Synthesis, spectral, and single crystal X-ray structural studies on (2,2′-bipyridyl)bis(dimethyldithiocarbamato) zinc(II) and (1,10-phenanthroline) bis(dimethyldithiocarbamato)zinc(II)

Synthesis, spectral, and single crystal X-ray structural studies on (2,2-bipyridyl)bis (dimethyldithiocarbamato)zinc(II) (1) and (l,10-phenanthroline)bis(dimethyldithiocarbamato)zinc(II) (2) complexes are reported in this paper. The complex (1) crystallizes in the orthorhombic lattice, space group Pcca, a = 18.456(3), b = 6.529(2), and c = 17.092(2) Å. The complex (2) crystallizes in the monoclinic space group C2/c, a = 13.372(2), b = 13.850(2), c = 24.680(3) Å, and = 102.71(4)°. IR spectra of the complexes (1) and (2) show the thioureide (C-N) bands at 1489 and 1510 cm^–1, respectively, which are lower than the value observed for the parent bisdithiocarbamate. Reduction in the thioureide stretching frequency is due to the increase in coordination around the zinc ion and the resultant increase in electron density. Thermal studies indicate that the 1,10-phenanthroline adduct is marginally more stable than the other complex. X-ray crystal structures of the two adducts show them to be octahedrally coordinated and monomeric in nature. The Zn-S distances are longer than those observed in the parent bisdithiocarbamate. The thioureide C-N bond distances in (1) and in (2) indicate the partial double bond character. The most important structural changes as a result of the adduct formation are observed in the Zn-S bond distances and S-Zn-S bond angles, in terms of very significant increases in Zn-S bond distances and reductions in S-Zn-S angles, compared to the parent bisdithiocarbamate. The observed changes are indicative of a strong steric force in operation in the adducts rather than electronic effects.     

Structure of bis(O,O′-diisopropyldithiophosphato-S,S′) (1,10-phenanthroline-N1,N10)zinc(II) complex, [Zn(phen)(S2P(OiPr)2)2]

The crystal and molecular structure of [Zn(phen)(S₂P(OiPr)₂)₂] (Phen = 1,10-phenanthroline) has been determined by X-ray crystallography. It crystallizes in the Monoclinic system, space group C2/c, with lattice parameters a = 19.315(4), b = 10.438(2), c = 16.567(3)Å, = 102.89 (3)°, and Z = 4. The complex has C₂ symmetry. The coordination geometry of each Zn atom, by two S atoms from two (O,O-diisopropyldithiophosphato) anions and by two N atoms from phenanthroline ligand, is that of a slightly distorted tetrahedron [Zn—S 2.2914(8)Å Zn—N 2.111(2)Å]. The Zn···S distances to the noncoordinated S atoms are long: 3.5276 Å, which are indicated that there are much weaker interactions between them.     

Crystal structures of bis(cyanido)bis(N,N′-diethylthiourea-κS) mercury(II) and bis(cyanido)bis(N,N′-dipropylthiourea-κS) mercury(II)

Two mercury(II) complexes containing cyanide and, N,N′-diethylthiourea (detu) and N,N′-dipropylthiourea (dprtu) ligands, [(detu)₂Hg(CN)₂] (1) and [(dprtu)₂Hg(CN)₂] (2), respectively, have been prepared and characterized by X-ray crystallography. In the both complexes Hg atom lies on a 2-fold rotation axis, and is coordinated to the sulfur atoms of two thiourea ligands and to two cyanide carbon atoms. Both have a distorted tetrahedral environment with bond angles about the Hg atoms in the range of 93.41(4)°–146.75(19)°. In the crystal structures symmetry related molecules are linked via N-H-N hydrogen bonds resulting in the formation of a two-dimensional network in 1, while in 2 a double stranded one-dimensional chain is formed.     

