Synthesis and crystal structures of (C8h8)Nd(C5H9C5H4) (THF)2 and [(C8H8)Gd(C5H9C4H4(THF)][(C8H8)GD(C5H9C5H4(THF)2]

LnCl₃ (Ln=Nd, Gd) reacts with C₅H₉C₅H₄Na (or K₂C₈H₈) in THF (C₅H₉C₅H₄ = cyclopentylcyclopentadienyl) in the ratio of 1 : to give (C₅H₉C₅H₄)LnCl₂(THF)_n (orC₈H₈)LnCl₂(THF)_n], which further reacts with K₂C₈H₈ (or C₅H₉C₅H₄Na) in THF to form the litle complexes. If Ln=Nd the complex (C₈H₈)Nd(C₅H₉C₅H₄)(THF)₂ (a) was obtained: when Ln=Gd the 1 : 1 complex [(C₈H₈)Gd(C_%H₉)(THF)][(C₈H₈)Gd(C₅H₉H₄)(THF)₂] (b) was obtained in crystalline form.

The crystal structure analysis shows that in (C₈H₈)Ln(C₅H₉C₅H₄)(THF)₂ (Ln=Nd or Gd), the Cyclopentylcyclopentadieny (η⁵), cyclooctatetraenyl (η⁸) and two oxygen atoms from THF are coordinated to Nd³⁺ (or Gd³⁺) with coordination number 10.

The centroid of the cyclopentadienyl ring (Cp′) in C₅H₉C₅H₄ group, cyclooctatetraenyl centroid (COTL) and two oxygens (THF) form a twisted tetrahedron around Nd³⁺ (or Gd³⁺). In (C₈H₈)Gd(C₅H₉C₅H₄)(THF), the cyclopentyl-cyclopentadienyl (η⁵), cyclooctatetraenyl (η⁸) and one oxygen atom are coordinated to Gd³⁺ with the coordination number of 9 and Cp′, COT and oxygen atom form a triangular plane around Gd³⁺, which is almost in the plane (dev. -0.0144 Å).     

配合物Zn(C3H4N2)2(C8H6O2Br)2的水热合成、晶体结构及性质

在140℃下,以3-溴-4-甲基苯甲酸和咪唑为配体,通过水热法在甲醇/水混合溶剂中反应24 h合成了锌(Ⅱ)配合物Zn(C3H4N2)2(C8H6O2Br)2。通过元素分析、红外光谱、热重分析和X射线粉末衍射对配合物进行了结构表征,同时用X射线单晶衍射分析确定了其晶体结构。结果表明,其晶体属单斜晶系,空间群为C2/c,晶胞参数:a=13.257(3),b=9.765(2),c=20.494(4),β=107.79(3)°,V=2526.3(9)3,Dc=1.655g·cm-3,μ=4.170mm-1,F(000)=1248,Z=4,最终残差因子R1=0.0552,wR2=0.1378。配合物为单核结构,中心锌(Ⅱ)离子与来自2个3-溴-4-甲基苯甲酸根的2个O原子及2个咪唑分子的2个N原子配位,形成了畸变的四方锥几何体。晶体内,分子间则通过N—H…O氢键作用在ab面形成了层状结构。研究了配合物的发光性质。     

[Mo(C9H6NO)2O2]的合成和晶体结构

合成了标题化合物[Mo(C9H6NO)2(O)2](C9H6NO=8-羟基喹啉),测定了化合物的晶体结构.晶体属单斜晶系,空间群Cc,a=13.372(3),b=9.421(2),c=13.554(3)A,β=109.71(3)°,V=1607.6(8)A3.结构由直接法解出,最后可靠性因子R=0.0473,Rw=0.062.Mo原子为6配位,位于八面体的中心.两个配体氧相互处于邻位,分别与8-羟基喹啉中的N原子处于对位.     

