[COH(NH2)2]2[Cu(pic)2(ClO4)2]的合成与晶体结构

The title compound was synthesized by reaction of Cu(ClO₄)₂， picolinic acid and carbamide in C₂H₅OH/CH₃CN solution， and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system， space group Pbca with a=14.0481(8)， b=9.0130(5)， c=18.626(1)?， V=2358.3(2)?³， Z=4， D_x=1.771g·cm^-3， μ=1.235mm^-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane， while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances， resulting in a 4+2 elongated octahedral environment. In the compound， there also exist two protonated carbamide cations for charge balance. CCDC： 195354.     

Synthesis and structure of cobalt complexes [Me3EtN] 2+ [CoI4]2? and [Me3BuN] 2+ [CoI4]2?

Complexes [Me₃EtN]₂⁺[CoI₄]²⁻ (I) and [Me₃EtN]₂⁺[CoI₄]²⁻ (II) were synthesized by reacting trimethylalkylammonium iodide with cobalt(II) iodide in acetone. According to X-ray diffraction data, complexes I and II consist of tetrahedral tetraalkylammonium cations (for I, N-C is 1.481(5)–1.590(8) CNC is 107.3(3)°–111.6(3)°; for II, N-C is 1.485(8)–1.506(10) ? and CNC is 106.9(7)°–111.7(5)°) and [CoI₄]²⁻ anions (for I, Co-I is 2.5951(5)–2.6127(5) ? and ICoI is 104.67(2)°–113.23(2)°; for II, Co-I is 2.5914(8)–2.5943(9) ? and ICoI is 107.05(2)°–114.42(5)°).     

Crystal structure of [Pd(NH3)4]3[Ir(NO2)6]2·H2O

A single crystal of [Pd(NH₃)₄]₃[Ir(NO₂)₆]₂·H₂O double complex salt is studied by X-ray diffraction. Crystallographic characteristics are as follows: a = 21.0335(5) ?, b = 8.0592(2) ?, c = 21.3452(5) ?, β = 91.254(1)°, V = 3617.43(15) ?³, P2₁/c space group, Z = 4, d _x = 2.714 g/cm³. Single-layer pseudohexagonal packing of complex anions is determined along the [−1 0 1] direction in the structure. Complex cations and crystallization water molecules are located between the mentioned layers.     

Double complex salts [Pd(NH3)4]3[Rh(NO2)6]2, [Pd(NH3)4]3[Rh(NO2)6]2·H2O as promising precursors to prepare Pd-Rh nanoalloys

Two new double complex salts [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂ (I) and [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂·H₂O (II) are synthesized and characterized. The techniques to produce one-phase residues of the salts are developed. The crystallographic data for I: a = 18.915(2) ?, V = 6767.4 ?³, F-43c space group, Z = 8, d _x = 2.548 g/cm³; II: a = 21.160(6) ?, b = 8.085(7) ?, c = 21.363(4) ?, β = 91.71(4)°, V = 3661.1(6) ?³, P2₁/c space group, d _x = 2.357 g/cm³. Thermal properties of the obtained compounds in the hydrogen and helium atmosphere are studied. It is shown that the final product of their decomposition both in the inert and reducing atmosphere is a powder consisting of bimetallic nanosized particles (nanoalloy) of Pd_0.59Rh_0.41 (Fm-3m space group, a = 3.856(2) ?, crystallite size of 8–11 nm).     