Structure,bonding, and magnetic behavior of bis(μ-chloro)-and (μ-bromo)-bridged Cu(II) dimers

It has been previously reported that dimeric compounds of the general formula [L₃Cu(II)]₂(-Cl)₂ exhibit a correlation between their magnetic coupling constantJ and the bridging Cu-Cl-Cu angle. A full survey of the published structural and magnetic data on these compounds confirms this correlation but leads to the conclusion that its physical significance is questionable. EHMO calculations on Cu₂Cl ₈ ^4– and its bromo analog show that the molecular orbitals responsible for the magnetic behavior of the dimers are not the orbitals responsible for the bonding interactions in these dimers. Therefore, they are very weakly affected by variations of the molecular structure, and no significant correlation betweenJ and any of the structural parameters is theoretically predicted. However, this situation changes when the coordination around the Cu atoms is strongly and dissymmetrically pyramidalized.     

Synthesis,Spectral, Thermal and Structural Study of Monoaquabis(Acetylsalicylato-κO)bis(Nicotinamide-κN)Copper(II)

Abstract  

The compound has been formed by mononuclear [Cu(C₉H₇O₄)₂(C₆H₆N₂O)₂(H₂O)] units in which the metal ion as well as the water ligand lies on a twofold symmetry axis, so that only one acetylsalicylate ligand and one nicotinamide ligand are independent. The distortion from ideal five-coordinate geometries can be described best by the degree of trigonality τ. For a regular square-pyramidal (SQP) geometry the trigonality parameter is 0 and for a trigonal–bipyramidal (TBP) structure it increases to 1. The copper coordination geometry is that of a square pyramid (τ = 0.23), with the N atoms from nicotinamide ligands and the bonded carboxylate O atoms from acetylsalicylate ligands defining the quasi-planar square base. The apical site is occupied by the aqua ligand, a bond which coincides with the twofold symmetry axis and is thus exactly perpendicular to the basal plane. The thermal decomposition takes place in four steps: removing of moisture, dehydration of aqua ligand, the elimination of the nicotinamide (na) ligand and the decomposition of acetyl-groups and oxidation of salicylate ion ligands. In complex, all ligands are coordinated to the metal ion as monodendate. The IR spectra of the intermediate products showed similar results.     

Complexes in the Ni2+-imidazole-RN(CH2COO−)2 systems. The crystal structures of tris(imidazole)iminodiacetatonickel(II) monohydrate, hexa(imidazole)nickel(II) bis(N-methyliminodiacetato)nickelate(II) hexahydrate, and tetra(aqua)bis(imidazole)nickel(II) bis(N-benzyliminodiacetato)nickelate(II)

Crystals of different compositions, namely, [Ni(Ida)(Im)₃] ? H₂O (I), [Ni(Im)₆][Ni(Mida)₂] ? 6H₂O (II), and [Ni(Im)₂(H₂O)₄][Ni(Bida)₂] (III), have been precipitated from aqueous solutions of the Ni²⁺-Lig ^2?-Im systems, where Lig ^2? is Ida, Mida, and Bida, respectively. The crystal structures of I–III are determined by X-ray diffraction analysis (R = 0.0307, 0.0348, and 0.0302 for 3061, 4706, and 2882 reflections, respectively). Crystals I are built of monomeric mixed-ligand complexes and molecules of crystallization water, which are interlinked by hydrogen bonds into a three-dimensional framework. In II and III, the ligands Lig ^2? and Im form charged complexes separately. In II, the cationic and anionic layers of the complexes alternate along the c-axis. Numerous hydrogen bonds involving molecules of crystallization water link the layers into a three-dimensional framework. In III, the cationic and anionic complexes, which serve as proton donors and acceptors, respectively, are bound into layers parallel to the xy plane.     

