Orientation of guest benzene molecules in Hofmann-type and related clathrates by molecular mechanics calculation

Molecular mechanics calculations were carried out to interpret the observed orientational angle of the benzene molecule enclathrated in the Hofmann-type M(NH₃)₂Ni(CN)₄·2 C₆H₆ (M = Mn, Ni, Cu, and Cd), Hofmann-en-type Cd(en)Ni(CN)₄·2 C₆H₆ (en = NH₂CH₂CH₂NH₂), and Hofmannmea-type(2) Cd(mea)Ni(CN)₄·2 C₆H₆ (mea = NH₂CH₂CH₂OH) clathrates using the van der Waals potential functions in Molecular Mechanics Version 2. The angle is most influenced by the guest-to-guest contact in the interlayer space between the two-dimensionalcatena-[metal(II) tetra--cyanonickelate(II)] networks for the Hofmann-type series. The discrepancy between the calculated and the observed angles in each crystal structure was at largest 3.5°; the structures of Cd(NH₃)₂Ni(CN)₄·2 C₆H₆ and Cd(en)Ni(CN)₄·2 C₆H₆ have been revised using new data collected by counter-methods.     

Dinuclear tetrapyridyl pendant-armed azamacrocyclic complexes of Co(II), Ni(II), Cu(II) and Cd(II)

The coordination capability of the new tetrapyridyl pendant-armed azamacrocyclic ligand L, towards Co(II), Ni(II), Cu(II) and Cd(II) ions was studied. The ligand and the complexes were characterized by microanalysis, LSI mass spectrometry, IR, UV-Vis and NMR spectroscopy, magnetic studies and conductivity measurements. Crystal structures of [Co₂L(CH₃CN)₂](ClO₄)₄·2CH₃CN and [Cd₂L(NO₃)₂](NO₃)₂·2H₂O complexes have been determined. The X-ray studies show the presence of dinuclear endomacrocyclic complexes with the metal ion in a similar distorted octahedral environment, coordinated by one pyridyl bridgehead group, two amine nitrogen atoms and two pyridyl pendant-arms. The sixth coordination position around the metal ion is completed by one acetonitrile molecule in [Co₂L(CH₃CN)₂](ClO₄)₄·2CH₃CN and by one monodentate nitrate anion in [Cd₂L(NO₃)₂](NO₃)₂·2H₂O. Different sort of intramolecular non-classical hydrogen bonds were found in the crystal lattice of both structures.     

Cubane Tellurido Clusters [Zn(NH3)4]3[Mo4Te4(CN)12] and [Cd(NH3)4]3[W4Te4(CN)12]: Syntheses and Crystal Structures

Single crystals of [Zn(NH₃)₄]₃[Mo₄Te₄(CN)₁₂] (I) and [Cd(NH₃)₄]₃[W₄Te₄(CN)₁₂] (II) were obtained by applying solutions of K₇[Mo₄Te₄(CN)₁₂] · 11H₂O and K₆[W₄Te₄(CN)₁₂] · 5H₂O in aqueous ammonia over solutions of ZnCl₂ and Cd(NO₃)₂ in glycerol and were characterized by X-ray diffraction analysis. The IR spectra and thermal properties of compounds I and II were examined.     

Preparation of CdS by thermal decomposition of double salts and saturated solutions of the systems Cd(HCOO)2-CS(NH2)2-CH3OH and Cd(CH3COO)2-CS(NH2)2-CH3OH

Summary The solubility isotherms of the systems Cd(HCOO)₂-CS(NH₂)₂-CH₃OH and Cd-(CH₃COO)₂-CS(NH₂)₂-CH₃OH have been investigated at 25°C. Reagents for the equilibrium existence of the salts Cd(HCOO)₂, Cd(HCOO)₂·2CS(NH₂)₂, CS(NH₂)₂, Cd(CH₃COO)₂, Cd(CH₃COO)₂·CS(NH₂)₂, and Cd(CH₃COO)₂·2CS(NH₂)₂ are found. The preparation of CdS by thermal decomposition of double salts and from saturated solutions by the dip technique are discussed.