蝎型铜配合物：Cu2[ μ-pz]2[HB(pz)3]2和Cu[B(pz)4]2的合成、结构及热分解动力学性质

本文设计合成了两种以聚吡唑硼酸盐、吡唑为配体的铜配合物Cu₂[ μ-pz]₂[HB(pz)₃]₂(1)和Cu[B(pz)₄]₂(2)(pz：吡唑(C₃H₄N₂))。运用元素分析、红外光谱对配合物进行了表征，并用X-ray衍射测定了它们的晶体结构。非等温热分解动力学研究表明：配合物1的热分解反应分两步，配合物2的热分解反应一步进行。通过计算，配合物1热分解的第一步反应的可能机理为成核与生长，n=1/4；第二步反应的可能机理为化学反应。其非等温动力学方程分别为：dα/dT=A/β e^-E/RT·1/4(1-α)[-ln(1-α)]^-3和dα/dT=A/β e^-E/RT·(1-α)²。分解反应的表观活化能分别是520.37 kJ·mol^-1和149.65 kJ·mol^-1；指前因子lnA分别是118.06 s^-1和28.10 s^-1。配合物2热分解的可能机理为化学反应。其非等温动力学方程为：dα/dT=A/β e^-E/RT·(1-α)²。分解反应的表观活化能是111.41 kJ·mol^-1；指前因子lnA是21.20 s^-1。     

Phosphonium salts [Ph3AlkP] 2+ [Hg2I6]2? and [Ph3AlkP] 2+ [Hg4I10]2?: Synthesis and structure

Mercury complexes [Ph₃AlkP]₂⁺[Hg₂I₆]²⁻ and [Ph₃AlkP]₂⁺[Hg₄I₁₀]²⁻ (R = Me, Et, Pr, iso-Pr, Bu, iso-Bu) are synthesized by the reactions of triphenylalkylphosphonium Ph₃AlkPI with mercury iodide in acetone with the mole ratio 1: 1 and 1: 2, respectively. According to X-ray diffraction data, the phosphorus atom in the cations of the [Ph₃(iso-Pr)P]₂⁺[Hg₂I₆]²⁻, [Ph₃BuP]₂⁺[Hg₂I₆]²⁻, and [Ph₃(iso-Pr)P]₂⁺[Hg₄I₁₀]²⁻ complexes has a distorted tetrahedral coordination. The CPC bond angles and P-C bond lengths vary within 107.3(4)°-112.0(4)° and 1.774(8)-1.827(7) ?. In the [Hg₂I₆]²⁻ centrosymmetric binuclear anions, the mercury atoms of tetrahedral coordination lie in two near-perpendicular Hg₂I₆planes. Hg₄I₄ eight-membered cycles of the [Hg₄I₁₀]²⁻ tetranuclear anion are joined into polymeric chains through Hg … I coordination bonds (3.334, 3.681 &OA) due to which Hg atoms have a trigonal bipyramidal coordination. Original Russian Text ? V.V. Sharutin, V.S. Senchurin, N.N. Klepikov, O.K. Sharutina, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 2, pp. 267–273.     

[Ni(dien)2]2[Mn(NCS)6]·H2O的合成、晶体结构

The crystal of [Ni(dien)₂]₂[Mn(NCS)₆]·H₂O was synthesized and the structure of its single crystal was determined by X-ray diffraction. The crystal is monoclinic system, space group P2₁/c with a=16.544(3),b=15.137(2), c=17.334(3)?, β=99.90(1)°, V=4276.3(12)?³, Z=4, D_c=1.479g·cm^-3, M_r=951.55, F(000)=1998, μ=1.489mm^-1, R=0.0399, R_w=0.0958. IR was also determined.     

有机-无机杂化材料[Na2(H2O)4]2[γ-Mo8O26·(Gly-Gly)2]·4H2O的合成及晶体结构

多金属氧酸盐因其独特的结构而具有较高的抗肿瘤及抗病毒活性,蛋白质和肽是氨基酸的聚合体,氨基酸侧链官能团能与多金属氧酸盐形成新型配合物.了解氨基酸和肽与多金属氧酸盐的相互作用对于深入研究多金属氧酸盐抗肿瘤及抗病毒机理很有意义.我们曾报道了赖氨酸、丙氨酸及甘氨酸二肽与钼磷酸所形成化合物的晶体结构.     

