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.     

CRYSTAL STRUCTURES OF Cd(H2O)2Cu(CN)3·2H2O,K[Cd(H2O)2Cu2(CN)5]·2H2O AND K2[Cd(H2O)Cu4(CN)8]·1.5H2O. STRUCTURES OF MULTI-DIMENSIONAL FRAMEWORKS FORMED WITH CADMIUM(II), COPPER(I) AND BRIDGING CYANO GROUPS

Abstract

In an attempt to form new multi-dimensional structures of cyano complexes including cadmium(II) and copper(I), four new complexes were obtained successively from an aqueous solution at intervals of from a few days to a few months. The complex 1 obtained first was unstable in the atmosphere. The crystal structures of the other complexes (2–4) obtained from second to fourth were determined by single crystal X-ray structure determinations. Their crystal data are as follows: 2 Cd(H₂O)₂ Cu(CN)₃·2H₂O, monoclinic, C2/m, a = 14.038(1), b = 9.944(1), c = 7.738(1) Å, β = 116.019(7)°, Z = 4; 3 K[Cd(H₂O)₂Cu₂(CN)₅]·2H₂O, triclinic, PI, a = 17.429(9), b = 16.519(7), c = 10.085(5) Å, α = 128.60(3), β = 137.44(2), γ = 45.82(2)°, Z = 4; 4 K₂[Cd(H₂O)Cu₄(CN)₈]·1.5H₂O, monoclinic, C2/c, a = 19.387(2), b = 16.056(3), c = 12.663(2)Å, β = 110.419(9)°, Z = 4. The main structural feature found in the complexes is that the whole framework consists of two networks, a Cd-Cu(I)-CN complex network that has an infinite network formed with bridging cyano groups between the metal atoms and a network formed with hydrogen bonding among water molecules. The second network is connected to Cd in the Cd-Cu(I)-CN complex network via a water ligand coordinated to Cd. In 2 a planar network of [CdCu(CN)₃] complexes are stacked along the c axis and the second network links the stacked complexes. 3 has a stacked structure of [Cd(H₂O)₂Cu(CN)₅]^2? in a bi-layered structure. The second network of 3, which includes K⁺ ions with an electrostatic interaction, spreads over the crystal, penetrating vacant spaces of the metal complex network. 4 has a double lattice structure with a pair of enantiomeric three-dimensional [Cd(H₂O)Cu₄(CN)₈]^2? complexes inter-penetrating each other. There are three structural factors for forming these framwork structures: (1) a non-planar coordination structure for Cd(II) that extends the planar structure of the Cu(I)-CN complex to a three-dimensional structure for the Cd-Cu(I)-CN complex; (2) a trigonal planar coordination structure for Cu(I) that generates vacant space in the metal complex network and makes possible hydrogen bonds to form the second network; (3) structural distortions of bridging cyano groups and a coordination structure of Cu(I) that cause variations of the metal complex network structure.     

The magnetochemistry of novel cyano-bridged complexes Ln(DMF)4(H2O)2Mn(CN)6 · H2O (Ln = Tb,Dy, Er)

Using K₃Mn(CN)₆, DMF and Ln(NO₃)₃ · 6H₂O (Ln = Tb, Dy or Er), novel cyano-bridged complexes Ln(DMF)₄(H₂O)₂Mn(CN)₆ · H₂O (TbMn, DyMn and ErMn, respectively) were prepared and their magnetochemical properties were studied in detail. A weak antiferromagnetic interaction was found to exist between the rare earth ions and the manganese ion. Er(DMF)₄(H₂O)₂Mn(CN)₆ · H₂O, in particular, exhibits long-range magnetic ordering, a higher critical temperature (T _c = 17.5 K) and a stronger coercive force (H _c = 980 Oe).     

