Syntheses,Crystal Structures and Characterization of Two Zeotype Crystals of K_4Cr_3O(H_2O)_3(OOCH)_6]_2[P_2W_(18)O_(62)]·9.5H_2O and K_4[Cr_3O(H_2O)_3(OOCH)_6]· [H_3P_2W_(17) Co(H_2O)O_(61)·20H_2O

IntroductionPolyoxometalates are used as the versatile inorga-nic building blocks for the construction of molecular-based materials[1—7]. Nanosized polyoxometalates aresuitable building blocks for the construction of crystal-line microporous structural m…     

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ce(DMSO)4(H2O)3Fe(CN)6]·H2O and [La(DMSO)4(H2O)3Co(CN)6]·H2O (DMSO = Dimethylsulfoxide)

Two new bimetallic cyano-bridged complexes [Ce(DMSO)4(H2O)3Fe(CN)6]·H2O 1 and [La(DMSO)4(H2O)3Co(CN)6]·H2O 2 have been prepared by the ball milling reaction method and structurally characterized by X-ray single-crystal structure analyses. Crystallographic data for 1:C14H32CeFeN6O8S4, Mr = 736.67, monoclinic, space group P21/n, a = 14.952(1), b =13.7276(9), c = 15.392(1) (A), β = 108.288(1)°, V = 2999.6(4) (A)3, Z = 4, Dc= 1.631 g/cm3,μ =2.304 mm-1, F(000) = 1480, R = 0.0593 and wR = 0.1611; and those for 2: C14H32CoLaN6O8S4,Mr=738.54, monoclinic, space group P21/n, a = 14.945(3), b = 13.731(3), c = 15.300(3) (A), β=107.806(1)°, V= 2989.3(11) (A)3, Z = 4, Dc = 1.641 g/cm3,μ = 2.288 mm-1, F(000) = 1480, R =0.0383 and wR = 0.1132. In both complexes the lanthanide ion is eight-coordinated in a square antiprism arrangement, and the Fe(Ⅲ) or Co(Ⅲ) ion in a nearly regular octahedral environment.The [LnM(CN)6(DMSO)4(H2O)3]·H2O (Ln = Ce and M = Fe for 1; Ln = La and M = Co for 2)species are held together via hydrogen bonds by coordinated water molecules, lattice water molecules and nitrogen atoms of cyanide groups to form a three-dimensional framework.     

Syntheses and Crystal Structures of (H3O)(C3H5N2)[Mn(OH)6 Mo6O18]·3.5H2O and (H3O)3[Co(OH)6Mo6O18]·7H2O

The crystals of the title compounds (H3O)(C3H5N2)[Mn(OH)6Mo6O18]·3.5H2O 1 and (H3O)3[Co(OH)6Mo6O18]·7H2O 2 have been prepared and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 21.5018(9), b = 10.9331(5), c = 11.8667(5)A,β = 95.3570(10)o, V = 2777.5(2)A3, Z = 4, Dc = 2.802 g/cm3, Mr = 1171.80,μ(MoKα) = 3.173 mm-1, F(000) = 223, the final R = 0.0458 and wR = 0.1041 for 2093 observed reflections (I>2σ(I)); Compound 2 crystallizes in monoclinic, space group P21/c with a = 11.4042(12), b = 10.9481(11), c = 11.6722(12)A, β= 99.948(2)o, V = 1435.4(3)A3, Z = 2, Dc = 2.794 g/cm3, Mr = 1207.80,μ(MoKα) = 3.223 mm-1, F(000) = 1160, the final R = 0.0544 and wR = 0.1066 for 1906 observed reflections (I > 2σ(I)). Both compounds 1 and 2 adopt the Anderson structure, in which the anion is of centrosymmetry and formed by six octahedral edge-sharing MoO6 units surrounding the central MO6 (M = Mn or Co) octahedron.     

Crystal structure of [CoEn3]2(W7O24)·6H2O

Crystal structure of a complex salt [CoEn₃]₂(W₇O₂₄)·6H₂O is determined by X-ray crystallography. Powder X-ray diffraction is applied for the phase identification of the products of thermal decomposition of the salt in the helium atmosphere.     