[C4N2H12]1.5[Zn2(PO4)(HPO4)2]·H2O晶体的合成与表征

由于在电学、磁学、光学、吸附、离子交换和催化等领域具有潜在的应用价值,具有开放骨架结构的金属磷酸盐的合成一直受到人们的广泛关注.在这些磷酸盐微孔化合物中,磷酸锌晶体是拓扑结构最为丰富的一种.     

Synthesis and structure of cobalt complexes [Ph3(n-Pr)P 2+ [CoI4]2? and [Ph3(n-Am)P 2+ [CoI4]2?

Complexes Ph₃(n-Pr)P₂⁺[CoI₄]²⁻ (I) and [Ph₃(n-Am)P]₂⁺ [CoI₄]²⁻ (II) were synthesized by reactions of triphenyl(alkyl)phosphonium iodide with cobalt(II) iodide in acetone. According to the X-ray diffraction data, complexes I and II consist of tetrahedral triphenyl(alkyl)phosphonium cations (for I, P-C is 1.787(4)–1.804(4) ? and CPC is 106.73(18)°–111.4(18)°; for II P-C is 1.786(6)–1.802(6) ? and CPC is 107.6(3)°–111.7(3)°) and [CoI₄]²⁻ anions (Co-I 2.5923(6)–2.6189(6) ?, ICoI 101.86(2)°–113.25(2)° for I; Co-I 2.5899(9)–2.6171(9) 107.01(3)°–110.47(3)° for II).     

[C6N2H18]2[Mo5O15(HPO4)2]·H2O的水热合成与结构表征

通过水热法合成了一个新化合物[C6N2H18]2[Mo5O15(HPO4)2]·H2O,并通过IR光谱、ICP、元素分析、差热与热重分析和X射线单晶衍射分析等手段进行了表征.结果表明,晶体属三方晶系,P3(2)21空间群,a=1.1231(1)nm,c=2.2802(5)nm,V=2.4911(7)nm3,Dx=2.835Mg/m3,Z=6,最后的一致性因子R=0.0227,wR=0.0675.阴离子中Mo5O15构成一环状结构,2个HPO4一个连在环的下方,一个连在环的上方,形成类似于“飞碟”状的结构,阳离子为2个质子化的四甲基乙二胺.     

Synthesis, structure, and thermal decomposition of [H2(4,4′-Bipy)][In(H2O)2(NCS)4]2 and [HUr]2[In(H2O)(NCS)5] · 2H2O

The reaction of indium thiocyanate with bipyridine (4,4-Bipy) and urotropine (Ur) gave [H₂(4,4′-Bipy)][In(H₂O)₂(NCS)₄]₂ (I) and [HUr]₂[In(H₂O)(NCS)₅] · 2H₂O (II), which were identified using elemental analysis, IR spectra, and thermogravimetric analysis. The thermal decomposition of compound I and II ends at 650 and 640°C, respectively, and gives In₂O₃. X-Ray diffraction analysis of compound I showed that complex anions in the crystal form chains through O-H…S hydrogen bonds. The anion chains form a close packing of columns with bipyridine cations located in the voids. Original Russian Text ? S.P. Petrosyants, A.B. Ilyukhin, V.A. Ketsko, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 6, pp. 951–955.     

[Co(amp)2Cl2]2[ZnCl4]体系中两对称异构体的2D NMR研究

The two symmetrical isomers in [Co(amp)₂Cl₂]₂[ZnCl₄](amp=2-(Aminomethyl)pyridine) system were syn-thesized by general oxidation method and were separated by chromatography and recrystallization method. Their configurations were assigned by using 2D NMR techniques, particularly the NOESY NMR spectra. Solvent used was Me₂SO-d₆ with the central peak of the CD₃ septet as the reference ( ₁₃C,δ 39.37; ₁H,δ 2.49 relative to SiMe₄). Cation exchange media used was Dowex 50Wx 2(H⁺ form, 200～400mesh; Biorad).     