Structure,magnetic and IR studies of copper(II) diphenylphosphate dihydrate,Cu(DPhP)2·(H2O)2

The title compound has been synthesized, and characterized by means of X-ray, magnetic, and IR-spectroscopic measurements.The crystals of Cu(DPhP)₂(H₂O)₂(DPhP=diphenylphosphate) are monoclinic, space groupI2/c witha=24.126(6),b=8.510(2),c=12.333(3) Å,=90.73(5)° andZ=4. The structure was solved by the heavy-atom technique, and refined by full-matrix least-squares calculations to a finalR of 0.040 for 1494 reflections.The complex is centrosymmetric, and the Cu atom at a center of symmetry is four-fold coordinated with two oxygen atoms from two phosphate groups and two water molecules. The coordination about the Cu atom is square-planar, with Cu-O and Cu-O(W) distances 1.926(3) and 1.912(3) Å, respectively.The O(2) phosphate oxygen is an acceptor of two H bonds; one of them is an intramolecular O(W)-H(2)O(2) of 2.714(4) Å, and the other is an intermolecularO(W)-H(1)O(2ⁱ) of 2.667(4) Å. Their presence is also deduced from the IR spectrum of this compound at 3250 and 3000 cm^–1, respectively.The calculated magnetic moment value of 1.92 B.M. corresponds to that of the monomeric copper(II) complexes including those of some alkyl phosphates.     

Phenylmercury(II) dithiophosphates. Crystal structure of (O,O′-diethyldithiophosphate) phenylmercury(II)

The phenylmercury(II) derivatives PhHgS₂P(OR)₂ (R=C₂H₅, C₆H₁₁ and C₆H₅) have been synthesized. (O,O-diethyldithiophosphate) phenylmercury(II), C₁₀H₁₅HgO₂PS₂, crystallizes in the monoclinic space groupP2₁/c (n° 14) witha=7.330(5),b=18.085(2),c=11.552(4)Å,=105.96(5)°,V=1472.3(6)ų,Z=4,D=2.088 g.cm^–3. The mercury atom is coordinated to the phenyl carbon atom and to a ligand sulphur atom in an almost linear arrangement (C-Hg-S angle, 176.0(2)°. The ligand is almost monodentate, its second sulphur atom only being involved in a weak secondary intermolecular bond.IR and Raman studies of the other two compounds suggest the same coordination scheme. Positive ion FAB and¹³C,³¹P and¹⁹⁹Hg NMR spectra are also discussed.     

4-Methoxypyridine-(pyridine-2,6-dicarboxylato-N,O,O′) copper(II)

The synthesis and X-ray crystal structure of [Cu(C₇H₃NO₄)(C₆H₇NO)], [Cu(dipic)(4-MeO-Py)], (dipic = pyridine-2,6-dicarboxylate, 4-MeO-Py = 4-methoxypyridine), is described. Molecules of [Cu(dipic)(4-MeO-Py)] are formed {via} coordination of the copper(II) cation to two nitrogen atoms, from the dipic and 4-MeO-Py ligands respectively, and to two oxygen atoms from the carboxylate groups of the dipic ligand. The molecules pack in a non-centrosymmetric manner, stacked eclipsed with respect to one another along the b-axis and aligned parallel in a head-to-tail motif. The title compound crystallizes in the orthorhombic space group, Pca2(1), with a = 27.339(3) Å, b = 3.7130(4) Å, c = 11.6859(12) Å, V = 1186.2(2) ų, and Z = 4. The structure was solved by direct methods and refined by least-squares methods to a final R-factor of 0.0327 for 2648 independent reflections.     

Crystal structure of (4α,4aα,8aα)-(±)-octahydro-2-(phenylmethyl)-2H-1,2-benzoxazin-4-ol, 4-methylbenzenesulfonate(ester)

The title compound, a bicyclic tetrahydro-1,2-oxazine, crystallizes in a monoclinic lattice, space group P2₁/c, with a = 12.9809(18)Å, b = 12.920(2)Å, c = 13.631(2)Å, = 110.713(12)°, and Z = 4. The structure found in the solid state for this conformationally mobile molecule shows the tosyl group in an axial position and a benzyl group in an equatorial position of the bicyclic system.     

