasing temperature.     

New crystal structure of molecular complex 1-piperidine carboxylate-piperidinium-H<Subscript>2</Subscript>O studied by X-ray single crystal diffraction

Piperidine absorbs CO2 and H2O in air to form a molecular complex： piperidium-l-piperidinecarboxylate-H2O. The structure of the complex was characterized by X-ray single crystal diffraction. The crystal structure was determined to be triclinic, space group P1^-with a=0.648 6（8） nm, b=0.809 200） nm, c= 1.357 1（16） nm, a=96.96706）°, β =102.506（15）°,γ=104.202 05）°, Z=2. The complex is stabilized via five hydrogen bonds between the three components, N-O electrostatic interaction and O-O interaction （electron transfer） betweenl-piperidinecarboxylate and H2O. Due to electron transference of carbamate ion, the oxygen atom in water molecule is strongly negatively charged and the O-H bond is considerably shorter than that of the free molecule of water. The formation of the molecular complex is a reversible process and will decompose upon heating. The mechanism of formation and stabilization is further investigated herein.     

Crystal structure determination of Jatrorrhizine chloride

Optimum resolution data of powder X-ray diffraction （PXRD） for Jatrorrhizine （Jat） were collected by an X＇ Pert Pro MPD diffractometer with an X＇celerator detector under the stepwise scanning condition as 8.255 ms and 0.00836° per step, 20range of 5°-80° and total scanning period of 8-10 min. Indexing of the crystal system and a search of the space group from the powder X-ray diffraction data were conducted by the computational crystallography method. The pilot crystal models of Jat were globally optimized with Monte Carlo method and then refined with the Rietveld method. In parallel with PXRD test, single crystals of Jat were cultured in an aqueous solution by a slow-decreasing temperature method, then its crystal structure was determined by single crystal X-ray diffraction （SCXRD）. Both crystal structures from PXRD and SCXRD are identical. The results show that the crystal structure of Jat belongs to a monoclinic system and the space group P21/c. The parameters of cell dimensions from PXRD are a =7.69 A, b = 12.55 A, c = 20.89 A ,β= 106.53°, Z= 4, and V= 1933.4 A^3, meanwhile the parameters from SCXRD are a = 7.72 A, b = 12.61 A, c =20.99 A, β=106.38°, Z=4, and V=1961.3 A^3.     

Assignment of the μ4-O5 atom in catalytic center for water oxidation in photosystem II

The detailed structure of catalytic center of water oxidation, Mn4Ca-cluster, in photosystem ⅡI (PSII) has been reported recently. However, due to the radiation damage induced by X-ray and the complexity of the Mn4Ca-cluster, the assignment of the μ4-O5 atom coordinated by three Mn and one Ca2+ ions is still lack of essential evidences. In this article, we synthesized one Mn complex containing two μ4-O atoms. It is found that the lengths of all μ4-O-Mn bonds in this Mn complex are in the range of 1.89-2.10 , which are significantly shorter than 2.40-2.61 distance of μ4-O5-Mn bonds in Mn4Ca-cluster observed in the crystal structure of PSII. In addition, DFT calculations have been carried out on the Mn4Ca-cluster. It is found that the O atom of μ4-O or μ4-OH always trends to deviate from the center position of four metal ions, resulting in unequal bond lengths of four μ4-4-M (M=Mn or Ca), which is obviously different with larger and nearly equal distances between μ4-O and four metal ions observed in the crystal structure. Based on these results, we suggest that the μ4-atom in Mn4Ca-cluster of PSII is unlikely to be a μ4-O, μ4-OH or μ4-OH2 , and its assignment is still an open question.     

Synthesis and reaction of 16-electron Cp<Superscript>t</Superscript>Rh halfsandwich complexes containing 1,2-dichalcogenolate carborane ligands

The reactions of [Cp^tRhCi(μ-Ci)]2 (1) (Cp^t=^tBu2C5H3) with Li2E2C2B10H10 (E = S, Se) lead to the green 16-electron dichaicogenolate complexes Cp^tRh(E2C2B10H10) [E = S(2a), Se(2b)]. The 16-electron complexes 2a and 2b can take up two-electron donor ligands such as tert-butyi isonitrile and carbon monoxide to give the 18-electron dichaicogenolate derivatives Cp^t(L)(E2C2B10H10) [L = ^tBuNC, E =S(3a), Se(3b); L = CO, E = S(4a), Se(4b)]. The molecular structures of complexes 2a and 3a were determined by X-ray crystal structure analysis. The molecular structure of 16-electron complex 2a shows the pseudoaromatic system in IrSe2C2 five numbered ring.     