Synthesis, Crystal Structure and Cubic Order NLO Property of Square Compound [PPh4]2[Ni（CN）4Cu（PPh3）2]2·2CH3OH

A new tetranuclear cyanide-bridged complex [PPh4]2[NiⅡ(CN)4CuⅠ(PPh3)2]2·2CH3OH ([PPh4]+ = tetraphenylphosphine cation, PPh3 = triphenylphosphine) 1 has been synthesized and characterized by IR spectroscopy, elemental analysis, electronic absorption spectra and single-crystal X-ray diffraction. This complex crystallizes in triclinic, space group Pí with a = 10.910(5), b = 15.777(7), c = 18.275(8), α = 68.752(12), β = 79.776(13), γ = 81.400(14)°, NiCuC65H50N4OP3, Mr = 1122.25, V = 2873(2)3 , Z = 2, Dc = 1.293 g/cm3, F(000) = 1156, μ = 0.826 mm-1, the final R = 0.0755 and wR = 0.2155 for 7324 observed reflections (I > 2σ(I)). The title compound exhibits a discrete square tetranuclear structure and a cubic order NLO property.     

三维超分子化合物[H2bbi]3[α-PMo12O40]2的水热合成与晶体结构

利用水热技术合成了一个以Keggin型多金属氧酸盐和柔性有机配体为建筑块的三维超分子化合物[H2bbi]3[α-PMo12O40]2(1)(bbi=1,4-双-(咪唑-1-基)丁烷),用X-射线单晶衍射、元素分析、红外光谱和X-射线粉末衍射对晶体结构进行了表征.X-射线单晶衍射显示,该晶体属于三斜晶系,P-1空间群,a=1.183 60(9)nm,b=1.209 32(10)nm,c=1.77728(15)nm,α=74.089 0(10)°,β=70.949 0(10)°,γ=71.816 0(10)°,V=2.242 1(3)nm3,Z=2,Dc=3.109g/cm3,F(000)=2 300,μ=3.39mm-1,S=1.047,R1=0.035 0,wR2=0.077 6[I>2σ(I)].     

新型氰基桥联配位聚合物[Ni(en)2]2[Ni(CN)4]2·5H2O的合成、晶体结构和磁性质

分子组装在材料科学、催化和生物化学中具有潜在的应用前景,所以分子组装引起了化学、固体物理学和生物学等领域科学家们的普遍关注.分子组装常用的方法是使用具有配位能力的金属配合物作为建筑块与过渡金属阳离子反应.     

Synthesis and structure of [Ni(dien)2]3[W4S4(CN)2]·20H2O and [Cu(dien)(Hdien)]2[W4S4(CN)12]·8H2O

[Ni(dien)₂]₃[W₄S₄(CN)₁₂]·20H₂O and [Cu(dien)(Hdien)]₂[W₄S₄(CN)₁₂]·8H₂O were obtained by evaporating water-ammonia solutions containing K₆[W₄S₄(CN)₁₂]·2H₂O·2CH₃OH, diethylene triamine, and NiCl₂·6H₂O or CuCl₂·6H₂O. The crystals of the complex compounds were obtained within 3 days. The complex compounds were characterized by IR spectroscopy and by XRD and elemental analysis. XRD data for the complex [Ni(dien)₂]₃[W₄S₄(CN)₁₂]·20H₂O are: triclinic system, , a = 14.671(2) Å, b = 16.448(3) Å, c = 19.814(3) Å, α = 67.841(3)°, β = 68.996(3)°, γ = 67.527(3)°, V = 3961.6(11) ų, Z = 2; for the complex [Cu(dien)(Hdien)]₂[W₄S₄(CN)₁₂]·8H₂O: monoclinic system, C2/c, a = 37.4290(1) Å, b = 17.7370(1) Å, c = 25.7370(2) Å, β = 105.3840(2)°, V = 16474.02(16) ų, Z = 12. Original Russian Text Copyright ? 2005 by I. V. Kalinina, D. G. Samsonenko, Z. A. Starikova, A. A. Korlyukov, J. Lipkowski, V. P. Fedin, and M. Yu. Antipin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 1, pp. 139–148, January–February, 2005.     

