一维链状铜配位聚合物[Cu(bpb)(PPh3)2]n·nClO4·nCH2Cl2·nH2O的合成、晶体结构与荧光性质研究

A coordination polymer of [Cu(bpb)(PPh₃)₂]_n·nClO₄·nCH₂Cl₂·nH₂O(bpb=1,4-bis(pyridine-3-aminome-thyl)benzene) has been synthesized and characterized by elemental analysis, IR, TG, PL and X-ray single crystal diffraction. The title complex crystallized in triclinic with space group P1, a=1.065 8(4) nm, b=1.542 4(6) nm, c=1.690 8(6) nm, α=80.11(10)°, β=76.00(10)°, γ=82.72(10)°, and V=2.646 5(17) nm³, Z=2, R=0.068 4. In the title complex, each Cu(Ⅰ) ion displays a distorted tetrahedron coordination configuration, defined by two N atoms from two different bpb groups, and two P atoms from PPh₃. Two adjacent Cu(Ⅰ) tetrahedron units are linked into a one-dimensional chain by the bpb ligands, which are further connected by hydrogen bonds to form a two-dimensional layer structure. Furthermore, the solid-state fluorescent property of the title complex was studied at room temperature. CCDC: 743417.     

配合物[Tb(p-ClBA)3(phen)]2的结构和性能

Terbium p-chlorobenzoate complex with 1,10-phenanthroline, [Tb(p-ClBA)₃(phen)]₂(1) has been obtained in the ethanol solution, where p-ClBA=p-chlorobenzoate and phen=1,10-phenanthroline. It crystallizes in the triclinic system, space group P1, a=1.008 1(2) nm, b=1.185 7(2) nm, c=1.431 1(3) nm, α=110.826(4)°, β=96.436(4)°, γ=101.737(4)°, Z=2. The two Tb(III) ions are linked by four carboxylate groups through their bidentate bridging modes, forming a dimeric unit with crystallographic inversion center. Each terbium ion has an eight-coordinate geometry with four of the coordination sites occupied by four oxygen atoms from the four bridging carboxylates, respectively, two oxygen atoms from bidentate carboxylate, and the remaining positions occupied by two nitrogen atoms from a 1,10-phenanthroline molecule. The Tb(III) ion adopt a distorted square antiprism coordination geometry. The excitation and luminescence data observed at room temperature show that the title complex emits very intensive green fluorescence under ultraviolet light. The result of thermal analysis indicates the complex [Tb(p-ClBA)₃(phen)]₂ is quite stable to heat. CCDC: 221921.     

配合物[Cu(NPA)2(Im)2(H2O)]·H2O的合成、晶体结构及电化学性质

A novel copper(II) complex [Cu(NPA)₂(Im)₂(H₂O)]·H₂O has been synthesized (NPA=N-phenylanthranilic acid and Im=imidazole) and characterized by IR, elemental analysis and X-ray single crystal diffraction methods. It Crystallizes in Triclinic system, space group P1 with a=0.987 9(2) nm, b=1.075 7(3) nm, c=1.559 7(5) nm, α=104.18(10)°, β=108.14(10)°, γ=92.69(10)°, V=1.513 39(7) nm³, Z=2, D_c=1.447 g·cm^-3, F(000)=684, R₁=0.028 0, wR=0.083 1. The Cu(II) ion in the title complex is coordinated with two oxygen atoms from two N-phenylanthranilic acid in monodenate mode, two nitrogen atoms form two imidazole, and one oxygen atom from water, forming a distorted square-pyramid coordination geometry. CCDC: 638653.     

[Cu(TO)2(H2O)4](PA)2的合成和晶体结构

[Cu(TO)₂(H₂O)₄](PA)₂ was prepared by mixing the aqueous solution of 1,2,4-triazol-5-one(TO) and Cu(PA)₂. The molecular structure and crystal structure of the title complex was determined by X-ray single crystal diffraction method. The crystal is triclinic, space group with a=0.7321(1)nm,b=0.7474(2)nm,c=1.3649(3)nm;α=88.65(2)°,β=85.63(1)°,γ=63.35(1)°;V=0.6655(2)nm³,Z=1. The Cu²⁺ coordinated with two TO molecule through its 2-nitrogen atom and four water molecules and showed an octahedral configuration.     