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Herstellung von CdS durch thermische Zersetzung von Doppelsalzen und gesättigten Lösungen der Systeme Cd(HCOO)₂-CS(NH₂)₂-CH₃OH und Cd(CH₃COO)₂-CS(NH₂)₂-CH₃OH

Zusammenfassung Untersucht werden die Löslichkeitsisothermen der Systeme Cd(HCOO)₂-Cs(NH₂)₂-CH₃OH und Cd(CH₃COO)₂-CS(NH₂)₂-CH₃OH bei 25 °C. Die Kristallisationsfelder der Salze Cd(HCOO)₂, Cd(HCOO)₂·2CS(NH₂)₂, CS(NH₂)₂, Cd(CH₃COO)₂, Cd(CH₃COO)₂·CS(NH₂)₂ und Cd(CH₃COO)₂·2CS(NH₂)₂ werden bestimmt. Die Herstellung von CdS durch thermische Zersetzung von Doppelsalzen und gesättigten Lösungen anhand des Tauchverfahrens wird diskutiert.

     

Vibrational spectroscopic studies on the hofmann-Td-type clathrates: M(NH3)2M′(CN)4·2C6H6 (M=Mn or Cd and M′=Cd or Hg0

IR spectra of Mn(NH₃)₂M(CN)₄·2C₆H₆ (M=Cd or Hg), and IR and Raman spectra of Cd(NH₃)₂M(CN)₄·2C₆H₆ (M=Cd or Hg) are reported. The spectral data suggest that the former two compounds are similar in structure to the latter two Td-type clathrates.     

The crystal structures ofα,ω-diaminoalkane-cadmium(II) tetracyanonickelate(II) — Aromatic molecule inclusion compounds. VII: Three-dimensional host structures built ofcatena-[cadmium(II) tetra-μ-cyanonickelate(II)] layers and 1,3-diaminopropane, 1,5-diaminopentane or 1,7-diaminoheptane pillar

The crystal structures of four novel Hofmann-diam-type clathrates [Cd(tn)Ni(CN)₄]·1.72(o-MeC₆H₄NH₂),3-o, [Cd(tn)Ni(CN)₄]·0.5(m-ClC₆H₄NH₂),3-m, [Cd(daptn)Ni(CN)₄]·1.5(p-MeC₆H₄NH₂),5-p and [Cd(dahpn)Ni(CN)₄]·1.5(2-MeC₉H₆N),7-q have been determined by single crystal X-ray diffraction method [tn:n=3, daptn:n=5, dahpn:n=7 for NH₂(CH₂) _n NH₂.3-o crystallizes in the monoclinic space groupP2/m,a=7.538(2),b=9.314(5),c=7.670(2) Å, =91.03(2)°,Z=1,R=0.047 for 1252 reflections;3-m: orthorhombicPbam,a=12.1714(7),b=15.798(1),c=7.737(1) Å,Z=4,R=0.044 for 1871;5-p: monoclinicP2₁/a,a=13.736(3),b=22.014(4),c=7.762(3) Å, =91.04(3)°,Z=4,R=0.047 for 5281; and7-q: orthorhombicPbam,a=13.599(2),b=27.938(4),c=7.619(2) Å,Z=4,R=0.054 for 3098. Their host structures are topologically the same to those of the previously reported Hofmann-diam-type clathrates: the two-dimensional [CdNi(CN)₄] networks are spanned by NH₂(CH₂) _n NH₂ at every Cd atom to build up the three-dimensional hosts. The number of cavities available for the guest is regulated by the deformation of the 2D networks and the diamine ligand in the host structure. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82192 (37 pages).     