配合物Cu(C14H10N2O2)(C5H5N)的合成和晶体结构

The novel copper(Ⅱ) complex with salicylaldehyde benzoylhydrazone and pyridine ligands， Cu(C₁₄H₁₀N₂O₂)(C₅H₅N)， has been synthesized and characterized by elemental analysis， IR and thermal analysis. The crystal structure of the title complex has been determined by single crystal X-ray diffraction techniques. The crystal belongs to monoclinic with space group P2₁/c. The cell parameters are： a=1.6362(9)nm， b=1.7140(9)nm， c=1.2255(7)nm， β=105.168(9)°， V=3.317(3)nm³， Z=8， D_c=1.525g·cm^-3， μ(MoKα)=1.334mm^-1， F(000)=1560. The structure was refined to final R₁=0.0376， wR₂=0.0909. The copper(Ⅱ) ion lies in a dis-torted square-planar environment composed of two oxygen atoms， one nitrogen atom of tridentate acyhydrazone Schiff base ligand and one nitrogen atom of the pyridine ligand. CCDC： 193111.     

The crystal and molecular structure of dicarbonylbis(diphenylethylphosphine) platinum(0) Pt(CO)2[P(C6H5)2(C2H5)]2

The complex dicarbonylbis(diphenylethylphosphine)platinum, Pt(CO)₂[P(C₆H₅)₂(C₂H₅)]₂, crystallizes in either of the enantiomorphous space groups P3₁21 (No. 152) and P3₂21 (No. 154) with cell dimensions a = 10.64(1), c = 22.06(1) Å, U = 2163 ų; p_c = 1.564 g/cm³ for Z = 3, p_m = 1.55(3) g/cm³. The intensities of 1177 independent reflections have been determined by counter methods with MoKα monochromatized radiation. The structure has been solved by the heavy atom method. The refinement, carried out by full-matrix least squares down to a final R factor of 0.042, has enabled the absolute configuration of the crystal sample (space group P3₁21) to be ascertained. The molecule is roughly tetrahedral, and has the metal atom lying on a two-fold axis of the cell. Bond parameters are: PtC = 1.92(2) Å, PtP = 2.360(4) Å, CPtC = 117(1)° and PPtP = 97.9(2)°. The PtC₂ and PtP₂ moieties make a dihedral angle of 86.0(3)°. The overall C₂ symmetry of the molecule is probably only a statistically averaged situation, a disorder in the PtCO interactions being apparent from the orientations of the thermal ellipsoids of the C and O atoms.     

Synthesis and reactivity of [N(C6H4Br)3][B(C6F5)4]: the X-ray crystal structure of [Fe(C5H5)2][B(C6F5)4]

A new chemical oxidant [N(4-C₆H₄Br)₃][B(C₆F₅)₄], was prepared and used to synthesize [Fe(C₅H₅)₂][B(C₆F₅)₄]. The crystal structure of [Fe(C₅H₅)₂][B(C₆F₅)₄] was determined.     

三维异核Mn-Na配合物[MnNa(N3)4(C5H5N)4]的合成与表征

Azide-containing coordination polymers have received considerable attention for the construction of new molecule-based magnets. A three dimensional heteronuclear Mn-Na compound [MnNa(N₃)₄(C₅H₅N)₄] was obtained by reaction of [Mn₃O(O₂CCH₃)₆(py)₃]ClO₄ and NaN₃ in pyridine solvents. The title compound crystallizes in monoclinic space group C2/c, a=1.536 6(2), b=1.045 3(2), c=1.576 3(2) nm, β=90.309(3)°, V=2.531 8(6) nm³, Z=4. In the structure, each Mn³⁺ and Na⁺ ion coordinated with four N atoms from four N₃^- and two N atoms from two pyridine molecules. Each pair of Mn³⁺ and Na⁺ ion are linked by N₃^- bridges into a 3D polymer with PtS topology. CCDC: 706250.     

Synthesis and crystal structure of the double cluster [Cp3Fe4(CO)4(C5H4)]2(p-C6H4)

[Cp₄Fe₄(CO)₄] (1) reacts with p-BrC₆H₄Li and MeOH in sequence to afford the functionalized cluster [Cp₃Fe₄(CO)₄(C₅H₄-p-C₆H₄Br)] (2), while the reaction of 2 with n-BuLi and MeOH produces [Cp₂Fe₄(CO)₄(C₅H₄Bu)(C₅H₄-p-C₆H₄Br)] (3). The double cluster [Cp₃Fe₄(CO)₄(C₅H₄)]₂(p-C₆H₄) (4) has been prepared by treatment of [Cp₄Fe₄(CO)₄] with p-C₆H₄Li₂ and MeOH in sequence. The electrochemistry of 2 and 4, as well as the crystal structure of 4 have been investigated.     