二维层状铜配位聚合物[Cu2(3-PyOH)2(EDTA)]n的合成与结构研究

A 2D copper coordination polymer of [Cu₂(3-PyOH)₂(EDTA)]_n (EDTA^4-=ethylenediaminetetraacetate quadrivalent anion C₁₀H₁₂N₂O₈, 3-PyOH=3-hydroxypyridine) was synthesized and characterized by the element analysis, IR and single crystal X-ray diffraction. The title complex crystallizes in monoclinic system with space group P2₁/c, a=1.327 5(3) nm, b=0.930 39(19) nm, c=0.948 44(19) nm, β=108.21(3)°, and V=1.112 8(4) nm³, Z=2, R=0.025 2, wR=0.066 1. Each copper(Ⅱ) atom is five-coordinated by three O atoms and one N atom from two different EDTA^4- groups and one N atom from 3-PyOH ligand, forming a distorted square-pyramidal coordination geometry. Two adjacent copper(Ⅱ) atoms are bridged by the bis-tetradentate EDTA^4- groups, constructing a two-dimensional layer structure along bc plane. The adjacent Cu…Cu distances are 0.502 5(3) and 0.611 3(3) nm. CCDC: 618806.     

配合物[Co(phen)2(m-chlorobenzoic acid)2·(H2O)]·(H2O)2的水热合成、晶体结构电化学分析

The title complex has been synthesized with m-chlorobenzoic acid, 1,10-phenanthroline and cobalt perchlorate anhydrous in the solvent mixture of water and methanol. Crystal data for this complex: triclinic, space group P1, a=0.870 7(3) nm, b=1.284 4(4) nm, c=1.692 9(5) nm; α=75.430(5)°, β=77.562(5)°, γ=86.346(5)°, V=1.789 4(9) nm³, D_c=1.456 g·cm^-3, Z=2, F(000)=806. Final GooF=1.065, R₁=0.068 4, wR₂=0.127 5. The crystal stru-cture shows that the Cobaly ion is coordinated with four nitrogen atoms from two 1,10-phenanthroline molecules and two oxygen atoms from one m-chlorobenzoic acid molecule and one water molecule respectively, forming a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex is also reported. CCDC: 619087.     

镧系四元混合阴离子配合物［Ce(p-MBA)2(NO3)(phen)］2的合成和晶体结构

We synthesized new mixed anion complex of lanthanide ［Ce(p-MBA)₂(NO₃)(phen)］₂ in slightly acidic solution of ethanol and determined the single crystal structure. The title complex is triclinic, space group P1, a=1.1027(4) nm, b=1.2511(5) nm, c=1.0633(3) nm, α=106.90(3)°, β=96.73(3)°, γ=86.85(3)°, V=1.3937(9) nm³, D_C=1.555 g·cm^-3, Z=1, F(000)=650.00 and μ(MoKα)=16.82 cm^-1. The four p-MBA ligands have two kinds of coordination modes and the coordination number of the Ce³⁺ is nine. There is some aromatic-stacking interaction in the benzene rings of two p-MBA ligands.     

三维网状的4-羧基苯氧乙酸锶(Ⅱ)配位聚合物[Sr2(4-CPOA)2(H2O)5]n的合成、结构与热稳定性研究

A novel coordination polymer of [Sr₂(4-CPOA)₂(H₂O)₅]_n (where 4-CPOA^2- is 4-carboxylphenoxyacetate) has been synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. The title complex belongs to monoclinic system with space group C2/c, a=2.563 9(5) nm, b=1.162 7(2) nm, c=0.742 96(15) nm, β=99.64(3)°. V=2.183 5(7) nm³, Z=4, M_r=653.60, D_c=1.988 g·cm^-3, R=0.027 8, wR=0.058 1. The strontium atom has a bicapped triangular prismatic coordination geometry, involving four oxoacetate oxygen atoms, one ether oxygen atom from different 4-CPOA^2- ligands and three water molecules. The strontium(Ⅱ) ions are linked by 4-CPOA^2- ligands and water molecules to form a 3D network structure. CCDC: 223313.     