Syntheses and Crystal Structures of Two Ion Pair Complexes, [Ru(bpy)3]2[Fe(CN)6]I · 7H2O and [Ru(bpy)3]- [Fe(CN)5NO]CH3OH · H2O

Two ion pair complexes, [Ru(bpy)₃]₂[Fe(CN)₆]I [sdot] 7H₃O (1) and [Ru(bpy)₃][Fe(CN)₅NO](CH₃OH) [sdot] H₂O (2) (bpy = 2,2-bipyridine) have been synthesized and structurally characterized. X-Ray crystallographic structures of 1 and 2 both show Fe(III) and Ru(II) in distorted octahedral environments. In both complexes, H-bonding interactions between an uncoordinated water molecule and the nitrogen atom of a cyano group exist.     

The Synthesis and Characterization of [4-CH3OC6H4CH2NH3]4P2O7·6H2O

Inorganic–organic hybrid compounds exhibit interesting properties in several application areas. In this regard, chemical preparation and characterization by X-ray diffraction, thermal analysis, and IR spectroscopy are given for a new organic cation diphosphate [4-CH₃OC₆H₄CH₂NH₃]₄P₂O₇·6H₂O. This later crystallizes in a C2/c unit cell with a = 38.238(6)Å, b = 6.453(1)Å, c = 16.942(7)Å; β = 97.60(4)°; Z = 4; and V = 4144(2)ų and D_x = 1.377 g·cm^?3. Its crystal structure has been determinated and refined to R = 0.044, using 7978 independent reflections. This atomic arrangement consists of inorganic layers built up from P₂O₇ ^4? anions and water molecules. On these layers, which are parallel to the (b, c) planes, the (4-CH₃OC₆H₄CH₂NH₃)⁺ cations are anchored through multiple hydrogen bonds.     

Crystal structure and Raman spectra of [Fe(H2O)6]3+(ClO 4 ? )3·3H2O

Single crystal X-ray diffraction is used to study the structure of colorless crystals isolated from the saturated aqueous solution of trivalent iron perchlorate (TIP) in 67.5% perchloric acid. It is found that the compound crystallizes in the trigonal crystal symmetry; parameters of the hexagonal unit cell: a = b = 16.079(2) ?, c = 11.369(2) ?, ?? = ?? = 90°, ?? = 120°, space group R{ie907-1}(S ₆), Z = 6, ??_calc = 2.021 g/cm³. The structural form of the crystal hydrate is [Fe(H₂O)₆]³⁺(ClO ₄ ^? )₃·3H₂O. The structure contains two independent complex iron cations. Each of them is in the special position {ie907-2}, but retains the regular octahedral structure: average bond lengths are r(Fe-O) = 1.997(1) ?, {ie907-3}O-Fe-O bond angles differ from 90° by only 0.93°. Independent [Fe(H₂O)₆]³⁺ cations form short H-bonds (O??O 2.64 ?) with three crystallization water molecules and somewhat longer H-bonds (O??O 2.73 ?) with three ClO ₄ ^? anions. The ClO ₄ ^? anion is disordered over two positions with occupancies of 0.62(2) and 0.37(2). Both positions correspond to the general position. The outer-sphere crystallization water molecule is characterized by the tetrahedral direction of H-bonds, which it forms with two anions and two independent [Fe(H₂O)₆]³⁺ cations. All water molecules are in the general position. The Raman spectroscopic study of polycrystalline samples reveals weak bands belonging to the internal vibrations of two types of water molecules. The least broad bands are assigned to the transitions of crystallization water molecules whose symmetry is insignificantly lowered by two anion-molecular Hbonds. Anomalously broad bands are assigned to the transitions of a coordinated water molecule whose symmetry is more lowered by intermolecular and anion-molecular H-bonds.     

Syntheses and Structural Researches of Nine-coordinate K3[TbIII(nta)2(H2O)]·5.5H2O and Eight-coordinate K3[YbIII(nta)2]·5H2O

