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.     

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.     

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.     

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, 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.     

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.     

三维孔道结构(H3 NCH2 CH2 NH3)2(H3 NCH2 CH2 NH2)[VⅢ(H2O)2(VⅣ O)8(OH)4(H(P,B)O4)4((P,B)O4)4(H2O)2]·3H2O的水热合成及晶体化学研究 --(2)晶体结构与晶体化学

在单晶X射线衍射实验的基础上,对孔道结构化合物V9P8-en的类质同象物V9(P,B)8-en的晶体结构和晶体化学进行了深入研究.结果表明,该化合物的晶体学数据为:P2(1)/n,a=1.43134(9)nm,b=1.01256(6)nm,c=1.83156(12)nm,β=90.280(2)°,V=2.6545(3)nm3,Z=2,R=0.0540,wR2=0.1551.结构中,沿着三个结晶轴方向发育复杂而规整的三维孔道,最大孔径达1.83nm(∥b轴),质子化乙二胺和水分子居于孔道中.硼部分替代四面体配位的磷,替代率为B8:P8=0.1838:7.8162;其中B与{P-OH}位P的替代量大于与[P-O]位P的替代量.相对于V9P8-en来说,V9(P,B)8-en的晶胞参数发生了变化,导致b轴增长(1.0150→1.0256nm)和c轴缩短(1.8374→1.8316nm),同时β角变小(90.39→90.278(2)°).二者的化学计量比也不同,体现在结构与孔容的关系、电荷平衡、满足亲水-疏水作用的结晶水的数量及有机模板分子的赋存状态等方面都有差异.     

三维孔道结构(H3NCH2CH2NH3)2(H3NCH2CH2NH2)[VⅢ(H2O)2(VⅣO)8(OH)4(H(P,B)O4)4(P,B)O4)4(H2O)2]·3H2O的水热合成及晶体化学研究——(1)水热合成与产物表征

为了探讨化学成份对VPO体系孔道结构化合物结构稳定性的影响,根据酸碱平衡原理进行了合成实验设计;利用V2O5、H3PO4、H3BO3等简单的无机前驱物、乙二胺作结构导向剂,水热法合成了孔道结构钒硼磷酸盐化合物(H3NCH2CH2NH3)2(H3NCH2CH2NH2)[VⅢ(H2O)2(VⅣO)8(OH)4(H(P,B)O4)4((P,B)O4)4(H2O)2]·3H2O(简称V9(P,B)8-en).典型的反应起始物摩尔比为n(V2O5):n(H3BO3):n(H3PO4):n(en):n(H2O)=0.89:3.50:3.50:3.60:265(pH值为6.5),在175℃、自生压力条件下恒温晶化6.5d(最终pH值为5.9).通过电子探针、粉末X射线衍射、红外吸收光谱、原子占位度修正等方法,对产物的化学成份、物相及其结构等进行了实验研究.证实V9(P,B)8-en为V9P8-en的类质同象化合物,不同晶粒中B与P的含量有差别,B与P之比为O.1:7.9～2.54:5.46(原子比),但恒有V:(P+B)≈9:8.表明通过合理设计和控制合成条件,可在保持V9P8-en基本结构不变的前提下通过同晶取代引入新的化学成份,并由此探讨成份与结构稳定性的关系.     

Synthesis, crystal structure, and thermal analyses of triaqua-(1,10-phenanthroline-N,N′) succinatomanganese(II) dihydrate, [Mn(H2O)3(phen)(C4H4O4)]·2H2O