一维链状锰配位聚合物[Mn(3,5-Me2PhCO2)2(phen)]n的合成与晶体结构

A manganese coordination polymer [Mn(3,5-Me₂PhCO₂)₂(phen)]_n(phen=1,10-phenanthroline) has been synthesized by hydrothermal methods. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a=0.770 3(4) nm, b=1.145 2(6) nm, c=1.537 0(9) nm, α=78.182(9)°, β=77.170(9)°, γ=89.784(9)°, V=1.292 8(12) nm³, Z=2, M_r=533.47, D_c=1.370 g·cm^-3, μ=0.549 mm^-1, F(000)=554, R_int=0.043 4, R=0.060 8 ,wR=0.148 4. In the crystal the manganese atom is six-coordinated by two nitrogen atoms from phen and four oxygen atoms from four 3,5-dimethylbenzolate molecules, completing an octahedral geometry. And the title complex forms one-dimensional chain structure through bridging 3,5-dimethylbenzolate molecules. CCDC: 642920.     

一维链状吡啶酮钙配位聚合物[Ca(μ-p-HPO)2(NO3)2]n的合成、晶体结构及热稳定性研究

A novel one-dimensional coordination polymer, [Ca(μ-p-HPO)₂(NO₃)₂]_n, (p-HPO=p-pyridone) was synthesized and characterized by the element analysis, IR, TG and X-ray single crystal diffraction. It crystallizes in the monoclinic space group C2/c with unit cell parameters: a=1.992 1(4) nm, b=0.374 96(7) nm, c=1.930 3(4) nm, β=109.21(3)°. V=1.361 6(5) nm³, Z=4, R=0.034 9, wR=0.084 4. The Ca atom is eight-coordinated by four O atoms from different p-pyridone ligands and four O atoms from two chelating nitrate anions, and displays a distorted square pyramidal coordination geometry. Each p-pyridone ligand bridges two adjacent Ca atoms, forming a infinite chain along the b direction. The Ca…Ca distance is 0.374 96(7) nm. A layer structure is further constructed by intermolecular hydrogen bonds and π-π interactions. The result of TG analysis shows that the title complex is stable under 185 ℃. CCDC: 241576.     

Synthesis and characterisation of HRuRh3(CO)12. Crystal structures of HRuRh3(CO)12, HRuRh3(CO)10(PPh3)2 and HRuCo3(CO)10(PPh3)2

A new ruthenium-rhodium mixed-metal cluster HRuRh₃(CO)₁₂ and its derivatives HRuRh₃(CO)₁₀(PPh₃)₂ and HRuCo₃(CO)₁₀(PPh₃)₂ have been synthesized and characterized. The following crystal and molecular structures are reported: HRuRh₃(CO)₁₂: monoclinic, space group P2₁/c, a 9.230(4), b 11.790(5), c 17.124(9) Å, β 91.29(4)°, Z = 4; HRuRh₃(CO)₁₀(PPh₃)₂·C₆H₁₄: triclinic, space group P$\text{1}$, a 11.777(2), b 14.079(2), c 17.010(2) Å, α 86.99(1), β 76.91(1), γ 72.49(1)°, Z = 2; HRuCo₃(CO)₁₀(PPh₃)₂·CH₂Cl₂: triclinic, space group P$\text{1}$, a 11.577(7), b 13.729(7), c 16.777(10) Å, α 81.39(4), β 77.84(5), γ 65.56°, Z = 2. The reaction between Rh(CO)₄^? and (Ru(CO)₃Cl₂)₂ tetrahydrofuran followed by acid treatment yields HRuRh₃(CO)₁₂ in high yield. Its structural analysis was complicated by a 80–20% packing disorder. More detailed structural data were obtained from the fully ordered structure of HRuRh₃(CO)₁₀(PPh₃)₂, which is closely related to HRuCo₃(CO)₁₀(PPh₃)₂ and HFeCo₃(CO)₁₀(PPh₃)₂. The phosphines are axially coordinated.     

