Syntheses, structural determination, and binding studies of nine-coordinate mononuclear complexes (EnH2)3[EuIII(Etha)]2 · 11H2O and (EnH2)[EuIII(Egta)(H2O)]2 · 6H2O

Two novel ethylenediaminium salt of europium complexes with aminopolycarboxylic acid ligands, (EnH₂)₃[Eu^III(Ttha)]₂ · 11H₂O (I) (En is ethylenediamine, H₆Ttha is triethylenetetramine-N,N,N′,N″,N‴,N‴-hexaacetic acid) and (EnH₂)[Eu^III(Egta)(H₂O)]₂ · 6H₂O (II) (H₄Egta is ethyleneglycol-bis(2-aminoethylether)-N,N,N′,N′-tetraacetic acid) complexes were synthesized, and their crystal structures were determined by single-crystal X-ray diffraction techniques. Both of the two complexes adopt nine-coordinate structures with the pseudo-monocapped square antiprism and crystallize in the monoclinic crystal system with the P2₁/n space group. The crystal data for complex I are as follows: a = 17.8262(8), b = 19.3137(5), c = 20.6233(8) ?, β = 111.301(2)°, V = 6615.3(4) ?³, Z = 8, ρ _c = 1.677 mg/m³, μ = 1.981 mm⁻¹, F(000) = 3432, R = 0.0308, and wR = 0.0737 for 43622 observed reflections with I ≥ 2σ(I). The crystal data for complex II are as follows: a = 12.952(3), b = 12.618(2), c = 14.809(3) ?, β = 105.695(2)°, V = 2330.0(8) ?³, Z = 4, ρ _c = 1.800 mg/m³, μ = 2.765 mm⁻¹, F(000) = 1276, R = 0.0297, and wR = 0.0638 for 18416 observed reflections with I ≥ 2σ(I). One remarkable feature of the two complexes is that the protonated [EnH₂²⁺] cations conjugating to [Eu^III(Ttha)]₂⁶⁻ and [Eu^III(Egta)(H₂O)]₂²⁻ complex anions are reviewed, respectively, which open the path for the Eu^III complexes conjugating with other various biomolecules.     

Syntheses of the eight-coordinate NH4[ErIII(Cydta)(H2O)2] · 4.5H2O and (NH4)2[Er 2III (Pdta)2(H2O)2] · 2H2O complexes and their structural investigation

In this work, the title complexes, NH₄[Er^III(Cydta)(H₂O)₂] · 4.5H₂O (I) (H₄Cydta = trans-1,2-cyclo-hexanediamine-N,N,N′,N′-tetraacetic acid) and (NH₄)₂[Er₂^III(Pdta)₂(H₂O)₂] · 2H₂O (II) (H₄Pdta= propylene-diamine-N,N,N′,N′-tetraacetic acid), were prepared, respectively, and their composition and structures were determined by elemental analyses and single-crystal X-ray diffraction techniques. Complex I selects a mononu-clear structure with pseudosquare antiprismatic geometry crystallized in the triclinic crystal system with space group $ P\bar 1 $ P\bar 1 and the central Er³⁺ ion is eight-coordinated by the hexadentate Cydta ligand and two water molecules. The crystal data are as follows: a = 8.568(3), b = 10.024(3), c = 14.377(4) ?, α = 88.404(4)°, β = 75.411(4)°, γ = 88.332(4)°, V = 1194.2(6) ?³, Z = 1, ρ _c = 1.793 g/cm³, μ = 3.586 mm⁻¹, F(000) = 648, R = 0.0257, and wR = 0.0667 for 4169 observed reflections with I ≥ 2σ(I). Complex II is eight-coordinated as well, which selects a binuclear structure with two pseudosquare antiprismatic geometry and crystallizes in the monoclinic crystal system with space group P2₁/n. The central Er³⁺ ion is coordinated by two nitrogens and four oxygens from one hexadentate Pdta ligand. Besides, two oxygens come from one carboxylic group of the neighboring Pdta ligand and one water molecule, respectively. The crystal data are as follows: a = 12.7576(8), b = 9.3151(6), c = 14.3278(9) ?, β = 96.1380(10)°, V = 1692.93(19) ?³, Z = 4, ρ _c = 2.054 g/cm³, μ = 5.015 mm⁻¹, F(000) = 1028, R= 0.0228, and wR = 0.0534 for 2984 observed reflections with I ≥ 2σ(I).     