Synthesis and Crystal Structure of a Cyano-bridged Bimetallic Complex [La(betaine)2(H2O)6Fe(CN)6]·2H2O

The title complex [La(betaine)2(H2O)6Fe(CN)6](2H2O (betaine = (CH3)3NCH2CO2) has been synthesized and characterized by X-ray single-crystal structure analysis. The crystal crystallizes in monoclinic, space group P21/n with a = 15.793(5), b = 8.927(3), c = 22.257(7) (A), β = 110.147(5)°, C16H38FeLaN8O12, Mr = 729.31, Z = 4, V = 2946.0(15) (A)3, Dc = 1.640 g/m3, μ(MoKα) = 1.988 mm-1, F(000) =1476, R = 0.0388 and wR = 0.0827 for 4237 observed reflections (I > 2σ(I)). The La3+ ion is nine-coordinated by one cyano nitrogen atom and eight oxygen atoms of two betaine and six water molecules. Each complex molecule is connected to form a 3D network structure by some O-H…O and O-H…N hydrogen bonds.     

Synthesis, properties, and thermal decomposition of compounds [Co(En)3][Fe(CN)6] · 2H2O and [Co(En)3]4[Fe(CN)6]3 · 15H2O

Binary complex salts, [Co(En)₃][Fe(CN)6] · 2H₂O and [Co(En)₃]₄[Fe(CN)₆]₃ · 15H₂O, are synthesized. The properties of the salts and their thermolysis in air, dihydrogen, and argon are studied. Oxides of the central ions of the binary complex salts are found to be the thermolysis products in an oxidative atmosphere. Solid solutions (intermetallic compounds) CoFe are the thermolysis products in the reductive atmosphere, whereas intermetallides containing considerable amounts of C and N and an impurity of Co and Fe oxides are the thermolysis products in an inert atmosphere. Gaseous thermolysis products in dihydrogen and argon are NH₃, hydrocarbons, and ethylenediamine.     

23-Electron Re6 metal clusters: syntheses and crystal structures of (Ph4P)3[Re6S8(CN)6], (Ph4P)2(H)[Re6Se8(CN)6]·8H2O,and (Et4N)2(H)[Re6Te8(CN)6]·2H2O

The cluster anions [Re₆X₈(CN)₆]^34– (X = S, Se, or Te) containing 23 cluster valence electrons in the Re₆ octahedron were synthesized and isolated as salts with organic cations. The crystal structures of the (Ph₄P)₃[Re₆S₈(CN)₆], (Ph₄P)₂(H)[Re₆Se₈(CN)₆]·8H₂O, and (Et₄N)₂(H)[Re₆Te₈(CN)₆]·2H₂O clusters were solved by X-ray diffraction analysis. Removal of one electron has virtually no effect on the geometry and interatomic distances in the cluster anion but leads to a substantial change in the electronic spectrum and to an increase in stretching vibration frequencies _CN compared to those of the [Re₆X₈(CN)₆]^4– anions.     

An analysis of the vibrational frequencies and amplitudes of the H5O+2 ion in H4SiW12O40·6H2O (TSA·6H2O) and H3PW12O40·6H2O (TPA·6H2O)

The infrared, Raman and inelastic neutron scattering (INS) spectra of TSA·6H₂O and TPA·6H₂O are in agreement with those expected for the presence of H₅O⁺₂ ions. Force fields for different assignment schemes are compared with the observed vibrational frequencies and the INS spectral profile. All but two schemes are eliminated. Whilst low-resolution INS spectroscopy cannot distinguish between these two schemes, the orientations of the vibrational ellipsoids for one scheme are in better agreement with those reported from low-temperature crystallographic studies of the H₅O⁺₂ ion.     

Crystal structure of [{Cu(H2O)(en)2}{Cu(en)2}Re6Te8(CN)6]·3H2O

The reaction of Cs₄[Re₆Te₈(CN)₆]·2H₂O with Cu(en)₂Cl₂ in water affords crystals of a cluster complex [{Cu(H₂O)(en)₂}{Cu(en)₂}Re₆Te₈(CN)₆]·3H₂O. The structure of the compound is determined by single crystal X-ray diffraction (a = 10.8082(4) Å, b = 16.5404(6) Å, c = 24.6480(7) Å, β = 92.696(1)°, V = 4401.5(3) ų, Z = 4, space group P2₁/n, R ₁ = 0.0331, wR ₂ (all data) = 0.0652). In the complex, cluster [Re₆Te₈(CN)₆]^4? anions are linked by Cu²⁺ cations into zigzag chains through cyanide bridges. The coordination environment of the copper cations is complemented by ethylenediamine molecules. Each of the cluster anions is additionally coordinated by a terminal fragment {Cu(H₂O)(en)₂}.     