Synthese von Clathratverbindungen des Typs Cd(mea) m [Pd(CN)4] ·nG

The preparation, identification and some properties of three new clathrate compounds Cd(mea)[Pd(CN)₄] · 2C₆H₆, Cd(mea)₂[Pd(CN)₄] · C₄H₄S and Cd(mea)₂[Pd(CN)₄] · C₄H₄NH (mea = HO-CH₂-CH₂-NH₂) are described.

     

NEW THREE DIMENSIONAL [Cd(CN)2]n FRAMEWORK FORMED WITH CADMIUM CYANIDE AND Cd(CN)2·(18-CROWN-6): CRYSTAL STRUCTURE OF [Cd(CN)2]·1/2[Cd(CN)2 (18-CROWN-6)]·3/2EtOH+

Abstract

The cadmium complex Cd(CN)₂·(18-crown-6) (1) was synthesized and its structure was determined by X-ray crystallography. The cadmium ion in 1 has a hexagonal bipyramidal geometry containing six equatorial oxygen atoms from the crown ether and two axial CN ligands. The NC-Cd-CN ‘rod’ is perfectly linear with an end-to-end distance of 6.509 (12) Å. When 1 was allowed to diffuse into a cadmium cyanide solution, the infinite coordination complex [Cd(CN)₂]·1/2[(Cd(CN)₂·(18-crown-6)]·3/2EtOH (2) was obtained in which the cadmium macrocycle 1 was trapped in a 10-faced-cage formed by the [Cd(CN)₂]n framework. The terminal nitrogen atoms of 1 bind two Cd centers across the cage. The trapped Cd(CN)₂·(18-crown-6) has a significantly bent NC-Cd-CN unit and the crown ether ligand disordered over two orientations. The [Cd(CN)₂]_n framework viewed down the c axis shows two types of channels, one octagonal and one tetragonal, which are filled with Cd(CN)₂·(18-crown-6) and ethanol molecules, respectively. Crystallographic data of 1: trigonal, space group R·3 (hexagonal axis), a = 11.757 (1), c = 12.105 (1) Å, V = 1449.1 (2) ų, Z = 3, R = 0.0566, R_w = 0.0674 for 827 unique reflections (I>3σ(I)). Crystallographic data of 2: orthorhombic, Pbcn, a = 16.632 (1), b = 17.391 (3), c = 15.685 (2) Å, V = 4536.8 (9) ų, Z = 8. R = 0.0486, R_w = 0.0492 for 929 unique reflections (I>3σ(I)).     

Darstellung und Röntgenstrukturanalyse von 26 Thiomolybdato- bzw. Thiowolframato-und eines Selenowolframato-Komplexes

Summary The preparation and characterization by X-ray structure analysis of the following chalcogenometalato complexes are reported: 1: [(Ph ₃P)₂N]₂(NEt ₄)[Fe(WS₄)₂]·2MeCN; 2: [(Ph ₃P)₂N]₂(NEt ₄)[Cu(WS₄)₂]·2MeCN; 3: [(Ph ₃P)₂N]₂(NEt ₄)[Ag(MoS₄)₂]·MeCN; 4: [(Ph ₃P)₂N]₂(NEt ₄)[Ag(WS₄)₂]·MeCN; 5: (PPh ₄)₂[Hg(WS₄)₂]; 6: (PPh ₄)₂[Au₂(WOS₃)₂]; 7: (PPh ₄)₄[Pb₂(MoS₄)₄]; 8: (PPh ₄)₄[Pb₂(WS₄)₄]; 9: (NEt ₄)₂[Fe(WS₄)₂(H₂O)₂]; 10: [Fe(DMSO)₆][Cl₂Fe(MoS₄)]; 11: [Fe(DMSO)₆][Cl₂Fe(MoOS₃)]; 12: (PPh ₄)(NMe ₃CH₂ Ph)[Cl₂Fe(WS₄)]; 13: [Fe(DMF)₆][Cl₂Fe(WS₄)]; 14: (PPh ₄)₂[Cl₂Fe(WS₄)]; 15: (PPh ₄)₂[Cl₂Fe(WS₄)]·2 CH₂Cl₂; 16: (PPh ₄)₂[NCCu(MoS₄)]; 17: (PPh ₄)₂[NCAg(MoS₄)]; 18: (PPh ₄)₂[NCAg(WS₄)]; 19: (PPh ₄)₂[Cu₃Cl₃(MoOS₃)]; 20: (PPh ₄)₂[Cu₃Br₃(MoS₄)]·MeCN; 21: (PPh ₃)₃Cu₂(MoOS₃)·0.8 CH₂Cl₂; 22: (PPh ₃)₃Cu₂(WOS₃)·0.8 CH₂Cl₂; 23: {Cu₃MoS₃Br}(PPh ₃)₃O·0.5Me ₂CO; 24: (PPh ₃)₃Ag₂(WSe₄)·0.8 CH₂Cl₂; 25: [(Ph ₃P)₂N]₂(NEt ₄)₂[Fe₂S₂(WS₄)₂]·3MeCN; 26: (PPh ₄)₂[MoO(MoS₄)₂]; 27: (PPh ₄)₂[Br₂Fe(WOS₄)]·DMF.