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.     

Syntheses,spectral, thermal and structural characterization of dinuclear and polynuclear copper(II) orotate complexes, [Cu2(HOr)2(H2O)4] and [Cu(μ-HOr)(ba)2]n

The novel catena-poly-μ-orotatobis(butylamine)copper(II), [Cu(μ-HOr)(ba)₂]_n (1), and diaqua(orotato)copper(II), [Cu₂(HOr)₂(H₂O)₄] (2), complexes have been prepared and characterized by elemental analysis, magnetic measurements, FT-IR spectroscopy, EPR spectroscopy, thermal analysis and X-ray diffraction. Both complexes crystallize in the monoclinic space group, C2/c in 1 and P2₁/n in 2. In the complexes, the copper(II) ion is chelated by a deprotonated pyrimidine nitrogen atom and a carboxylate oxygen atom of the orotate. While the coordination sphere around Cu(II) is completed by two N atoms from butylamine groups and a carboxylic O atom in the axial position from a neighboring molecule in 1, the square-planar environment of Cu(II) is completed by two water atoms and one axial position is occupied by the carbonyl oxygen atom from the symmetry related molecule in 2. The coordination sphere should be described as a square pyramid and (4+1)-geometry in 1 and 2, respectively. While complex 1 shows a polymeric arrangement, compound 2 has a dimeric arrangement. The non-covalent Cu(II)-π binding force is very important for stabilizing the crystal structure of 2. The thermal decomposition of the complexes has been predicted by the help of thermal analysis (TG, DTG and DTA).     

Nine-coordinate dinuclear Na6[Gd 2III (Ttha)2] · 8H2O and mononuclear (H2En)3[GdIII(Ttha)]2 · 11H2O complexes: Synthesis and structural determination

The Na₆[Gd₂^III(Ttha)₂] · 8H₂O (I) (H₆Ttha = triethylenetetramine-N,N,N′,N″,N‴,N‴-hexaacetic acid) and (H₂En)₃[Gd^III(Ttha)]₂ · 11H₂O (II) (En = ethylenediamine) complexes were prepared with heat-refluxing and acidity-adjusting methods, respectively. Their composition and structures were determined by elemental analysis and single-crystal X-ray diffraction techniques. Complex I shapes a binuclear and nine-coordinated structure and crystallizes in the orthorhombic crystal system with space group Pccn. The central Gd³⁺ ion is coordinated with one Ttha ligand by three N atoms and four O atoms and with one adjacent Ttha ligand by two O atoms. The crystal data are as follows: a = 26.036(13) ?, b = 21.007(10) ?, c = 22.694(12) ?, V = 12412(11) ?³, Z = 8, c = 1.699 g/cm³, μ = 2.254 mm⁻¹, F(000) = 6368, R = 0.0602, and wR = 0.1146 for 3434 observed reflections with I ≥ 2σ(I). The GdN₃O₆ part in the [Gd₂^III(Ttha)₂]⁶⁻ complex anion forms a pseudo-tricapped trigonal prismatic geometry. Complex II is also nine-coordinate, but mononuclear and crystallizes in the monoclinic crystal system with space group P2₁/n. While the central Gd³⁺ ion is coordinated by four nitrogen atoms and five oxygen atoms from the same Ttha ligand. The crystal data are as follows: a = 17.7726(17) ?, b = 19.2942(17) ?, c = 20.6045(19) ?, β = 111.4600(10)°, V = 6575.6(10) ?³, Z = 8, c = 1.693 g/cm³, μ = 2.102 mm⁻¹, F(000) = 3428, R = 0.0333 and wR = 0.0827 for 14792 observed reflections with I ≥ 2σ(I). Otherwise, the GdN₄O₅ part in each [Gd^III(Ttha)]³⁻ complex anion adopts a pseudo-monocapped square antiprismatic polyhedron.     