Synthesis, crystal structures, and properties of [Ca(H2O)2(Dmf@CB[6])(Bdc)] · DMF · 4H2O and [Ca(H2O)3(Dmf@CB[6])]Cl2 · 2H2O

Complexes [Ca(H₂O)₂(Dmf@CB[6])(Bdc)] · DMF · 4H₂O (I) and [Ca(H₂O)₃(Dmf@CB[6])]Cl₂ · 2H₂O (II) are synthesized by the heating (95°C) of a mixture of calcium chloride and cucurbit[6]uril (CB[6]) in a mixture of dimethylformamide (DMF) and water with the addition of terephthalic acid (H₂Bdc) in the case of complex I or triethylamine for complex II. The compounds are characterized by X-ray diffraction analysis, IR spectroscopy, and thermogravimetric and elemental analyses. The luminescence spectra are also recorded. According to the X-ray diffraction data, the calcium atom is coordinated by the oxygen atoms of the cucurbit[6]uril molecule, water molecules, and terephthalate anion (for I). The internal cavity of the cavitand is occupied by DMF.     

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.     

(enH2)5[(VO)12O6B18O36(OH)6]·2(H3O)·6H2O的水热合成和晶体结构

以NH4VO3,H3BO3,乙二胺,MoO3,H2O为原料,按物质的量比2∶20∶9∶3∶222,在180℃条件下晶化,得到黑色棱形晶体(enH2)5[(VO)12O6B18O36(OH)6].2(H3O).6H2O.单晶结构分析结果表明该化合物属三斜晶系,Pī空间群,晶胞参数a=1.336 8(3)nm,b=1.599 8(3)nm,c=1.663 4(3)nm,α=94.040(1)°,β=91.530(1)°,γ=95.830(1)°,V=3.528 1(12)nm3,Z=2,Dc=2.099 g/cm3,μ=1.649 mm-1,F(000)=2 228,15 641个可观察独立衍射点射点(I>2σ(I)),最后结构精修到偏离因子R1=0.047 5,wR2=0.150 4,S=1.039.该化合物的结构主要由阴离子簇[(VO)12O6B18O36(OH)6]12-构成.该阴离子簇由B18O36(OH)6十八元环夹在两个以共边交替相连形成的V6O18簇中间,通过共用氧原子形成三明治式结构新颖的硼-钒-氧离子簇,簇间填充了一些(enH2)2+离子和水分子.     

Solid state structures of the chiral heterobimetallic complexes [Cu(dach)2][Pt(CN)4] · 2H2O, [Ni(dach)3][Pt(CN)4] · 2DMF · H2O,and [Pd(dach)2][Pt(CN)4] · H2O (dach = 1 R , 2 R -diaminocyclohexane)

The chiral dinuclear heterometallic complexes [Cu(dach)₂][Pt(CN)₄]?·?2H₂O (1), [Ni(dach)₃][Pt(CN)₄]?·?2DMF?·?H₂O (2), and [Pd(dach)₄][Pt(CN)₄]?·?H₂O (3) (dach?=?1R,2R-cyclohexanediamine) have been prepared and characterized by X-ray diffraction analysis. Crystal data: 1, monoclinic, P2₁, a?=?8.108(3), b?=?15.552(6), c?=?9.914(4)?Å, β?=?110.931(6)°, V?=?1167.6(8)?ų, Z?=?2, R ₁?=?0.0420, wR ₂?=?0.1122; 2, monoclinic, P2₁, a?=?13.264(11), b?=?9.285(7), c?=?16.211(13)?Å, β?=?111.640(9)°, V?=?1856(3)?ų, Z?=?2, R ₁?=?0.0276, wR ₂?=?0.0698; 3, monoclinic, P2₁, a?=?6.887(2), b?=?12.809(4), c?=?12.975(4)?Å, β?=?94.865(4)°, V?=?1140.6(6)?ų, Z?=?2, R ₁?=?0.057, wR ₂?=?0.156. In complex 1, the Pt and Cu atoms are linked by a CN bridge that presents a very bent C=N–Cu angle [136.8(8)°].     