[Mn(H₂O)₃(phen)(C₄H₄O₄)]·2H₂O was obtained by reaction of freshly prepared MnCO₃, phen and succinic acid in CH₃OH/H₂O (1:1 v/v), and its crystal structure has been determined by single crystal X-ray diffraction methods. The title mixed ligand complex crystallizes in the triclinic space group with cell dimensions a = 7.590(1) Å, b = 9.324(1) Å, c = 13.917(1) Å, = 85.64(1)°, = 74.56(1)°, = 77.10(1)°, and D _calc = 1.584 g/cm³ for Z = 2. The crystal structure consists of the [Mn(H₂O)₃(phen)(C₄H₄O₄)] complex molecules and lattice H₂O molecules. The Mn atoms are each octahedrally coordinated by two N atoms of one phen ligand and four O atoms of three H₂O molecules and one succinato ligand with d(Mn—N) = 2.271 and 2.299 Å, and d(Mn—O) = 2.133–2.239 Å. Through intermolecular hydrogen bondings, the complex molecules are interlinked to form 2D layers, which are assembled by – stacking interactions into 3D framework with tunnels occupied by the lattice H₂O molecules. Thermal analyses showed that the title compound decomposes in two steps over the range 25–600°C upon heating in flowing Ar.     

A dinuclear cyanide-bridged complex, [(DMF)4(H2O)3LuCo(CN)6]·H2O

The crystal structure of the bimetallic cyanide bridged complex [(DMF)₄(H₂O)₃LuCo(CN)₆]·H₂O (1) was obtained by single-crystal X-ray diffraction. The central lutetium(III) ion is eight coordinate arranged in a square antiprism while the cobalt(III) ion is six coordinate, oriented octahedrally. Molecules in the crystal lattice are held together by a network of hydrogen bonding. Crystallization of 1 occurs in the centrosymmetric monoclinic space group P2₁/c (No. 14) with a = 13.875(2), b = 8.8352(9), c = 24.633(2) Å = 96.392(8)° and Z = 4.     

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.     

Synthesis and crystal structure of trans-bis(O, O′-diisopropylthiophosphoryl-1H-imidazole-N3) bis(O,O′-diisopropyldithiophosphato) nickel(II) complex: Ni[N3-ImSP(OiPr)2]2[S2P(OiPr)2]2 (Im = imidazole; iPr = isopropyl)

The mononuclear complex, Ni[N³-ImSP(OiPr)₂]₂[S₂P(OiPr)₂]₂ (Im = imidazole; iPr = isopropyl), was unexpectedly obtained in a reaction of bis(O,O-diisopropyl-dithiophosphato) nickel(II) complex with imidazole ligand, and its structure was determined by X-ray crystallography. It crystallizes in the triclinic system, space group P , with lattice parameters a = 12.437(3) Å, b = 13.181(3) Å, c = 8.4580(17) Å, = 93.16(3)°, = 101.93(3)°, = 65.26(3)°, and Z = 1. The Ni atom has almost perfect octahedral coordination geometry and is coordinated by two N atoms of imidazole from two O,O-diisopropylthiophosphoryl-1H-imidazole ligands in axial positions and four S atoms from two (O,O-diisopropyldithiophosphato) anions which act as bidentate ligands forming a four-membered chelate ring in the equatorial plane. The Ni—S bond distances are 2.469(1) and 2.507(1) Å, and the Ni—N bond distances are 2.097(2) Å. The IR spectra data are in agreement with the structural data.     

Structure of a Cu(II)-containing peptide,diaquo-gly-l-tyr Cu(II) dihydrate, [Cu(C11N2O4H13)(H2O)2·2H2O

The structure of the Cu(II) complex of gly-l-tyr [Cu(C₁₁N₂O₄H₁₃) (H₂O)₂]·2H₂O has been solved by X-ray diffraction methods. The compound crystallizes in the orthorhombic space groupP2₁2₁2₁ witha=11.970(2) Å,b=12.485(2) Å andc=10.418(3) Å, respectively, (MoK)=0.710 Å,D _c =1.59 Mgm^–3,D _m =1.59 Mgm^–3, finalR=0.04. The structure was solved by heavy atom (Cu) phased Fourier and refined by full-matrix least squares methods. The coordination geometry of the ligand around the Cu(II) ion has been established as a distorted tetragonal pyramid. The peptide molecule behaves as a tridentate ligand via its amino (N2), amido (N1) nitrogens and carboxyl (O2) oxygens. The peptide nitrogen is found to be deprotonated.     