     

Supramolecular framework adducts constructed of hexamethylenetetramine,aquated alkali metal cationic clusters,and hexacyanoferrates(II/III)

The reaction of alkali metal hexacyanoferrate(II/III) with (CH₂)₆N₄ (hexamethylenetetramine, abbreviated HMT) in an acidic medium yielded crystalline compounds of stoichiometries HK₂[Fe¹¹¹(CN)₆]·2HMT·4H₂O, H₂K₂[Fe¹¹(CN)₆]·2HMT·4H₂O, and HNa₂[Fe¹¹¹(CN)₆]· 2HMT·5H₂O. Their crystal structures are based on a packing of three molecular components: neutral and/orprotonated HMT, hexacyanoferrate, and an alkali metal ion-water cluster. The resulting three-dimensional supramolecular framework is constructed from the coordination of the alkali metal ion by aqua ligands as well as [Fe(CN)₆]{n–} and HMT units, and further stabilization is achieved by hydrogen bonding between water molecules and the noncoordinated nitrogen atoms of HMT and hexacyanoferrate.     

Neutral solvent/crown ether interactions, 4. Crystallization and low temperature (−150°C) structural characterization of 18-crown-6 · 2(CH3CN)

The crystal structure of 18-crown-6 · 2(CH₃CN) has been determined via data collection at –150°C. The structure consists of two crown molecules each hydrogen bonded to two acetonitrile moieties in the asymmetric unit, each residing around a center of inversion. The crown ethers display their fullD _3d symmetry; methyl ... O contacts range from 3.189(8) to 3.598(8) Å. There are no close contacts indicative of any interaction between the crown/2(CH₃CN) units. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82056 (14 pages).For Part 3, see reference [1]     

Fluordiazadiphosphetidine, 20. Mitt. Die Dehydrofluorierung zwitterionischer und die Hydrofluorierung neutraler,hydrazinsubstituierter Fluordiazadiphosphetidine

In the presence ofEt ₃N·PF₅, F₄P^–(CH₃N)₂PF₂NHNH⁺(CH₃)₂ (I) looses one molecule of HF to yield F₃P(CH₃N)₂PF₂NHN(CH₃)₂ (II). The reaction ofI withDABCO (1,4-diazabicyclo[2.2.2]octane) yieldsDABCO·2H⁺⁺(CH₃NPF₄) ₂ ^–– (III) and [CH₃NPF₂NHN(CH₃)₂]₂ (IV). Even in the presence of CsF,II does not react with HF.