Structure of two new borates YCa3(AlO)3(BO3)4 and YCa3(GaO)3(BO3)4

By replacing Mn in YCa₃(MnO)₃(BO₃)₄ with trivalent Al and Ga, two new borates with the compositions of YCa₃(MO)₃(BO₃)₄ (M=Al, Ga) were prepared by solid-state reaction. Structure refinements from X-ray powder diffraction data revealed that both of them are isostructural to gaudefroyite with a hexagonal space group P6₃/m. Cell parameters of a=10.38775(13)Å, c=5.69198(10)Å for the Al-containing compound and a=10.5167(3)Å, c=5.8146(2)Å for the Ga analog were obtained from the refinements. The structure is constituted of AlO₆ or GaO₆ octahedral chains interconnected by BO₃ groups in the ab plane to form a Kagomé-type lattice, leaving trigonal and apatite-like tunnels. It is found that most rare-earth and Cr, Mn ions can be substituted into the Y³⁺ and M³⁺ sites, respectively, and the preference of rare-earth ions to locate in the trigonal tunnel is correlated to the sizes of the M³⁺ ions.     

Crystal structures of phosphomolybdyl salts: Pb(MoO2)2(PO4)2 and Ba(MoO2)2(PO4)2

Crystal structures of Pb(MoO₂)₂(PO₄)₂ and Ba(MoO₂)₂(PO₄)₂ were determined. Both compounds contain the molybdyl group MoO₂. The monoclinic unit-cell parameters are a = 6.353(7), b = 12.289(4), c = 11.800 Å, β = 92°56(6), and Z = 4 for the lead salt and a = 6.383(8), b = 7.142(7), c = 9.953(8) Å, β = 95°46(8), and Z = 2 for the barium salt. $\text{P2}{}_1\text{c}$ is the common space group. The R values are respectively R = 0.027 and R = 0.031 for 1964 and 1714 independent reflections. The frameworks built up by a three-dimensional network of monophosphate PO₄ and molybdyl MoO₂ groups are similar, characterized mainly by corner-sharing PO₄ and MoO₆ polyhedra. Two oxygen atoms of each MoO₆ group are bonded to the molybdenum atom only as in other molybdyl salts.     

Re4(CO)12[μ3-InRe(CO)5]4 und Re2(CO)8[μ-InRe(CO)5]2-cluster aus dem reaktionssystem In/Re2(CO)10 in xylol

The thermally stable solids Re₂(CO)₈[μ-InRe(CO)₅]₂ and Re₄(CO)₁₂[μ₃-InRe(CO)₅]₄ could be obtained by treatment of In with Re₂(CO)₁₀ in a bomb tube. A mechanism of the formation of the latter cluster from the first one is proposed. Compared with Re₂(CO)₈[μ-InRe(CO)₅]₂, Re₄(CO)₁₂[μ₃_InRe(CO)₅]₄ shows in polar solvents an unusual high stability, which can be explained by the higher coordination number of In with rhenium carbonyl ligands. Re₄(CO)₁₂-[μ₃-InRe(CO)₅]₄ dissolves monomerically in acetone, where as Re₂(CO)₈[μ-InRe(CO)₅]₂ dissociates yielding Re(CO)₅^? anions. Single-crystal X-ray analyses of Re₄(CO)₁₂[μ₃-InRe(CO)₅]₄ establish the metal skeleton. The central molecular fragment Re₄(CO)₁₂ contains a tetrahedral arrangement of four bonded Re atoms [ReRe 302.8 (5) pm]. The triangles of this fragment are capped with a μ₃-InRe(CO)₅ group each [InRe(terminal) 273.5 (7) pm; InRe (polyhedral) 281.8 (7) pm]. The bridging type of In atoms with the Re₄ tetrahedron and the metal skeleton was realized for the first time. By treating Re₄(CO)₁₂[μ₃-InRe(CO)₅]₄ with Br₂ the existence of Re(CO)₅ ligands could be proved by isolating BrRe(CO)₅.     