配合物Ni(C14H10N2O3)(C5H5N)的合成和晶体结构

A novel nickel(Ⅱ) complex with 2,4-dihydroxybenzalidene benzoylhydrazone and pyridine ligands, Ni(C₁₄H₁₀N₂O₃)(C₅H₅N), has been synthesized and characterized by elemental analysis and IR. The crystal structure of the title complex has been determined by single crystal X-ray diffraction techniques. The crystal belongs to orthorhombic, space group Pbca. The cell parameters are: a=1.580 20(19) nm, b=1.362 18(16) nm, c=1.616 50(19) nm, and V=3.479 5(7) nm³, Z=8, D_c=1.497 Mg·m^-3, μ(MoKα)=1.139 mm^-1, F(000)=1 616, R=0.032 9 and wR=0.077 0 for 2 772 observed reflections (I>2σ(I)) out of 3810 unique ones. The nickel(Ⅱ) ion lies in a distorted square-planar environment composed of two oxygen atoms, one nitrogen atom of tridentate acyhydrazone schiff base ligand and one nitrogen atom of the pyridine ligand. The analysis of the crystal structure indicates that the complex has a one-dimensional chain structure, which is formed by intermolecular hydrogen bonds. CCDC: 244668.     

The crystal structure of tetrakis(methyldiphenylphosphine)iridium(I) tetrafluoroborate with cyclohexane of solvation: Ir[P(C6H5)2CH3]4BF4 - C6H12

The crystal structure of tetrakis(methyldiphenylphosphine)iridium(I) tetrafluoroborate with cyclohexane of solvation, [Ir(PPh₂Me)₄]BF₄·C₆H₁₂, has been determined from a three-dimensional X-ray analysis. The compound has been analysed in space group C₂/c of the monoclinic system. There are twelve molecules (i.e. 1.5 molecules per asymmetric unit) in a cell of dimensions a = 36.804(8), b = 22.93(2), c = 21.676(4) Å, β = 121.41(1)°. Block-diagonal least-squares refinement has given a final R-factor of 0.060 for 7905 reflections having I > 3σ(I).The structure consists of two crystallographically distinct, but structurally similar molecules, one on a general position and one on a crystallographic two-fold axis. The phosphine ligands around the iridium atoms are in a very distorted square-planar arrangement. The reactions of the cation axe discussed in terms of this structure.     

Cu[C5H3N(CCH3=N-C6H5)2]2(PF6)2配合物的合成、晶体结构和热分解反应动力学

The title complex Cu[C₅H₃N(CCH₃=N-C₆H₅)₂]₂(PF₆)₂ has been synthesized by reaction of Schiff base C₅H₃N(CCH₃=N-C₆H₅)₂ and cupric sulfate in toluene solution. The crystal structure was determined by X-ray diffraction method and the chemical formula weight of the complex is 1041.85. The crystal structure belongs to triclinic system with space group P1 and cell parameters: a=12.6470(10)?, b=14.123(2)?, c=15.613(2)?;α=66.150(10)°,β=79.470(10)°,γ=78.290(10)°, V=2481.6(5)?³, Z=2, D_c=1.394Mg·m^-3 and F(000)=1064. The final R[I >2σ(I)]:R₁=0.0668, wR₂=0.1927; R(all data): R₁=0.1133, wR₂=0.2357. The Cu(Ⅱ) was coordinated by six nitrogen, at the same time the Cu(Ⅱ) formed a distorted octahedron, besides the angles and planes of this compound were discussed . The result of kinetics of the thermal decomposition indicated that the first step of it is 2 series chemical reactions, the function of machanism is f(a)=(1-a)², and the activation energy is 144.64E/kJ. CCDC: 180872.     