Tetraphenylantimony(V) hexachloroplatinate, tetrachloroaurate, and hexachlorostannate [Ph4Sb] 2+ [PtCl6]2?, [Ph4Sb]+[AuCl4]?, and [Ph4Sb] 2+ [SnCl6]2?: Synthesis and crystal structures

The reactions of tetraphenylantimony with hexachloroplatinic and chloroauric acids in benzene afford bis(tetraphenylantimony) hexachloroplatinate (I) and tetraphenylantimony tetrachloroaurate (II), respectively. Compound II is also synthesized from tetraphenylantimony chloride and chloroauric acid in acetone. Bis(tetraphenylantimony) hexachlorostannate (III) is synthesized from tin dichloride and tetraphenylantimony chloride in acetone or from tin tetrachloride and tetraphenylantimony chloride in benzene. The crystal structures of compounds I–III are determined by X-ray diffraction analysis. The antimony atoms in the [Ph₄Sb]⁺ cations have a distorted tetrahedral coordination (CSbC bond angles range from 105.7(1)° to 118.5(1)° (I), from 106.2(3)° to 114.4(3)° (II), and from 106.0(1)° to 117.1(1)° (III)). The Sb-C bond lengths vary in intervals of 2.094(2)–2.098(2), 2.087(7)–2.111(7), and 2.093–2.100(3) ?, respectively. The coordination of the Pt and Sn atoms in complexes I and III is close to an ideal octahedral coordination with ClPtCl and ClSnCl bond angles of 88.68(2)°–91.32(3)° and 88.84(3)°–91.16(3)°, respectively. The square coordination of the Au atom in complex II is slightly distorted: the Au-Cl bond lengths are 2.266(2)–2.277(2) ?, the ClAuCl bond angles are equal to 89.7(1)°–90.5(1)°, the root-mean-square deviation of the atoms from the coordination plane being 0.004 ?. Original Russian Text ? V.V. Sharutin, V.S. Senchurin, O.A. Fastovets, A.P. Pakusina, O.K. Sharutina, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 5, pp. 373–379.     

2D层状焦磷酸锰(Ⅱ)[NH4]2[Mn3(P2O7)2(H2O)2]的结构和磁性研究

A two-dimensional layered manganese(Ⅱ) pyrophosphate, [NH₄]₂[Mn₃(P₂O₇)₂(H₂O)₂] (1), has been synthesized hydrothermally. Its structure is determined by single-crystal X-ray diffraction analysis. Its structure is built up by MnO₆ octahedra and P₂O₇ units, with ammonium NH₄⁺ cations residing in the interlayer regions. The manganese pyrophosphate layer consists of infinite chains of cis and trans edge sharing MnO₆ octahedra linked by P₂O₇ units. Magnetic susceptibility measurements show that this compound exhibits ferrimagnetic-like ordering below 3.2 K. Further study shows that there are two possible superexchange pathways via the oxygen anions in Mn²⁺ ions. Owing to the different bridging modes of O^2-, the competition between ferromagnetic interactions and antiferromagnetic interactions in Mn²⁺ ions results in the ferrimagnetic behavior of 1.     

含双蝶状[2Fe2S]骨架的新型[FeFe]氢化酶模型物{（μ-FcS2）[Fe2（CO）6]2（μ-SMe）2}的合成及其晶体结构

利用1,1’-双锂二茂铁与(μ-S2)Fe2(CO)6和MeI反应,合成了一种新型的含二茂铁基[FeFe]氢化酶活性中心模型化合物——(μ-FcS2)[Fe2(CO)6]2(μ-SMe)2(1),其结构经1H NMR,IR和X-射线单晶衍射表征。1属于斜方晶系,Pbca空间群,晶胞参数a=10.705 8(13),b=21.721 0(3),c=21.721 0(3),V=6 533.2(14)3,Z=8,Dc=1.834 g·cm-3,μ=2.480 mm-1,F(000)=3 584,R1=0.038 8,wR2=0.085 6。