New Layered Polymer [{Mn(H2O)3}2{Re6Se8(CN)6}] · 3.3H2O: Synthesis and Properties

The [{Mn(H₂O)₃}₂{Re₆Se₈(CN)₆}] · 3.3H₂O complex was produced on slow evaporation of an aqueous solution containing the salt of a cluster complex K₄Re₆Se₈(CN)₆ · 3.5H₂O and a 23-fold excess of Mn²⁺. The cluster complexes [Re₆Se₈(CN)₆]^4– are linked in a crystal into the charged coordination layers [{Mn(H₂O)₃}₄{Re₆Se₈(CN)₆}₃]^4– ₂ through the Mn²⁺ cations. The Mn²⁺ cations are coordinated in a layer by three cyano nitrogen atoms of the cluster complexes; the Mn–N bond lengths are 2.13(4) and 2.21(2) Å. Each [Re₆Se₈(CN)₆]^4– anion is bonded to three manganese cations Mn(1). The anions are bonded additionally to the Mn(2) cations disordered over two close positions.     

(NH4)(CN3H6)2[UO2(C2O4)2(NCS)] · 2H2O: Synthesis and crystal structure

A single-crystal X-ray diffraction study (NH₄)(CN₃H₆)₂[(UO₂(C₂O₄)₂(NCS)] · 2H₂O (I) was carried out. The crystals are orthorhombic, space group P2₁2₁2₁, Z = 4, with the unit cell parameters a = 6.668(2) Å, b = 13.463(4) Å, c = 23.086(6) Å. The main structural units of the crystals of I are insular complex anions [(UO₂)(C₂O₄)₂(NCS)]^3?. They belong to the crystal-chemical group AB ₂ ⁰¹ M¹ (A = UO ₂ ²⁺ ) of uranyl complexes and are linked into a three-dimensional framework through electrostatic interactions and hydrogen bonds with the participation of ammonium and guanidinium cations and crystal water molecules.     

Synthesis, crystal structure, and thermal stability of [Mo2O4(μ2-O)(C6H4O2)2(H2O)] · (C8H9N2)2 · 2H2O

From hydrothermal treatment of benzene-1,2-diamine, pyrocatechol, and MoO₃ in acetic acid solution, a new compound, [Mo₂(μ₂-O)₂(C₆H₄O₂)₂(H₂O)] · (C₈H₉N₂)₂ · 2H₂O (I), constructed from pyrocatechol chelated dinuclear molybdenum units and 2-methylbenzimidazole has been synthesized. Single-crystal structure analysis reveals that the compound crystallizes in the monoclinic space group P2₁/c with a = 23.365(2), b = 7.2214(5), c = 19.3021(16) β = 97.929(4), V = 3225.6(5), Z = 4, M = 808.46, ρ_c = 1.665 g/cm³, μ(MoK _α) = 0.84 mm^?1, F(000) = 1608, the final R = 0.0622 and wR = 0.1484 for 7385 independent reflections with R _int = 0.0393. Interestingly, an in situ condensation between acetic acid and benzene-1,2-diamine has occurred, and the unexpected 2-methyl-1-H-benzo[d] imidazoles serve as counterions and N-H donors to form stable hydrogen-bond network in the crystal. Furthermore, intermolecular hydrogen bonds are found among the cations, anions and crystalline water molecules. The double nuclear molybdenum units are connected by O-H...O hydrogen bonds with the crystalline water molecules to form one-dimensional chains, and the chains are further joined together by N-H...O to form a quasi-two dimensional structure.     