A novel three-dimensional malonate-bridged complex {[Cu4(4,4′- bpy)8(mal)2(H2O)4](ClO4)2(H2O)4(CH3OH)2}n

A novel malonate-bridged copper (II) compound of formula {[Cu₄(4,4′-bpy)₈(mal)₂(H₂O)₄](ClO₄)₂(H₂O)₄(CH₃OH)₂}_n (4,4′-bpy = 4,4′-bipyridine; mal = malonate dianion) has been prepared and structurally characterized by X-ray crystallography. This compound exhibits a novel three-dimensional network being composed of Cu-4,4′-bipyridine layers which are pillared by malonate bridge ligands. The copper(II) ions has two different coordination environment.     

Ba3 (VO4)2-K2 Ba(MoO4)2 and Pb3 (VO4)2-K2 Pb(MoO4)2 systems

Phase equilibria in the Ba₃(VO₄)₂-K₂Ba(MoO₄)₂ and Pb3(VO₄)₂-K₂Pb(MoO₄)₂ systems have been investigated. In the first system, a continuous series of substitutional solid solutions with the palmierite structure is formed, and in the second one, the polymorphic transition in lead orthovanadate at 100°C restricts the extent of the palmierite-type solid solution to 10–100 mol % K₂Pb(MoO₄)₂. Original Russian Text ? V.D. Zhuravlev, Yu.A. Velikodnyi, A.S. Vinogradova-Zhabrova, A.P. Tyutyunnik, V.G. Zubkov, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 10, pp. 1746–1748.     

[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.     

A new three-dimensional cobalt phosphate: Co5(OH2)4(HPO4)2(PO4)2

A three-dimensional (3D) cobalt phosphate: Co₅(OH₂)₄(HPO₄)₂(PO₄)₂ (1), has been synthesized by hydrothermal reaction and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and magnetic techniques. The title compound is a template free cobalt phosphate. Compound 1 exhibits a complex net architecture based on edge- and corner-sharing of CoO₆ and PO₄ polyhedra. The magnetic susceptibility measurements indicated that the title compound obeys Curie-Weiss behavior down to a temperature of 17 K at which an antiferromagnetic phase transition occurs.     

Cluster condensation reactions. The synthesis and crystal and molecular structure of Os6(CO)14(μ2-PPh2)2(μ3-S)3(μ4-S)

Thermal degradation of the cluster compound Os₃(CO)₈(PPh₂H)(μ₃-S)₂ (I) at 125°C leads to decarbonylation and formation of the new ligand bridged hexanuclear cluster Os₆(CO)₁₄(μ-PPh₂)₂(μ₃-S)₃(μ₄-S) (II) in 11% yield. Space Group: P$\text{1}$, No. 2, a 10.427(5), b 13.552(3), c 17.919(3) Å, α 84.87(2), β 75.41(3), γ 78.43(3)°, V 2399(2) ųZ = 2, _?calc 2.82 g cm^?3. The structure was solved by the heavy atom method and refined (3223 reflections) to the final residuals R = 0.042 and R_w = 0.036. The molecule consists of two sulfido bridged open triosmium clusters which are linked by a bridging sulfido ligand and a bridging diphenylphosphino ligand.     

Structural study of Mn2(CO)8[P(NMe2)3]2

An X-ray crystal structure determination for the bimetallic complex Mn₂(CO)₈-[P(NMe₂)₃]₂ reveals that the P(NMe₂)₃ ligands are trans to the Mn---Mn bond and the Mn---Mn bond distance is relatively long, 2.946(1) Å.