Synthesis, crystal structure, and properties of the adduct of bis(O,O′-diisopropyl dithiophosphato)nickel(II) with pyridine [Ni(i-Pr2dtp)2(py)2]

A new adduct bis(pyridine)-bis(O,O-diisopropyl dithiophosphato-S,S)nickel(II), [Ni(i-Pr₂dtp)₂(py)₂] (dtp = dithiophosphate, py = pyridine) has been obtained by re-crystallization from CH₃COCH₃. The crystal and molecular structure of the title complex has been determined by X-ray crystallography. It crystallizes in the monoclinic system, space group P2₁/c, with lattice parameters a = 6.4890(13) Å, b = 16.386(3) Å, c = 14.830(3) Å, = 99.74(3)°, V = 1554.1(5) ų, and Z = 2. The crystal structure consists of discrete molecules of [Ni(i-Pr₂dtp)₂(py)₂], which displays a slightly distorted octahedral geometry for the NiS₄N₂ chromophore. Two O,O-diisopropyl dithiophosphate ions act as bidentate ligands with their S atoms coordinated to Ni atom. Each forms a four-membered chelate ring in the equatorial plane. The N atoms from two pyridine ligands are axially coordinated to the Ni atom. The Ni S bond distances are 2.4492(8) Å and 2.5711(9) Å, and the Ni bond distances are 2.127(3) Å. Thermal analyses show that the thermal decomposition of this adduct is so unstable that loss of two pyridine ligands begins at about 65°C. Electronic and IR spectra data is in agreement with the structural data.     

Crystal structure of tisinalite Na2(Mn,Ca)1 − x (Ti,Zr,Nb,Fe3+)[Si6O8(O,OH)10]

Crystal structure of tisinalite from the Lovozero alkaline massif (the Kola Peninsula) was established by single-crystal X-ray diffraction analysis (SYNTEX $\bar P1$ diffractometer, λMoK_α radiation, 2θ/θ scanning mode). The structure solution (SHELX97 program package, R _hkl = 0.0565, 951 independent reflections, anisotropic refinement of thermal atomic displacements) confirmed that tisinalite belongs to the lovozerite structure type (sp. gr., $\bar P1$ , a = 10.036(5) Å, c = 12.876(9) Å, Z = 3). The difference between the structure of tisinalite and the structures of the minerals of the lovozerite group established earlier consists in the nature of the occupancy of both cation and anion positions.     

Pb(Zn,Nb)O3-(Pb(Zn,Ti)O3)1-x(LaySr1-y MnO3)x 固溶体系磁电特性研究

采用常规陶瓷制备工艺制备了xLaySr(1-y)MnO3+(1-x) [0.2PbZn0.5Yb0.5O3-0.8Pb0.33Zr0.67TiO3](x=0.025、0.05、0.075、0.1、0.15、0.2,y=0.7、0.9)三元体系陶瓷,系统研究了不同成分LSMO掺杂对FZN-PZT磁学及电学性能影响.结果表明,掺入不同比例的LSMO均溶解入PZN-FZT晶格,导致PZN-PZT峰位偏移;随着LSMO掺杂量的提高,陶瓷的矫顽场E及剩余极化强度Pr降低;原本分别呈现铁磁性和反铁磁性的LyS(1-y) MO3(y=0.7、0.9)磁性消失;随着LMSO掺杂量的提高,晶粒尺寸变大.     

Synthesis, redox chemistry, and X-ray structure of the mixed-metal cluster Fe2(CO)6(μ3-S)2Ni(dppf)