Crystal structures of seven-coordinate (NH4)2[MnII(edta)(H2O)]·3H2O, (NH4)2[MnII(cydta)(H2O)]·4H2O and K2[MNII(hdtpa)]·3.5H2O complexes

The title compounds, (NH₄)₂[Mn^II(edta)(H₂O)]·3H₂O (H₄edta = ethylenediamine-N,N,N′,N′-tetraacetic acid), (NH₄)₂[Mn^II(cydta)(H₂O)]·4H₂O (H₄cydta = trans-1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid) and K₂[Mn^II(Hdtpa)]·3.5H₂O (H₅dtpa = diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid), were prepared; their compositions and structures were determined by elemental analysis and single-crystal X-ray diffraction technique. In these three complexes, the Mn²⁺ ions are all seven-coordinated and have a pseudomonocapped trigonal prismatic configuration. All the three complexes crystallize in triclinic system in P-1 space group. Crystal data: (NH₄)₂[Mn^II(edta)(H₂O)]·3H₂O complex, a = 8.774(3) ?, b = 9.007(3) ?, c = 13.483(4) ?, α = 80.095(4)°, β = 80.708(4)°, γ = 68.770(4)°, V = 972.6(5) ?³, Z = 2, D _c = 1.541 g/cm³, μ = 0.745 mm⁻¹, R = 0.033 and wR = 0.099 for 3406 observed reflections with I ≥ 2σ(I); (NH₄)₂[Mn^II(cydta)(H₂O)]·4H₂O complex, a = 8.9720(18) ?, b = 9.4380(19) ?, c = 14.931(3) ?, α = 76.99(3)°, β = 83.27(3)°, γ = 75.62(3)°, V = 1190.8(4)?³, Z = 2, D _c = 1.426 g/cm³, μ = 0.625 mm⁻¹, R = 0.061 and wR = 0.197 for 3240 observed reflections with I ≥ 2σ(I); K₂[Mn^II(Hdtpa)]·3.5H₂O complex, a = 8.672(3) ?, b = 9.059(3) ?, c = 15.074(6) ?, α = 95.813(6)°, β = 96.665(6)°, γ = 99.212(6)°, V = 1152.4(7) ?³, Z = 2, D _c = 1.687 g/cm³, μ = 1.006 mm⁻¹, R = 0.037 and wR = 0.090 for 4654 observed reflections with I ≥ 2σ(I). Original Russian Text Copyright ? 2008 by X. F. Wang, J. Gao, J. Wang, Zh. H. Zhang, Y. F. Wang, L. J. Chen, W. Sun, and X. D. Zhang The text was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 49, No. 4, pp. 753–759, July–August, 2008.     

配位化合物[Cd(hca)2(H2O)3](H2O)2，[Cu(hca)2(phen)]的合成与表征

配合物1由醋酸镉和Nahca(对羟基肉桂酸钠)在水溶液中反应得到,配合物2由醋酸铜,Hhca和phen在水和乙醇混合溶液中反应得到。配合物1属正交晶系,Pbcn空间群。配合物2属单斜晶系,C2/c空间群。配合物1和2中配体中的羧酸根与金属离子都是螯合配位的,末端羟基没有参与配位。配合物1和2的结构中都包含了丰富的氢键。通过氢键作用,配合物1形成了三维网状超分子结构,配合物2形成了二维层状超分子结构。     