Synthesis and structure of three manganese oxalates: MnC2O4·2H2O, [C4H8(NH2)2][Mn2(C2O4)3] and Mn2(C2O4)(OH)2

Three manganese oxalates have been hydrothermally synthesized, and their structures determined by single-crystal X-ray diffraction. MnC₂O₄·2H₂O (I) is orthorhombic, P2₁2₁2₁, , , , , Z=4, final R, R_w=0.0832, 0.1017 for 561 observed data (I>3σ(I)). The one-dimensional structure consists of chains of oxalate-bridged manganese centers. [C₄H₈(NH₂)₂][Mn₂(C₂O₄)₃] (II) is triclinic, , , , , α=81.489(2)°, β=81.045(2)°, γ=86.076(2)°, , Z=1, final R, R_w=0.0467, 0.0596 for 1773 observed data (I > 3σ (I)). The three-dimensional framework is constructed from seven coordinate manganese and oxalate anions. The material contains extra-framework diprotonated piperazine cations. Mn₂(C₂O₄)(OH)₂ (III) is monoclinic, P2₁/c, , , , β=91.10(3)°, , Z=1, final R₁, wR2=0.0710, 0.1378 for 268 observed data (I>2σ (I)). The structure is also three dimensional, with layers of MnO₆ octahedra pillared by oxalate anions. The hydroxide group is found bonded to three manganese centers resulting in a four coordinate oxygen.     

配合物Cu(C15H12N2O3)(C5H5N)的合成和晶体结构

The title coordination compound with N-substituted-salicyl Schiff ligand, Cu(C₁₅H₁₂N₂O₃)(C₅H₅N), has been synthesized. The coordination compound crystallizes in orthorhombic system, space group Pbca with a=2.037 62(7) nm, b=0.698 45(2)nm, c=2.508 76(9)nm, V=3.570 4(2) nm³, Z=8, F(000)=1 688, D_c=1.529 g·cm^-3, M_r=410.91, μ=1.250 mm^-1, R=0.031 3 and wR=0.077 0. In the coordination compound, one phenolate oxygen, one carbonyl oxygen and one hydrazine nitrogen atom from the dianionic ligand N-salicylaldehyde-N′-(4-methoxybenzoyl) hydrazone and one pyridine nitrogen atom coordinate to Cu(Ⅱ) ion, forming a distorted square plane. CCDC: 218182.     

乳酸配合物(NH4)2[Sr(C3H5O3)4]的晶体结构、Hirshfeld表面分析和溶液化学性质

合成了无水乳酸配合物(NH₄)₂[Sr(C₃H₅O₃)₄]。用X射线单晶衍射仪对该配合物的晶体结构进行了表征,确定了其组成、空间结构和配位方式。绘制了配合物的Hirshfeld表面和2D指纹图,揭示了分子间的相互作用以及该配合物具有多个配位位点和较强的配位活性。根据相关的晶体数据计算出了该配合物的晶格能及其对应阴离子的摩尔体积,计算得到该配合物的晶格能为2742.9 kJ·mol^-1。用等温环境反应-溶解量热计测量了该配合物在298 K超纯水溶剂中的溶解焓。根据Pitzer电解质溶液理论,在298 K下获得了该配合物的无限稀释摩尔溶解焓△_sH_m^∞和Pitzer参数,确定该配合物的△_sH_m^∞为(114.01±0.04) kJ·mol^-1。计算了该配合物的表观相对摩尔焓(^ΦL)以及不同浓度下溶质和溶剂的相对偏摩尔焓(L₁和L₂)。最后,根据晶格能和△_sH_m^∞设计了热化学循环,并计算出了阴离子的水合焓值。热重和微商热重曲线进一步揭示了该配合物的结构。     

Synthesis and crystal and molecular structure of CdPhen( iso -C4H9OCS2)2 and CdPhen( n -C4H9OCS2)2 mixed-ligand complexes

Mixed-ligand complexes CdPhen(i-BuOCS₂)₂ (I) and CdPhen(n-BuOCS₂)₂ (II) have been synthesized. Their structures were solved using X-ray diffraction data (X8 APEX diffractometer, MoK _α radiation, 1641 and 2497 F _hkl , R = 0.0359 and 0.0389). Crystals I are orthorhombic with unit cell parameters a = 6.5883(3) Å, b = 19.7123(10) Å, c = 20.1936(11) Å, V = 2622.6(2) ų; Z = 4, space group Pbcn; crystals II are monoclinic, a = 6.5845(2) Å, b = 19.1522(6) Å, c = 20.7091(7) Å, β = 97.106(1), V = 2591.5(1) ų, Z = 4, space group C2/c. The structures consist of discrete mononuclear molecules in which the coordination polyhedron of the Cd atom is a distorted N₂S₄ octahedron. Molecular packing and interactions in the structures are discussed. Original Russian Text Copyright ? 2007 by R. F. Klevtsova, T. G. Leonova, L. A. Glinskaya, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No. 2, pp. 274–281, March–April, 2007.     