     

Syntheses,structures and luminescent properties of four d-metal coordination polymers based on the 2,4,5-tri(4-pyridyl)-imidazole ligand

Four d¹⁰-metal coordination polymers based on the 2,4,5-tri(4-pyridyl)-imidazole ligand (Htpim), {[Zn₂(Htpim)₄Cl₄] · 8H₂O}_n (1), {[Cd(tpim)₂(H₂O)₂] · 4CH₃OH}_n (2), {[Cu₂(Htpim)(PPh₃)₂I₂] · CH₃CN}_n (3) and {[Ag(Htpim)](NO₃) · CH₂Cl₂}_n (4), have been synthesized and characterized by elemental analyses, IR, thermogravimetric and X-ray structural analyses. Both complexes 1 and 2 show one dimensional ribbon-like structures. Via intermolecular hydrogen bonds, a 2D supramolecular network and 3D framework are formed for 1 and 2, respectively. Complex 3 shows a 1D zigzag chain with a CuI₂Cu rhomboid dimer. Complex 4 shows a 1D ladder-like polymer with two different metallacycles. The luminescent properties of all the complexes have been studied in the solid state.     

Das Thermische Verhalten von Na3[Fe(CN)5SO(CH3)2] · H2O

The thermal behaviour of Na₃ [Fe(CN)₅SO(CH₃)₂] · 2H₂O has been investigated by thermogravimetry and diferential thermal analysis. The results are briefly discussed.     

Complex Formation of Potassium Hexachloroplatinate with 18-Crown-6 and Dibenzo-18-Crown-6 in Acetonitrile

The products of the reactions between potassium hexachloroplatinate {K₂PtCl₆} and 18-crown-6 or dibenzo-18-crown-6 in acetonitrile were studied. Pure crystalline compounds [2K·2(18-crown-6)· 2CH₃CN]²⁺·[PtCl₆]^2-·2H₂O, [2K·dibenzo-18-crown-6·CH₃CN]^{2 +}·[PtCl₆]^{2 -}, and [2K·dibenzo-18-crown-6·CH₃CN]^{2 +}·[Pt₂Cl₁₀]^{2 -} were obtained. Physicochemical properties of these compounds were studied, and their near- and far-IR IR spectra and thermogravimetric curves were considered. The composition of the complexes is determined by metal:ligand molar ratio and crown ether nature. It was found that acetonitrile is coordinated via the nitrogen atom.     

Ligand substitution in the cluster complex [Mo3S7Cl6]2?: Synthesis and crystal structure of (Et4N)[Mo3S7Cl5(CH3CN)]

The crystal structure of the new cluster complex (Et₄N)₂[Mo₃S₇Cl₆] · CH₃CN · H₂O (I) was determined. Heating of a solution of I in CH₃CN under solvothermal conditions (120°C) induces replacement of one Cl⁻ ligand by CH₃CN to give (Et₄N)[Mo₃S₇Cl₅(CH₃CN)] (II). The product was also studied by X-ray diffraction analysis.     

The properties of tetracyanocomplexes after contact with ethyl alcohol

The clathrates Cd(NH₃)₂ Ni(CN)₄·2C₆H₆ (1) and Cd(en) Ni(CN)₄·2C₆H₆ (2) have been studied as separative materials for the separation of mixtures of alkanes, of benzene and its derivatives, and of the chloroderivatives of methane and pyridine.By identifying the chromatographically active solid form we could observe on the basis of the IR spectra and the thermal analysis that the ethylalcohol after contact with clathrate (1) substituted one mole of benzene. Clathrate (2) was not affected by the action of ethylalcohol. The facts agree with the interactions existing between the tetracyanocomplexes and the sorbates.     