SYNTHESIS,CHARACTERIZATION, AND CRYSTAL STRUCTURE OF A NOVEL DECAVANADATE Mg(H2O)6(C6H14N2)2V10O28·8H2O

Journal of Structural Chemistry - A novel decavanadate salt Mg(H2O)6(C6H14N2)2V10O28·8H2O is obtained by the reaction of vanadium oxide and 1,4-diazabicyclo [2.2.2] octane (DABCO). The title...     

Structure of the complex [trans-SnF4(H2O)2· (18-crown-6)· 2H2O]

The molecular and crystal structure of the title complex (I) obtained by addition of tin fluoride in a hydrofluoric acid solution to 18-crown-6 in methanol was investigated by X-ray structure analysis. The crystals are monoclinic, space group P2₁/n, a = 13.497(3), b = 7.806(2), c = 9.892(2) Å, β = 95.57(3)°, Z = 2 for C₁₂H₃₂F₄O₁₀Sn. In the polymer chain, the crown ether molecules alternate with the inorganic complexes [trans-SnF₄(H₂O)₂] and are linked to them by O-H...O type hydrogen bonds involving the intermediate water molecules. The weak C-H...F interactions bind the chains into the layers which are parallel to the xz plane.     

Synthesis of calcium titanate from [Ca(H2O)3]2[Ti2(O2)2O(NC6H6O6)2]·2H2O as a cheap single-source precursor

Calcium titanate (CaTiO₃) was conveniently synthesized by thermal decomposition of a single-source precursor [Ca(H₂O)₃]₂[Ti₂(O₂)₂O(NC₆H₆O₆)₂]·2H₂O at low temperature. This single-source precursor was characterized by elemental analysis, IR spectrum, thermal gravimetric analysis and X-ray single crystal diffraction. The calcined products at different temperature were further characterized by powder X-ray diffractions and IR spectra. The morphology, microstructure, and crystallinity of the resulting CaTiO₃ materials have been characterized by SEM and TEM. The BET measurement revealed that the CaTiO₃ powders had a surface area of 14.0 m²/g. In addition, the microwave dielectric properties of the resulting CaTiO₃ material have been measured.     

Unique seven-node rare-earth octacyanomolybdate(IV) three-dimensional molecular frameworks: {[Er(H2O)5(Er(H2O)4)3][Mo(CN)8]3·11H2O}n and {[Eu(H2O)5(Eu(H2O)4)3][Mo(CN)8]3·11H2O}n

The crystal structure analyses of {[Er(H₂O)₅(Er(H₂O)₄)₃][Mo(CN)₈]₃·11H₂O}_n (1) and {[Eu(H₂O)₅(Eu(H₂O)₄)₃][Mo(CN)₈]₃·11H₂O}_n (2), show that they are not only new neutral three-dimensional rare-earth octacyanomolybdate(IV) molecular frameworks, but that they also belong to an unknown structure type having seven different nodes. To the best of our knowledge this is different to any other known molybdenum(IV) octacyanide complexes published to date. Both compounds crystallize in the triclinic system, space group P-1, and are isostructural and isotypic. The coordination polyhedra of the molybdenum atoms in the three different [Mo(CN)₈]⁴⁻ anions are trigonal prisms, with two additional atoms. A new bridging mode for octacyanometallates is also observed with five of the eight cyanide groups involved in bridging either three or four rare-earth atoms, while the three remaining cyanide groups are terminal and are involved in hydrogen bonding. The four rare-earth atoms in 1 and 2 have different coordination polyhedra in the form of trigonal prisms with two additional atoms. The three-dimensional structures are made up of infinite two-dimensional slabs linked by one of the rare-earth metal atoms. In both compounds, apart from the 17 coordinated water molecules, there are 11 lattice water molecules of crystallization present in the cavities of the three-dimensional frameworks. The 28 water molecules and the terminal CN⁻ groups are involved in an extensive O–H⋯O and O–H⋯N hydrogen bonding network.