[Pb2(TNR)2(CHZ)2(H2O)2]·4H2O和[Cd(CHZ)2(TNR)(H2O)]快速热分解过程的研究

利用温度跃升傅立叶变换红外原位分析技术在0.1MPa氩气的条件下，对斯蒂酚酸碳酰肼铅和斯蒂酚酸碳酰肼镉的快速热分解过程进行了研究。研究结果表明，斯蒂酚酸碳酰肼铅的主要热分解气体为NH₃, H₂O和 HONO，而斯蒂酚酸碳酰肼镉的主要热分解气体为CO 和 NO，因此斯蒂酚酸碳酰肼镉不满足作为环境友好起爆药的使用要求。这两种化合物在快速热分解过程中均产生金属异氰酸盐、金属碳酸盐和金属氧化物。利用Real程序计算其燃烧温度可得斯蒂酚酸碳酰肼铅的燃烧温度要高于斯蒂酚酸碳酰肼镉，对其燃烧产物进行计算，发现HNCO不在燃烧产物之列，NO的含量也比实验得出的浓度要小。     

Hydrothermal Syntheses and Structural Characterization of Two Novel Arsenic–Vanadium Clusters: [Co(2,2′-bpy)3]2[As8V14O42(H2O)]·3H2O and [2,2′-bpy][Ni(2,2′-bpy)3]2[As8V14O42(H2O)]·3H2O

Two new arsenic–vanadium clusters, [Co(2,2- bpy)₃]₂[As₈V₁₄O₄₂(H₂O)] · 3H₂O (1), [2,2-bpy][Ni(2,2-bpy)₃]₂[As₈V₁₄O₄₂(H₂O)] · 3H₂O (2) (2,2-bpy=2,2-bipyridine), have been hydrothermally synthesized and characterized by IR, elemental analysis, UV–VIS, EPR, TGA, XPS, and single crystal X-ray diffraction analysis. Crystal data: 1, triclinic, P1, a=14.368(3) Å, b=16.753(3) Å, c=24.632(5) Å, =94.15(3)°, =93.16(3)°, =113.05(3)°, Z=2; 2, monoclinic, P2₁/c, a= 30.2150(4) Å, b=14.0690(3) Å, c=26.0536(3) Å, =106.8960(10)°, Z=4. X-ray crystallographic studies showed that crystals 1 and 2 are both composed of discrete cluster anion [As₈V₁₄O₄₂(H₂O)]^4– and transition metal coordination complexes [M(2,2-bpy)₃]²⁺ (M=Co or Ni). Interestingly, compound 2 contains another neutral organic space filler of 2,2-bpy. To the best of our knowledge, compounds 1 and 2 are the first examples of structurally characterized vanadium/2,2-bpy/arsenate polyoxometallates.     

Syntheses and crystal structures of nine-coordinate K2[EuIII(dtpa)(H2O)]·5H2O and Na2[TbIII(Httha)]·6H2O complexes

The title complexes, K₂[Eu^III(dtpa)(H₂O)]·5H₂O (H₅dtpa = diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid), Na₂[Tb^III(Httha)]·6H₂O (H₆ttha = triethylenetetramine-N,N,N′,N′,N″,N″-hexaacetic acid), were prepared, and their compositions and structures were determined by elemental analyses and single-crystal X-ray diffraction techniques. The crystal of K₂[Eu^III(dtpa)(H₂O)]·5H₂O belongs to triclinic crystal system and $ P\bar 1 $ P\bar 1 space group. The crystal data are as follows: a = 8.3540(17), b = 10.147(2), c = 15.059(3) α = 84.63(3)?, β = 82.02(3)°, γ = 83.96(3)°, V = 1253.1(4)?³, Z = 2, R = 0.0325 and wR = 0.1013 for 4407 observed reflections with I ≥ 2σ(I). The [Eu^III(dtpa)(H₂O)]²⁻ has a nine-coordinate pseudo-monocapped square antiprismatic structure, in which the nine coordinate atoms, three N and six O are from one dtpa ligand and one water molecule. The crystal of the Na2[Tb^III(Httha)]·6H₂O belongs to monoclinic system and P2₁/c space group. The crystal data are as follows: a = 10.3976(10), b = 12.7908(13), c = 23.199(2) ? = 90.914(2)°, V = 3084.9(5)?³, Z = 4, R = 0.0309 and wR = 0.0704 for 5429 observed reflections with I ≥ 2σ(I). In the [Tb^III(Httha)]²⁻, the Tb³⁺ ion is nine-coordinated yielding a pseudo-monocapped square antiprismatic conformation, in which the ttha ligand coordinates to the central Tb³⁺ ion with four N atoms and five O atoms. There is a free non-coordinate carboxyl group (−CH₂COOH) that can be modified by some biological molecules having target function.     