Synthesis, crystal structure and photoluminescence of a novel tetra-nuclear calcium complex [(Ca(C15H8O7S)-(H2O)(DMSO))3(Ca(C15H8O7S) (DMSO)2]·4DMSO

The sulfonate derivate of chrysin coordinates with Ca²⁺ to form a novel tetra-nuclear calcium complex [(Ca(C₁₅H₈O₇S)(H₂O)(DMSO)₃(Ca(C₁₅H₈O₇S)(DMSO)₂]·4DMSO. The structure of the complex is characterized by IR,¹H NMR and X-ray single-crystal diffraction analysis. The results show that the complex crystallizes in triclinic, space group PĪ, cell parametera = 1.4725(6) nm,b = 1.6480(7) nm,c = 2.1006(8) nm, α = 83.928(7)°, β= 85.938(7)°, γ= 85.212(7)°,V = 5.041(3) nm³,Dc = 1.476 g/cm³,Z = 2, μ=0.568 nm⁻¹,F(000) = 2324,R = 0.0778,wR = 0.1821. In the complex, four Ca²⁺ which are bridged by four 5-hydroxyanion-7-dihydro-xyfla-vone-6-sulfonate ligands with their carbonyl and 5-hydroxyanion group build an approximate square. The coordination number of Ca²⁺ is 7 and the coordinated atoms are all oxygen from the carbonyl, hydroxyl and suflo-group of 5-hydroxyanion-7-hydroxyflavone-6-sulfonate, H₂O and DMSO. Four ligands locate on two sides of the square. Two of them on the same side are almost paralleled and aromatic п-п stacking exists between them. Ligands on the opposite side are nearly perpendicular to each other. Meanwhile, the solid of title compound has the photoluminescent phenomenon. The title compound emits green fluorescence (λ_em = 520 nm) when it is excited at the wavelength of 410 nm and its photoluminescent mechanism is discussed.     

Synthesis and x-ray crystallographic structural determination of the acetylene complex (η5−C5H5)2W2(CO)4(C2H2)

Reaction of photogenerated (η⁵?C₅H₅)₂W₂(CO)₄ with acetylene at 25°C yields a complex of the formula (η⁵-C₅H₅)₂W₂(CO)₄(C₂H₂). The crystal structure of the complex shows it to have a tetrahedrane-like W₂C₂ core. The C—C bond distance of the C₂H₂ unit is 1.33 Å which is close to that of ethylene, considerably longer than the 1.20 Å for acetylenes. The W—W distance is 2.987 Å which is ～0.25 Å shorter than the W—W distance in (η⁵-C₅H₅)₂W₂(CO)₆ but longer than that expected for (η⁵-C₅H₅)₂W₂(CO)₄. By analogy to the parent (η⁵-C₅H₅)₂M₂(CO)₆ species, the near-UV absorption in (η⁵-C₅H₅)₂M₂(CO)₄(C₂H₂) is assigned to a σ_b → σ^* transition. Owing to the shorter M—M bond in the C₂H₂ adducts, the σ_b → σ^* absorption is at higher energy than in the (η⁵-C₅H₅)₂M₂(CO)₆ complexes.     

Thermal behaviour of two new salts of malonic acid: Cu(C3H2O4)·4H2O and Cu(NH4)2(C3H2O4)2

Two new salts of malonic acid have been prepared: the copper(II) malonate tetrahydrate and the copper(II)-ammonium double malonate. Their study by thermal analysis (TG and DTA) leads to the following results:Cu(C₃H₂O₄)·4H₂O: the dehydration is rather complex and it is only under careful conditions that an intermediate hydrate Cu(C₃H₂O₄)·3H₂O could be traced. At about 170°C the dehydration is not ended (the salt holds yet about 0.15H₂O) and the anhydrous salt occurs only at about 240°C. It decomposes immediately leading to residues the composition of which depends upon the surrounding atmosphere; the part played by the gas given off is discussed.Cu(NH₄)₂(C₃H₂O₄)₂: this salt melts and decomposes simultaneously at about 190°C. During the decomposition the copper nitride Cu₃N forms as intermediate compound (as well as copper metal). Concerning the final residues of the decomposition the results and the conclusions are the same as the ones of the previous case.     