The crystal and molecular structures of K3[TbIII(nta)2(H2O)](5.5H2O (nta = nitrilotriacetic acid) and K3[YbIII(nta)2](5H2O complexes have been determined by single-crystal Xray structural analyses. Because TbIII and YbIII have different ionic radii and electronic configura- tions, they take nine- and eight-coordinate structures with two nta ligands, respectively. The crystal of K3[TbIII(nta)2(H2O)](5.5H2O belongs to orthorhombic, space group Pccn with a = 1.6374(7), b = 1.9913(8), c = 1.5068(6) nm, V = 4.913(3) nm3, Z = 8, Mr = 769.54, Dc = 2.081 g/cm3, μ= 3.476 mm-1 and F(000) = 3048. The final R and wR are 0.0432 and 0.0916 for 4961 observed reflections (I > 2.0(σI)), and 0.0814 and 0.1042 for all 21921 reflections, respectively. The [TbIII(nta)2(H2O)]3- complex anion has a nine-coordinate pseudo-monocapped square anti-prismatic structure, in which two N and six O coordinated atoms are from two nta ligands and the left ninth O atom from one water molecule. The crystal of K3[YbIII(nta)2]·5H2O is of monoclinic, space group P21/c with a = 1.5579(5), b = 0.9981(3), c = 1.5956(5) nm, β = 109.776(5), V = 2.3348(13) nm3, Z = 4, Mr = 756.62, Dc = 2.153 g/cm3, μ= 4.624 mm-1 and F(000) = 1484. The final R and wR are 0.0253 and 0.0657 for 4123 observed reflections (I > 2.0(σI)), and 0.0320 and 0.0731 for all 9414 reflections, respectively. The [YbIII(nta)2]3- complex anion has an eight-coordination structure with a distorted square antiprismatic prism, in which each nta acts as a tetradentate ligand with one N atom from the amino group and three O atoms from the carboxylic groups.     

Syntheses and(Crystal Structures of Two New One-dimensional Double Hydrogen-bonding-chain Complexes [Ni(bipy)2Cl]·ClO4 and [Zn(bipy)2Cl]·BF4

Two new transition metal complexes, [Ni(bipy)2Cl]·ClO4 (bipy = 2,2'-bipyridine) 1 and [Zn(bipy)2Cl]·BF4 2, have been synthesized and characterized by single-crystal X-ray diffraction analysis. Both 1 and 2 crystallize in monoclinic space group P21/n with Z = 4. For 1, a = 10.776(1), b = 12.067(1), c = 16.146(2)(A), β= 93.021(2)o, V = 2031.9(4)(A)3, Mr = 505.98, Dc = 1.654 g/cm3, μ = 1.255 mm-1, F(000) = 1032, the final R = 0.0406 and wR = 0.1002 for 3983 observed reflections with Ⅰ ＞ 2σ(I). For 2, a = 10.758(4), b = 12.058(4), c = 16.135(5) (A), β = 104.57(1)o, V = 2025.7(12) (A)3, Mr = 500.00, Dc = 1.639 g/cm3, μ = 1.396 mm-1, F(000) = 1008, the final R = 0.0470 and wR = 0.1237 for 3759 observed reflections with Ⅰ ＞ 2σ(I). The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. A one-dimen- sional zigzag double hydrogen-bonding-chain is generated by the intermolecular M-bipy …anion…bipy--M hydrogen bonding interactions between the chelating ligands of bipy and anion.     

Synthesis and Crystal Structure of Two Decavanadates Cluster Metal Complexes: [Co(H2O)6]2[H2V10O28]·6H2O and (NH4)2[Ca(H2O)7]2[V10O28]

Two new decavanadate metal complexes, [Co(H₂O)₆]₂[H₂V₁₀O₂₈]·6H₂O (1) and (NH₄)₂[Ca(H₂O)₇]₂[V₁₀O₂₈] (2), have been synthesized under hydrothermal condition by using chlorhydric acid as the initiator at 120 °C. The aqueous NaVO₃ solution with an aqueous solution of CoCl₂·6H₂O were used for generating 1 and aqueous CaCl₂·2H₂O and NH₄VO₃ solution were employed for creating 2. Compound 1 consisted of discrete hexa-aqua-cobalt [Co(H₂O)₆]²⁺ cations, [H₂V₁₀O₂₈]⁴⁻ anions and non-coordination water molecules. Compound 2 were composed of hepta-aqua-calcium [Ca(H₂O)₇]²⁺ cations, ammonium NH₄ ⁺ and [V₁₀O₂₈]⁶⁻ anion. For compound 2, the distorted pentagonal bipyramid [Ca(H₂O)₇]²⁺ is uncommon. In the crystal lattice, hydrogen bonds played an important role on connecting cations, anions and non-coordinated water molecules to form the three-dimensional network.     