Synthesis and structures of nine-coordinate K[SmIII (Edta)(H2O)3] · 2H2O and Ten-Coordinate K2[SmIII(Pdta)(H2O)2]2 · 4.5H2O complexes

The title complexes, K[Sm^III(Edta)(H₂O)₃] · 2H₂O(I)(H₄Edta = ethylenediamine-N,N,N′,N′-tetraacetic acid) and K₂[Sm^III(Pdta)(H₂O)₂]₂ · 4.5H₂O (II) (H₄Pdta = propylenediamine-N,N,N′,N′-tetraacetic acid), were prepared and their compositions and structures were determined by elemental analyses and single-crystal X-ray diffraction techniques, respectively. Complex I has a mononuclear structure, and the Sm³⁺ ion is nine-coordinated by an Edta ligand and three water molecules, yielding a pseudo-monocapped square antiprismatic conformation, and the complex crystallizes in the orthorhombic crystal system with space group Fdd2. The crystal data are as follows: a = 19.84(5), b = 35.58(9), c = 12.15(3) ?, V = 8580(38) ?³, Z = 16, ρ _c = 1.925 g/cm³, μ = 3.010 mm⁻¹, F(000) = 4976, R = 0.0252, and wR = 0.0560 for 3510 observed reflections with I ≥ 2σ(I). Complex II has a binuclear structure and the Sm³⁺ ion is ten-coordinated by a Pdta ligand, two oxygen atoms from a carboxylic group of adjacent Pdta ligand and two water molecules, yielding a distorted bicapped square antiprismatic prism. The complex crystallizes in the triclinic crystal system with space group P $ \bar 1 $ \bar 1 . The crystal data are as follows: a = 8.9523(15), b = 10.7106(15), c = 11.6900(19) ?, α = 80.613(5)°, β = 80.397(5)°, γ = 76.530(4)°, V = 1065.7(3) ?³, Z = 1, ρc = 1.970 g/cm³, μ = 2.532 mm⁻¹, F(000) = 1620, R = 0.0332 and wR = 0.0924 for 5390 observed reflections with I ≥ 2σ(I).     

Synthesis and structures of nine-coordinate K[Dy(Edta)(H2O)3] · 3.5H2O, (NH4)3 [Dy(Ttha)] · 5H2O, and eight-coordinate NH4[Dy(Cydta)(H2O)2] · 4.5H2O complexes