Crystal structure of tetrakis (μ-betaine-O,O′) dichloro-dicopper(II) dichloride tetrahydrated

[Cu₂(bet)₄Cl₂]Cl₂·4H₂O (bet = betaine: IUPAC name: trimethylammonioacetate) is monoclinic, space group P2₁/c, a = 11.0510(10) Å, b = 14.7140(4) Å, c = 11.1620(15) Å, = 107.40(2)°. The dinuclear copper(II) cation [Cu₂(bet)₄Cl₂]²⁺ is counterbalanced by two naked Cl^– ions. The copper(II) ions have a square bipyramidal environment with oxygen atoms from the acetato groups in the basal planes and a chlorine and a copper atom occupying the apical positions. The metal atoms are ₂-bridged by four acetato groups and the molecular symmetry is close to C _2h. The two symmetry-independent chelating betaine molecules are present in their zwitterionic, neutral form.     

Crystal and molecular structure of di-μ-chlorobis[N-(2-hydroxyethyl)salicylideneiminato-N,O,O′ copper(II)] methanol solvate

The structure of the title compound, [Cu₂Cl₂(C₉H₁₀NO₂)₂]·CH₃OH, has been determined from single crystal X-ray diffraction data. The dinuclear units crystallize in the orthorhombic space group P2₁2₁2₁ with 4 formula units in a cell of dimensions:a=9.707(1),b=11.785(2),c=19.843(3)Å. The notable feature of the molecular structure is that it is dimeric with distorted square-pyramidal geometry at each, copper center. The two bridges are formed by C11 and C12 atoms where C11 is equatorial to Cu1 and apical to Cu2 and vice versa for atom C12. The apical Cu1–C12 and Cu2–C11 distances are 2.778(2) and 2.700(2)Å, respectively. The Cu1–Cu2 separation is 3.417(1)Å in the dimers. The geometry of the ligands and hydrogen bonds are discussed.     

Computer simulation of the self-assembly of crystal structures of zeolites Ca64(Sr,K,Ba)48(Cu12(O,Cl))4[Si192Al192O786](H2O) n (tschoertnerite, TSC, V = 31 614 Å3) and Ca2K2[Al6Si6O24](H2O)10 (willhendersonite, cha, V = 804 Å3) from template nanocluster precursors K48 and K12

The self-assembly of zeolites Ca₆₄(Sr,K,Ba)₄₈(Cu₁₂(O,Cl))₄[Si₁₉₂Al₁₉₂ O₇₈₆](H₂O) _n (tschoertnerite, TSC-type framework, V = 31614 ų) and Ca₂K₂[Al₆Si₆O₂₄] (H₂O)₁₀ (willhendersonite, CHA-type framework, V = 804 ų), which form paragenetic associations, has been simulated using computational methods (TOPOS program package). A new method for analyzing zeolites of any complexity has been used, which is based on the complete expansion of the three-dimensional structural graph (3D factor graph) in tiles and the selection of nonintersecting tiles forming a packing. The code of self-assembly of 3D structures from complementary linked nanocluster precursors is reconstructed: primary chain → microlayer → microframework. A supracluster precursor K48 with the symmetry $\bar 4$ 3m, formed of four K12 clusters corresponding to the t-hpr tile, is established for TSC. The K48 cluster contains Ca template cations, which stabilize its local region in the stages of K12 → K24 → K48 self-assembly. Bifurcations of evolution paths (structural branching points) during the self-assembly of TSC and CHA microframeworks are established in the stage of formation of the K24 supracluster from invariant templated K12 clusters. The models under consideration explain the 100% localization of B = Ca cations, which play the role of templates, and the 50% occupation of the positions of K, Sr, and Ba spacer cations (in TSC) and K spacer cations (in CHA).     