Syntheses, Crystal Structures and Properties of Two New W-Ag 1D Chain Complexes: [W2Ag2S8·Ca(DMF)6]n and [WAgS4·Na(DMF)3]n

Two new complexes, [W2Ag2S8(Ca(DMF)6]n 1 and [WAgS4(Na(DMF)3]n 2, have been synthesized and characterized. Single-crystal X-ray analyses show both 1 and 2 have {WAgS4}n anion linear chains, but 1 has a discrete [Ca(DMF)6]2+ cation while 2 is a linear chain. UV-Visible-Near-IR spectroscopy data show that the bandgaps of the two complexes are 1.86 and 1.99 eV, respectively. Electrical conductivity measurements reveal the conductivities of 1 and 2 are 10-7 and 10-8 Scm-1, respectively and they exhibit thermally activated temperature depen- dence, which may be attributed to semiconductors.     

Crystal structure of [Co(NH3)5Cl]2(W10O32)·4H2O

By single crystal X-ray diffraction the crystal structure of the complex salt [Co(NH₃)₅Cl]₂(W₁₀O₃₂)·4H₂O is determined and the IR spectrum is interpreted. The crystal chemical analysis of the structure of complex cations and decatungstate anions and their packing in the structure is performed.     

Two Light-Metal Dihydrogenisocyanurate Hydrates Linked by Diagonal Relationship: Syntheses,Crystal Structures,and Vibrational Spectra of Li[H2N3C3O3]·1.75 H2O and Mg[H2N3C3O3]2·8 H2O

Single-crystalline materials of Li[H₂N₃C₃O₃] · 1.75 H₂O and Mg[H₂N₃C₃O₃]₂ · 8 H₂O were obtained by dissolving stoichiometric amounts of the respective carbonates with cyanuric acid in boiling water followed by gentle evaporation of excess water after cooling to room temperature. Even though both of these compounds crystallize in the triclinic space group P1 according to X-ray structure analyses of their colorless and transparent single crystals, they adopt two new different structure types. Li[H₂N₃C₃O₃] · 1.75 H₂O exhibits the unit-cell parameters a = 884.71(6) pm, b = 905.12(7) pm, c = 964.38(7) pm, α = 67.847(2)°, β = 62.904(2)° and γ = 68.565(2)° (Z = 4), whereas the lattice parameters for Mg[H₂N₃C₃O₃]₂ · 8 H₂O are a = 691.95(5) pm, b = 1055.06(8) pm, c = 1183.87(9) pm, α = 85.652(2)°, β = 83.439(2)° and γ = 79.814(2)° (Z = 2). In both cases, the singly deprotonated isocyanuric acid forms monovalent anions consisting of cyclic [H₂N₃C₃O₃]^– units, which are arranged in ribbons typical for most hitherto known monobasic isocyanurate hydrates. The structures are governed by the oxophilic strength of the respective cation which means that they fulfil their oxophilic coordination requirements either solely with water molecules ([Mg(OH₂)₆]²⁺ for Mg²⁺) or with crystal water and one or two direct coordinative contacts to carbonyl oxygen atoms (O_(cy)) of [H₂N₃C₃O₃]^– anions ([(Li(OH₂)_2–3(O_(cy)1–2]⁺ for Li⁺). In both structures occur dominant hydrogen bonds N–H ··· O within the anionic [H₂N₃C₃O₃]^– ribbons as well as hydrogen bonds O–H ··· O between these ribbons and the hydrated Li⁺ and Mg²⁺ cations.     

Synthesis and Crystal Structure of K3[HO{VO(O2)2}2]·H2O

The title compound K3[HO{VO(O2)2}2]·H2O has been synthesized and its crystal structure was determined by X-ray diffraction method. The crystal is of monoclinic, space group P21/c with a = 6.7078(3), b = 9.9539(6), c = 15.8182(9)A, β = 93.702(3)0, V = 1053.96(10)A3, Mr = 414.20, Dc = 2.610 g/cm3, Z = 4, λ(MoKα) = 0.71073A, F(000) = 808, μ = 3.014 mm-1, the final R = 0.0173 and wR = 0.0466 for 2178 observed reflections with I > 2σ(I). X-ray diffraction reveals that the coordination polyhedra of V atoms are not chemically equivalent: the V(1) and V(2) polyhedra can be described as pentagonal pyramid and pentagonal bipyramid, respectively.     