The title complexes, K[Dy(Edta)(H₂O)₃] · 3.5 H₂O (I) (H₄Edta = ethylenediamine-N,N,N′,N′-tetraacetic acid), (NH₄)₃[Dy(Ttha)] · 5H₂O (II) (H₆Ttha = triethylenetetramine-N, N,N′,N″,N‴,N‴-hexaacetic acid), and NH₄[Dy(Cydta)(H₂O)₂] · 4.5H₂O (III) (H₄Cydta = trans-1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid), were prepared, and their compositions and structures were determined by elemental analyses and single-crystal X-ray diffraction techniques, respectively. In complex I, the Dy³⁺ ion is nine-coordinated by an Edta ligand and three water molecules, yielding a pseudo-monocapped square antiprismatic conformation, and the complex crystallizes in the orthorhombic crystal system with space group Fdd2. The crystal data are as follows: a = 19.751(7), b = 35.573(12), c = 12.227(4) ?, V = 8591(5) ?³, Z = 16, space group Fdd2 ρ_c = 1.877 g/cm³, μ = 3.742 mm⁻¹, F(000) = 4800, R = 0.0259, and wR = 0.0616 for 3218 observed reflections with I ≥ 2σ(I). For complex II, the Dy³⁺ ion is nine-coordinated by a Ttha ligand, yielding a pseudo-monocapped square antiprismatic conformation, and the complex crystallizes in the monoclinic crystal system with space group P2₁/c. In addition, there is a free non-coordinate carboxyl group (-CH₂COO⁻) in the [Dy(Ttha)]³⁻ complex anion. The crystal data are as follows: a = 10.353(3), b = 12.746(4), c = 23.141(7) ?, β = 91.005(5)°, V = 3053.2(15) ?³, Z = 4, space group P2₁/c ρ_c = 1.730 g/cm³, μ = 2.532 mm⁻¹, F(000) = 1620, R = 0.0332 and wR = 0.0924 for 5390 observed reflections with I ≥ 2σ(I). For complex III, the Dy³⁺ ion is eight-coordinated by a ligand Cydta and two water molecules, yielding a distorted square antiprismatic conformation, and the complex crystallizes in the triclinic system with space group P . The crystal data are as follows: a = 8.604(3), b = 10.012(4), c = 14.369(6) ?, α = 88.330(6)°, β = 75.363(6)°, γ = 88.285(6)°, space group P V = 1196.9(8) ?³, Z = 2, ρ_c = 1.776 g/cm³, μ = 3.194 mm⁻¹, F(000) = 644, R = 0.0445 and wR = 0.1041 for 3931 observed reflections with I ≥ 2σ(I). The article is published in the original.     

trans-dinitro- and trans-dinitratoruthenium complexes [RuNO(NH3)2(NO2)2(OH)] and [RuNO(NH3)2(H2O)(NO3)2]NO3·H2O

Methods for the synthesis of trans-diammino complexes [RuNO(NH₃)₂(NO₂)₂(OH)] (I) and [RuNO(NH₃)₂(H₂O)(NO₃)₂](NO₃)·H₂O (II) are suggested. The compounds were studied by IR spectroscopy and X-ray phase and X-ray structural analyses. Crystal data: space group P-1; a = 6.2328(2) ?, b = 11.0488(3) ?, c = 11.0981(4) ?, α = 71.942(1)°, β = 83.291(1)°, γ = 86.877(1)° (I); space group P2₁; a = 6.6290(2) ?, b = 13.4389(5) ?, c = 7.0180(2) ?, β 114.281(1)° (II). Complex II readily lost some part of crystal water on storage in open air. Original Russian Text Copyright ? 2009 by M. A. Il’in, E. V. Kabin, V. A. Emel’yanov, I. A. Baidina, and V. A. Vorob’yov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 2, pp. 341–348, March–April, 2009.     

Synthesis and crystal structure of [Na2(μ-H2O)(H2O)CB[5]]Cl2 · 6H2O, [Na3(μ-H2O)4(H2O)4(CNPy@CB[6])]Cl3 · 8H2O, and [Rb2(μ-H2O)2(CNPy@CB[6])]Cl · 8H2O

The chain coordination polymers [Na₂(μ-H₂O)(H₂O)CB[5]]Cl₂ · 6H₂O (I), [Na₃(μ-H₂O)₄(H₂O)₄(CNPy@CB[6])]Cl₃ · 8H₂O (II), and [Rb₂(μ-H₂O)₂(CNPy@CB[6])]Cl₂ · 8H₂O (III) were prepared by heating (110°C) of a mixture of sodium or rubidium chloride, cucurbit[n]uril (CB[n], where n = 5, 6), 4-cyanopyridine, and water. According to X-ray diffraction data, binding of polynuclear cations with CB[n] in I–III occurs through coordination of the oxygen atoms of the cucurbit[n]uril portals to alkali metal atoms. Complexes I–III of the above composition isolated to the solid phase as supramolecular compounds with CB[n] were structurally characterized for the first time.     

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.     