Structure and properties of NASICON synthesized by two different zirconium salts

ZrOCl₂·8H₂O and ZrO(NO₃)₂·2H₂O were used respectively to synthesize a NASICON solid electrolyte by a sol-gel method. The structure and properties of two samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS). The crystal structure was investigated by the Rietveld refinement. It is found that both the samples contain a monoclinic C2/c phase as the main conductive phase with the lattice parameters of a=1.56312 nm, b=0.90784 nm and c=0.92203 nm, though a small amount of rhombohedral phase is also detected in the final product. The sample synthesized by ZrO(NO₃)2·2H₂O contains more monoclinic phase (89.48wt%) than that synthesized by ZrOCl₂·8H₂O (74.91wt%). As expected, the ionic conductivity of the latter is higher than that of the former; however, the activation energy of the latter (0.37 eV) is slightly higher than that of the former (0.35 eV).     

Hydrothermal synthesis and crystal structure of copper （Ⅱ） coordination polymer composed of helix-like chains： [Cu（NIeH）（bpy）]

Hydrothermal reactions of Cu （Ⅱ） acetate, 2,2＇-bipyridyl （bpy） with 5-nitroisophthalic acid （H2NIPH） resulted in a new coordination polymer [Cu（NIPH）（bpy）] 1. Single crystal X-ray diffraction experiment indicates that 1 possesses a single helixlike chains, of which Cu atoms are coordinated by NIPH ligands and bpy ligands. Compound 1 crystallizes in the space group P2（ 1）/c, a = 0.955（19） nm, b = 1.259（3） nm, c = 1.3737（3） nm, ,6= 95.13（3）°, V= 1.6455（6） nm^3 and Z = 4. The TGA analysis shows that 1 has no remarkable weight loss up to 284℃, as a result of its high thermal stability. Magnetic measurements indicate an antiferromagnetic behavior of compound 1.     

Correlation between structure and hardness of magnetron sputtering deposited CNx films

Carbon nitride films are deposited on Si (001) substrates by reactive dc magnetron sputtering graphite in a pure N2 discharge. The structure of carbon nitride films has been probed using Fourier transformation infrared, near edge X-ray absorption fine structure (NEXAFS) and high resolution electron microscopy (HREM), and the hardness has been evaluated in nanoin-dentation experiments. FTIR spectra show that N atoms are bound to sp1, sp2, and sp3 hybridized C atoms. C1s NEXAFS spectra show that the intensity of π* resonance is the lowest for the film grown at substrate temperature TS = 350℃, with a turbostratic-like structure and high hardness, while it is the highest for the film grown at TS = 100℃, with an amorphous structure and low hardness. The correlation between the structure and hardness of carbon nitride films has been discussed.     

Theoretical calculations on the atomic and electronic structure of β-SiC(110) surface

We present a theoretical calculation of the atomic and electronic structure of β-SiC and its non-polar (110) surface using the full potential linear augmented plane wave (FPLAPW) approach. The calculated lattice constant and bulk modulus of β-SiC crystal are in excellent agreement with experimental data. The atomic and electronic structure of β-SiC(110) surface has been calculated by employing the slab and supercell model. It is found that the surface is characterized by a top-layer bond-length-contracting rotation relaxation in which the Si-surface atom moves closer towards the substrate while the C-surface atom moves outward. This relaxation is analogous to that of Ⅲ-Ⅴ semiconductor surface. The driving mechanism for this atomic rearrangement is that the Si atom tends to a planar sp²-like bonding situation with its three N neighbors and the N atom tends to a p³-like bonding with its three Si neighbors. Furthermore, surface relaxation induces the change from metallic to semiconducting characterization.