Four mono-/bi-nuclear palladium(II) complexes of triphenylphosphine and heterocyclic-N/NS ligands: Synthesis, structural characterization and luminescence properties

The reactions of palladium(II) chloride, PPh₃ and heterocyclic-N/NS ligand in a mixture of CH₃CN (5 ml) and CH₃OH (5 ml) produced [PdCl₂(PPh₃)(L1)]·(CH₃CN) (1) (L1 = ADMT = 3-amino-5,6-dimethyl-1,2,4-triazine), [PdCl₂(PPh₃)(L2)] (2) (L2 = 3-CNpy = 3-cyanopyridine), [PdCl(PPh₃)(L3)]₂·(CH₃CN) (3), [PdCl(PPh₃)₂(HL3)]Cl (4) (HL3 = Hmbt = 2-mercaptobenzothiazole). The coordination geometry around the Pd atoms in these complexes is a distorted square plane. In 3, L3 acts as a bidentate ligand, bridging two metal centers, while in 4, HL3 appears as monodentate ligand with one nitrogen donor atom uncoordinated. Complexes 1-4 are characterized by IR, luminescence, NMR and single crystal X-ray diffraction analysis. All complexes exhibit luminescence in solid state at room temperature.     

Organosilicon Amine Gels Based on 3-Aminopropyltriethoxysilane, Cobalt(II) or Chromium(III) Clorides, and Triethoxysilane

Organosilicon gels [Co(NH₂R²)₂Cl₂] and [Cr(NH₂R²)₃Cl₃], containing a diaminodichloride complex of cobalt(II) and triaminotrichloride complex of chromium(III) (R² = CH₂CH₂CH₂SiO(OEt)), were synthesized by the hydrolysis of complexes [Co(NH₂R¹)₂Cl₂] (I) and [Cr(NH₂R¹)₃Cl₃] (II) incorporating peripheral triethoxysilyl groups (R¹ = CH₂CH₂CH₂Si(OEt)₃). The coprecipitated [Co(NH₂R²)₂Cl₂] · 4NH₂R³, [Cr(NH₂R²)₃Cl₃] · 6NH₂R³, [Co(NH₂R²)₂Cl₂] · 2SiO₂, and [Cr(NH₂R²)₃Cl₃] ·xSiO₂ · (3 – x)SiHO_1.5 (R³ = CH₂CH₂CH₂SiO_1.5) gels were obtained by cohydrolysis of complexes I and II with 3-aminopropyltriethoxysilane or triethoxysilane. Interaction with SiH(OEt)₃ is accompanied by the decomposition of silicon hydride groups and the formation of tetraethoxysilane derivatives. The heating of dry gels in a flow of argon or oxygen to 600° results in the formation of amorphous silica having a specific surface area 2–467 m²/g and containing crystalline metals, their chlorides, oxides, silicates, or carbides.     

Uranyl carboxyphosphonates that incorporate Cd(II)

The hydrothermal treatment of UO₃, Cd(CH₃CO₂)₂·2H₂O, and triethyl phosphonoacetate results in the formation of Cd₂[(UO₂)₆(PO₃CH₂CO₂)₃O₃(OH)(H₂O)₂]·16H₂O (CdUPAA-1), [Cd₃(UO₂)₆(PO₃CH₂CO₂)₆(H₂O)₁₃]·6H₂O (CdUPAA-2), and Cd(H₂O)₂[(UO₂)(PO₃CH₂CO₂)(H₂O)]₂ (CdUPAA-3). CdUPAA-1 adopts a cubic three-dimensional structure constructed from planar uranyl oxide clusters containing both UO₇ pentagonal bipyramids and UO₈ hexagonal bipyramids that are linked by Cd(II) cations and phosphonoacetate to yield large cavities approximately 16 Å across that are filled with disordered water molecules. CdUPAA-2 forms a rhombohedral three-dimensional channel structure that is assembled from UO₇ pentagonal bipyramids that are bridged by phosphonoacetate. CdUPAA-3 is layered with the hydrated Cd(II) cations incorporated directly into the layers linking one-dimensional uranyl phosphonate substructures together. In this structure, there are complex networks of hydrogen bonds that exist within the sheets, and also stitch the sheets together.