Syntheses and structures of p-HOOCC6F4COOH · H2O (H2L · H2O) and luminescent coordination polymers [Tb2(H2O)4(L)3 · 2H2O] n and Tb2(Phen)2(L)3 · 2H2O

Compounds p-HOOCC₆F₄COOH · H₂O (H₂L · H₂O), [Tb₂(H₂O)₄(L)₃ · 2H₂O] _n (I), and Tb₂(Phen)₂(L)₃ · 2H₂O (II) are synthesized. According to the X-ray structure analysis data, the crystal structure of H₂L · H₂O is built of centrosymmetric molecules H₂L and molecules of water of crystallization. The crystal structure of compound I is built of layers of coordination 2D polymer [Tb₂(H₂O)₄(L)₃] _n and molecules of water of crystallization. The ligands are the L^2? anions performing both the tetradentate bridging and pentadentate bridging-chelating functions. The coordination polyhedron TbO₉ is a distorted three-capped trigonal prism. Acid H₂L manifests photoluminescence in the UV region (??_max = 368 nm). Compounds I and II have the green luminescence characteristic of the Tb³⁺ ions, and the band with ??_max = 545 nm (transition ⁵ D ₄?? ⁷ F ₅) is maximum in intensity. The photoluminescence intensity of compound II is higher than that for compound I.     

K3[Cr3O(OOCH)6(H2O)3][α-GeW12O40]·17H2O 的合成、结构及特性研究

研究了多金属氧酸盐分子基化合物K3[Cr3O(OOCH)6(H2O)3][α-GeW12O40]·17H2O的合成、晶体结构及其结晶水可逆脱附和吸附性能.该化合物属于单斜晶系,C2/m空间群,α=2.738 3(6)nm,b=1.58 3 0(3)nm,c=1.730 4(4)nm,β=102.43(3)°,V=7.325(3)nm3,Z=4,R1(wR2)=0.067 8(0.171 9).该晶体具有孔道结构,孔道内的结晶水能够可逆的脱附和吸附,而晶体结构随之恢复,因此具有分子筛的特性.     

Syntheses and Crystal Structures of Two New One-dimensional Double Hydrogen-bonding-chain Complexes [Ni(bipy)_2Cl]·ClO_4 and [Zn(bipy)_2Cl]·BF_4

Two new transition metal complexes, [Ni(bipy)2Cl]·ClO4 (bipy = 2,2'-bipyridine) 1 and [Zn(bipy)2Cl]·BF4 2, have been synthesized and characterized by single-crystal X-ray diffraction analysis. Both 1 and 2 crystallize in monoclinic space group P21/n with Z = 4. For 1, a = 10.776(1), b = 12.067(1), c = 16.146(2) , β = 93.021(2)o, V = 2031.9(4) 3, Mr = 505.98, Dc = 1.654 g/cm3, μ = 1.255 mm–1, F(000) = 1032, the final R = 0.0406 and wR = 0.1002 for 3983 observed reflections with I > 2σ(I). For 2, a = 10.758(4), b = 12.058(4), c = 16.135(5) , β = 104.57(1)o, V = 2025.7(12) 3, Mr = 500.00, Dc = 1.639 g/cm3, μ = 1.396 mm–1, F(000) = 1008, the final R = 0.0470 and wR = 0.1237 for 3759 observed reflections with I > 2σ(I). The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. A one-dimen-sional zigzag double hydrogen-bonding-chain is generated by the intermolecular M-bipy ···anion···bipy- M hydrogen bonding interactions between the chelating ligands of bipy and anion.     

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ce(DMSO)_4(H_2O)_3Fe(CN)_6]·H_2O and [La(DMSO)_4(H_2O)_3Co(CN)_6]·H_2O(DMSO = Dimethylsulfoxide)

1INTRODUCTION Recently,cyano-bridged lanthanide-transition me-tal complexes have been extensively investigateddue to their potential applications as precursors in the preparation of rare earth orthoferrites,fluores-cent and magnetic materials[1].Various complexes of this system have been obtained in order to ex-plore the relations between structures and pro-perties by using different ligands,such as DMF,4,4?-bipy,and so on,to fill the coordination sites of lanthanide ions[2～9].But up to…