The reaction between the dianion [Fe₂(CO)₆(₂-S)₂]^2– and NiCl₂(dppf) occurs readily at room temperature to give the mixed-metal cluster Fe₂(CO)₆(₃-S)₂Ni(dppf) in moderate yield. Fe₂(CO)₆(₃-S)₂Ni(dppf) was isolated by preparative chromatography and its solid-state structure established by X-ray diffraction analysis. Fe₂(CO)₆(₃-S)₂Ni(dppf) crystallizes in the monoclinic space group C2/c, a = 20.320(6), b = 13.114(2), c = 15.622(2) Å, = 110.25(2)°, V = 3905.4(11) ų, Z = 4, and d _calc = 1.630 g/cm.³ The X-ray structure of Fe₂(CO)₆(₃-S)₂Ni(dppf) exhibits an Fe₂S₂Ni arachno polyhedral core, with the pendant dppf ligand attached to an essentially square planar Ni center. The redox chemistry of Fe₂(CO)₆(₃-S)₂Ni(dppf) was investigated by cyclic voltammetry which showed a reversible, one-electron oxidation localized on the Fe₂S₂ core along with an irreversible, one-electron reduction that is antibonding with respect to the Fe—Fe and Fe—S bonds. The electrochemical assignments were confirmed by carrying out extended Hückel MO calculations on the model cluster Fe₂(CO)₆(₃-S)₂Ni(H₄-dppf).     

N-M(In,Ga,Al)共掺(6,6)型闭口氧化锌纳米管场发射第一性原理研究

运用以密度泛函理论为基础的第一性原理计算方法,研究了N-M(In,Ga,Al)共掺(6,6)型闭口氧化锌(ZnO)单壁纳米管的结构稳定性和场致发射特性.结果表明:共掺可增强体系帽端的稳定性;外加电场越大,各体系的态密度(DOS)分布越低,能隙和有效功函数越小,电荷向帽端聚集.DOS,最高占据分子轨道(HOMO)/最低未占据分子轨道(LUMO),Mulliken电荷和有效功函数分析结果一致表明,N-In共掺体系的场发射性能最优.     

Structure and spectral properties of (O-Cyclohexyldithiocarbonatio-S,S′) bis(triphesnylphosphine) copper(I) complex

The complex [(C₆H₁₁OCS₂)(PPh₃)₂Cu], was synthesized and characterized using IR, UV, and ¹H NMR. The crystal and molecular structure has been determined by X-ray diffraction. The yellow crystal of the complex is triclinic of space group , with parameters a=10.370(2)Å, b=13.530(3)Å, c=14.640(3)Å, =92.60(3)°, =108.00(3)°, =97.70(3)°, and Z=2. In the complex, the central Cu atom is in a distorted tetrahedral environment and chelated by two phosphorus atoms of the TRIPHOS and two sulfur atoms from the O-cyclohexyldithiocarbonate. The cyclohexane ring adopts a chair conformation. The thermal analytical data indicate that the complex begins to decompose at 101°C and stop at 360°C , leaving CuS. IR, UV, and NMR results supported the crystal structure.     

Novel manganese(III) oxidation chemistry: X-ray crystal structures of (1α,2α,4β)-1,2-diacetoxy-4-(4-methoxyphenyl)-6-methoxy-1,2,3,4-tetrahydronaphthalene (compound A) and (1α,2α,4β)-1,2-diacetoxy-4-(2-methoxyphenyl)-8-methoxy-1,2,3,4-tetrahydronaphthalene (compound B)

CompoundA is (1,2,4)-1,2-diacetoxy-4-(4-methoxyphenyl)-6-methoxy-l,2,3,4-tetrahydronaphthalene, C₂₂H₂₄O₆,M _r=384.43, monoclinic, P2₁/n, witha=11.074(3),b=10.353(4),c=17.616(4)Å,=94.96(2)°,V=2012.1ų,D _calc=1.27 g cm^–3 and=0.55 cm^–1 forZ=4. Least-squares refinement of 1371 observed [F ₀5 (F ⁰)] reflections led to the final agreement index ofR=0.052. A twofold disorder was observed for the 1-acetoxy group whereas the 2-acetoxy group was ordered. CompoundB, (1,2,4)-1,2-diacetoxy-4-(2-methoxyphenyl)-8-methoxy-l,2,3,4-tetrahydronaphthalene, C₂₂H₂₄O₆,M _r=384.43, crystallizes in the monoclinic space group, P2₁/c, witha=16.209(2),b=10.076(1),c=13.357(4)Å,=111.41(2)°,V=2030.9ų,D _calc=1.26 g cm^–3 and=0.54 cm^–1 forZ=4. A final agreement index ofR=0.045 was realized by least-squares refinement of 1486 observed [F _o5 (F _o)] reflections. Intermolecular interactions in the cell lattices of compoundsA andB are noted. The title compoundsA andB were prepared by manganese(III) acetate oxidative dimerization of two molecules of 4-methoxystyrene and 2-methoxystyrene, respectively.     