配合物[Mn2(α-Furacrylic radical)4(phen)2(H2O)]·H2O的合成、晶体结构及热稳定性

One novel manganese(Ⅱ) complex [Mn2(α-Furacrylic radical)4(phen)2(H2O)]·H2O with α-furacrylic acid radical and 1,10-phenanthroline has been synthesized and characterized. Crystal data for this complex:monoclinic,space group C2/c,a=1.082 34(16)nm,b=2.445 8(4) nm,c=1.857 4(3) nm,β=104.353(2)°,V=4.763 5(12) nm3,Dc=1.471 g·cm-3,Z=4,F(000)=2 168. Final GooF=1.004,R1=0.039 7,wR2=0.108 7. The crystal structure shows that two neighboring manganese(Ⅱ) ions are linked together by two bridging α-furacrylic acid radicals and one bridging water molecule,forming a cage structure. The Mn(1)…Mn(1A) bond distance is 0.357 6 nm. Each manganese(Ⅱ) ion is coordinated with two nitrogen atoms of one 1,10-phenanthroline molecule and four oxygen atoms from three α-furacrylic acid radicals and one water molecule,forming distorted octahedral coordination geometry. Thermal stability of the complex was also discussed.     

Synthesis, structure, and physicochemical properties of K[VO2(SeO4)(H2O)] and K[VO2(SeO4)(H2O)2] · H2O

The vanadium(V) complexes K[VO₂(SeO₄)(H₂O)] and K[VO₂(SeO₄)(H₂O)₂] · H₂O were synthesized using original procedures; their physicochemical properties were studied, and the crystal structure was determined on the basis of X-ray diffraction and neutron diffraction data. The structure of K[VO₂(SeO₄)(H₂O)₂] · H₂O is composed of VO₆ octahedra connected to form infinite chains by bridging SeO₄ tetrahedra. Each VO₆ tetrahedron has short terminal V-O bonds forming the bent dioxovanadium group VO₂⁺ The unit cell parameters of K[VO₂(SeO₄)(H₂O)₂] · H₂O are a = 6.4045(1) ?, b = 9.9721(2) ?, c = 6.6104(1) ?, β = 107.183(1)°, V = 403.34 ?³, Z = 2, monoclinic system, space group P2₁. The complex K[VO₂(SeO₄)(H₂O)] forms a two-dimensional layered structure composed of highly distorted VO₆ octahedra having two short terminal V-O bonds and SeO₄ groups coordinated simultaneously by three vanadium atoms. This compound crystallizes in the monoclinic system (space group P2₁/c): a = 7.3783(1) ?, b = 10.5550(2) ?, c = 10.3460(2) ?, β = 131.625(1)°, V = 602.894(5) ?³, Z= 4. The vibrational spectra of the studied compounds are fully consistent with their structural features.     

Structural determination of new eight-coordinate NH4[EuIII(Cydta)(H2O)2]·4.5H2O and K2[Eu 2III (pdta)2(H2O)2]·6H2O complexes