1-Allyl derivatives: Synthesis and crystal structures for [(NH2C5H4N(C3H5))2Cu3Cl3(NO3)2] and [C9H7N(C3H5)Cu(NO3)2]

1-Allyl-4-aminopyridinium chloride reacts with Cu(NO₃)₂ · 3H₂O in an ethanolic solution under the conditions of ac electrochemical synthesis at copper electrodes to form crystals of compound [(NH₂C₅H₄N(C₃H₅))₂Cu₃Cl₃(NO₃)₂] (I). The crystals of compound I are monoclinic: space group P2₁/c, Z = 4, a = 25.770(7), b = 7.230(4), c = 12.505(5) ?, β = 92.58(3)°, V = 2328(2) ?³. The direct interaction of 1-allylquinolinium nitrate with Cu(NO₃)₂ · 3H₂O in a methanolic solution in the presence of metallic copper yields crystals of compound [C₉H₇N(C₃H₅)Cu(NO₃)₂] (II). The crystals of compound II are triclinic: space group P , a = 6.756(3), b = 8.391(4), c = 12.489(5) ?, α = 77.18(3)°, β = 89.48(4)°, γ = 73.32(3)°, V = 662.0(5) ?³. The structure of compound I is built of infinite linear anions: polymeric fragments {(NH₂C₅H₄N(C₃H₅))₂Cu₃Cl₃(NO₃)₂} _n . Each of two copper atoms (Cu(1) and Cu(2)) π-coordinates the C=C bonds of the allyl groups of the 1-allyl-4-aminopyridinium cations, the oxygen atom of the nitrate ions, and two chlorine atoms. The third copper atom Cu(3) is linearly linked with two chlorine atoms. Particular polymeric fragments are additionally joined by the N-H…O, C-H…O, C-H…Cl hydrogen bonds. The crystal structure of compound II is built-up of the isolated L₂Cu₂(NO₃)₄ fragments (L is the 1-allylquinolinium cation). The metal atom is localized in the trigonal pyramidal coordination environment of three oxygen atoms of the nitrate ions and of the C=C bond of the allyl group of the cation. The particular L₂Cu₂(NO₃)₄ fragments are additionally joined by the C-H…O hydrogen bonds. Original Russian Text ? A.V. Pavlyuk, T. Lis, M.G. Mys’kiv, 2009, published in Koordinatsionnaya Khimiya, 2009, Vol. 35, No. 6, pp. 458–462.     

An organosilyl derivative of trivacant tungstophosphate. Synthesis, characterization and crystal structure determination of α-A-[NBu4]3[PW9O34(C2H5SiO)3(C2H5Si)]

In the presence of NBu₄ⁿBr acting as phase-transfer reagent, organosilicon trichloride C₂H₅SiCl₃ reacts in acetonitrile with the trivacant tungstophosphate sodium salt β-A-Na₈H[PW₉O₃₄]·24H₂O to give hybrid organosilyl polyoxotungstate derivative α-A-[NBu₄ⁿ]₃[PW₉O₃₄(C₂H₅SiO)₃(C₂H₅Si)]. X-ray single crystal structural analysis indicates that the title compound is monoclinic, space group Cc, with lattice constants a=26.828(5), b=22.459(5), c=17.517(4) Å, β=103.19(3)°, V=10,276(4) Å³, Z=4, R=0.0462. According to the result of X-ray single crystal diffraction and chemical analysis, the hybrid polyanion consists of one α-A-[PW₉O₃₄]⁹⁻ framework on which are grafted simultaneously three RSiO groups through six Si-O-W bridge bonds, each of which is attached to the fourth RSi group through three Si-O-Si bridge bonds. The hybrid polyanion becomes a partial saturated, closed cage structure and also has an assembly of virtual C_3V symmetry.