Synthesis, spectroscopy, and X-ray structure of the polymer catena-[bis(azido-N)-copper(II)-μ-bis(2-benzimidazolyl)butane]

The title compound, catena-[bis(azido-N)-copper(II)-(bis(2-benzimidazolyl)butane), [Cu(C₁₈H₁₈N₄)(N₃)₂]_n, was obtained from the reaction of the ligand bis(2-benzimidazolyl)butane and Cu(N₃)₂. The x-ray crystal structure is reported. The compound crystallizes in the monoclinic space group P2₁/c with a = 8.2524(10), b = 12.765(5), c = 9.1125(15) Å, = 106.423(12)°, Z = 2. The Cu(II) ions are square-planar coordinated with trans-oriented end-on binding azido ligands. The structure is a polynuclear chain with the benzimidazole bridging at each end. In addition a N_(ligand)-H···N_(azido) H-bridge [N_(ligand)···N_(azido) = 2.994(7) Å] is present, resulting in a pseudo 2-dimensional lattice. The characteristic azido infrared vibrations are found at 2060 and 2077 cm^–1 (_as(N₃)) and 1284 and 1297 cm^–1 ((N₃)).     

Structure of (meso-5,10,15,20-tetraphenylporphyrinato) dichlorophosphorus(V) chloride, [P(tpp)Cl2]+Cl−

The title compound [P(tpp)Cl₂]⁺Cl^– crystallizes in the space group P2₁/n witha=10.701(2),b=24.860(2),c=14.799(2), =94.24(2)°,Z=4. The phosphorus atom has an octahedral coordination geometry formed by the four nitrogen atoms (Np) of the porphyrinato group and the two chloride ions. The average phosphorus-chloride distance is 2.150(1) Å, with phosphorus situated 0.006 Å below the porphyrin ring.     

Bis(2,2′-biimidazoline)bis(isothiocyanato)Metal(II) compounds. Synthesis,characterization and lattice hydrogen bonding for Metal = Mn(II) and Ni(II)

The synthesis, characterization and X-ray structures of two compounds with the general formula trans-M(biz)₂(NCS)₂ (in which biz = 2,2′-biimidazoline and M = Mn(II) for compound 1 and Ni(II) for compound 2) are reported. Both compounds crystallize in the triclinic space group P-1 with a = 8.393(5), b = 8.946(5), c = 7.659(5) Å, α = 104.440(5), β = 106.880(5), γ = 66.180(5)^∘, V = 497.7(5) ų, Z = 1 for compound 1 and a = 8.155(2), b = 8.8190(10), c = 7.480(2) Å, α = 102.259(15), β = 106.135(13), γ = 67.706(14)^∘, V = 474.7(2) ų, Z = 1 for compound 2.Both metal ions show octahedral coordination with the four nitrogen atoms of two biz ligands in the equatorial plane and the two nitrogen atoms of two isothiocyanate anions in the axial positions. The M–N≡C angles are 166.5(2) and 167.7(2) for compounds 1 and 2, respectively. These values are in the usually obtained range for trans-isothiocyanate coordinated compounds. The sulfur atom of each isothiocyanate anion acts as acceptor for the hydrogen bond with the NH group of the biz ligands. In the IR spectrum the vibrations of the thiocyanate anion are observed at 2090 and 776 cm⁻¹ for compound 1 and at 2108 and 778 cm⁻¹ for compound 2, and these values are typical for linear-bond isothiocyanate complexes of transition metals.