The NH₄[Eu^III(Cydta)(H₂O)₂]·4.5H₂O (I) (H₄Cydta = trans-1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid) and K₂[Eu₂^III(pdta)₂(H₂O)₂]·6H₂O (II) (H₄pdta = propylenediamine-N,N,N′,N′-tetraacetic acid) complexes are prepared by heat-refluxing and acidity-adjusting methods respectively, and their composition and structures are determined by elemental analyses and single crystal X-ray diffraction techniques. The complex I has a mononuclear structure, crystallizes in the triclinic crystal system with the P[`1]P\bar 1 space group; the central Eu^III ion is eight-coordinated by a hexadentate Cydta ligand and two water molecules. The crystal data are as follows: a = 8.653(4) ?, b = 10.041(4) ?, c = 14.405(6) ?, α = 88.469(6)°, β = 74.892(6)°, γ = 88.256(7)°, V = 1207.5(9) ?³, Z = 1, D _c = 1.731 g/cm³, μ = 2.669 mm⁻¹, F(000) = 638, R = 0.0257, and wR = 0.0667 for 3807 observed reflections with I ≥ 2σ(I). The EuN₂O₆ part in the [Eu^III(Cydta)(H₂O)₂]⁻ complex anion forms a pseudo-square antiprismatic polyhedron. The complex II is eight-coordinate as well; it is a binuclear structure that crystallizes in the monoclinic crystal system with the C ₂/c space group; half of the central Eu^III ion is coordinated by two nitrogen atoms from one hexadentate pdta ligand and six oxygen atoms from the same pdta ligand, one water molecule and carboxylic group from the neighboring pdta ligand respectively. The crystal data are as follows: a = 19.866(3) ?, b = 9.1017(12) ?, c = 21.010(3) ?, β = 104.972(2)°, V = 3670.1(9) ?³, Z = 8, D _c = 2.046 g/cm³, μ = 3.710 mm⁻¹, F(000) = 2240, R = 0.0213 and wR = 0.0460 for 4183 observed reflections with I ≥ 2σ(I). Otherwise, the two EuN₂O₆ parts in the [Eu₂^III(pdta)₂(H₂O)₂]²⁻ complex anion form a pseudo-square antiprismatic polyhedron.     

一个新的夹心型杂多钨酸盐Na6(C5N2H7){[Na(H2O)2]3Co(H2O)5-[Co(H2O)]3(AsW9O33)2}•27H2O的晶体结构及性质

在pH＝7.5的水溶液中, Na₂WO₄•2H₂O, NaAsO₂, CoCl₂•6H₂O与对氨基吡啶反应, 得到了一种新的夹心型杂多钨酸盐Na₆(C₅H₇N₂){[Na(H₂O)₂]₃Co(H₂O)₅[Co(H₂O)]₃(AsW₉O₃₃)₂}•27H₂O单晶, 用X射线单晶衍射法及元素分析确定了其结构, 晶体属三斜晶系, P 空间群, 其晶胞参数为: a＝1.3276(8) nm, b＝1.7581(10) nm, c＝2.4381(14) nm, α＝70.954(9)°, β＝86.663(9)°, γ＝72.885(9)°, V＝5.136(5) nm³, Z＝2, R₁＝0.0608, wR₂＝0.0848 [I＞2σ(I)]. 在{[Na(H₂O)₂]₃Co(H₂O)₅[Co(H₂O)]₃(AsW₉O₃₃)₂}^7－阴离子中, 一个Co^2＋与聚阴离子{[Na(H₂O)₂]₃[Co(H₂O)]₃(AsW₉O₃₃)₂}^9－的一个端基氧共价连接, Co^2＋呈现出5和6两种配位数, 质子化的氨基吡啶正离子作为抗衡离子存在于晶体之中. 对标题化合物进行了IR, UV-Vis, TG-DSC表征. 对该化合物、Na₂WO₄•2H₂O及CoCl₂•6H₂O催化H₂O₂氧化乙醛的活性进行了比较研究, 该化合物的催化活性远优于简单化合物Na₂WO₄•2H₂O和CoCl₂•6H₂O.     

Crystal structure of metal-organic coordination polymers [Cu(bpy)2(H2O)2](NO3)2·4.5C2H5OH and [Cu2(bpy)(H2O)(L-pha)2](NO3)2·H2O

Two metal-organic coordination polymers [Cu(bpy)₂(H₂O)₂](NO₃)₂·4.5C₂H₅OH (1) and [Cu₂(bpy)(H₂O)(L-pha) ₂](NO₃)₂·H₂O (2) (L-Hpha = L-phenylalanine, bpy = 4,4′-bipyridyl) are prepared by slow evaporation of an aqueous alcoholic solution of copper nitrate, L-phenylalanine, and 4,4′-bipyridyl. The structure and composition of the obtained compounds are determined by single crystal XRD. The framework of compound 1 is positively charged and forms two types of intersecting channels. Compound 2 is a homochiral metal-organic coordination polymer whose structure contains L-phenylalanine anions.