Crystal and molecular structure of four copper(II) ethylenediaminedisuccinates, [Cu2(RR,SS-Edds)] · 6H2O, Ba2[Cu(RR,SS-Edds)](ClO4)2 · 8H2O, Ba[Cu(SS-HEdds)]ClO4 · 2H2O, and Ba3[Cu2(RR,SS-Edds)2](ClO4)2 · 6H2O

Four Cu(II) complexes with the RR,SS-Edds ^4? and SS-HEdds ^3? anions are synthesized, and their crystal structures are studied. In the compounds [Cu2(RR,SS-Edds)] · 6H₂O (I) and Ba2[Cu(RR,SS-Edds)](ClO₄)₂ · 8H₂O (II), the ligand forms hexacoordinate chelate [Cu(Edds)]^2? complexes with the N atoms and O atoms of the propionate groups in the equatorial positions and the O atoms of the acetate groups in the axial vertices. In the compounds Ba[Cu(SS-HEdds)]ClO₄ · 2H₂O (III) and Ba3[Cu2(RR,SS-Edds)₂](ClO₄)₂ · 6H₂O (IV), one of the propionate arms, the protonated arm in III and the deprotonated arm in IV, does not enter into the coordination sphere of the Cu atom. An acetate arm moves to its position in the equatorial plane, and the free axial vertex is occupied by an O atom of the perchlorate ion. In I–IV, the lengths of the equatorial Cu-N and Cu-O bonds fall in the ranges 1.970–2.014 and 1.921–1.970 Å, respectively. The axial Cu-O bonds with the acetate groups and ClO ₄ ^? anions are elongated to 2.293–2.500 and 2.727–2.992 Å, respectively. In structure I, the second Cu atom acts as a counterion forming bonds with the O atoms of two water molecules and three O atoms of the Edds ligands. In II–IV, the Ba²⁺ cations are hydrated and bound to the O atoms of the anionic complexes and (except for one of the cations in IV) ClO ₄ ^? anions. The coordination number of the Ba cations is nine. The structural units in I–IV are connected into layers. In I, an extended system of hydrogen bonds links the layers into a framework. In II and III, the layers are linked only by weak hydrogen bonds, one bond per structural unit. In IV, ClO ₄ ^? anions are bound to the Ba and Cu atoms of neighboring layers, thus serving as bridges between the layers.     

The Crystal Structure and Magnetic Susceptibility of Tetrakis-(μ2-phenylacetato-O,O′)-bis(caprolactam-O)copper(II)

Abstract  

Tetrakis-(μ₂-phenylacetato-O,O′)-bis(caprolactam-O)copper(II) (1) was synthesized and characterized by X-ray crystallography, magnetic susceptibility and FT-IR spectroscopy. The title compound (1) crystallized in the monoclinic space group P2₁/n with unit cell parameters a = 18.2242(4) ?, b = 10.0994(2) ?, c = 23.0696(5) ?, β = 101.117(2)°; V = 4166.37(15) ?³; Z = 4. The molecular structure of (1) consists of a copper dimer bridged by four phenylacetate ligands in the paddlewheel geometry with caprolactam coordinated in both axial sites. The copper dimers of (1) are organized into one-dimensional columns by N–H···O interactions between bound caprolactam ligands. Magnetic susceptibility studies indicate antiferromagnetic coupling between the Cu⁺² ions with a singlet ground-state and triplet excited-state separated by |2J = 319(1) cm⁻¹ |.     

硅基(001)取向Pb(Mn1/3Nb2/3)O3-Pb(Zr,Ti)O3薄膜的制备及其铁电性能研究

采用磁控溅射法在LaNiO3/Si衬底上制备了6;Pb(Mn1/3Nb2/3)O3-94; Pb(Zr0.52 Ti0.48) O3 (PMnN-PZT)铁电薄膜,对其微结构和铁电特性进行了研究.结果表明,该铁电薄膜呈(001)高度择优取向,取向度高达98;.经过1010次铁电循环测试,铁电薄膜无疲劳现象;在104 s时间内,薄膜的铁电保持和印记特性稳定,无明显退化.该结果说明LaNiO3氧化物电极会降低PMnN-PZT薄膜的氧空位浓度,有效地缓解了电荷注入的问题,因此改善了PMnN-PZT薄膜的铁电性能.