Phenol as a guest molecule in clathrate compounds

Phenol, having favourable physical and chemical properties, can be enclosed as the guest component in the clathrates of tetracyano complexes. Six compounds of Hofmann and similar type clathrates M(NH₃)₂M' (CN)₄.nG and M(en)_m M'(CN)₄.nG were prepared and identified: Ni(NH₃)₂Pt.2C₆H₅OH; Ni(en)₂Pt(CN)₄.O.14C₆H₅OH; Ni(NH₃)₂Pt(CN)₄.C₆H₅OH.H₂O; Zn(NH₃)₂Ni(CN)₄.O.1C₆H₅OH.H₂O; Cu(NH₃)₂Ni(CN)₄. 2C₆H₅OH and Fe(NH₃)₂Ni(CN)₄.2C₆H₅OH. The phenol containing clathrates are more stable than clathrates containing other guest molecules. In the case of Ni(en)₂ Pt(CN)₄.O.14C₆H₅OH thermal loss of the guest molecule leaves the host lattice intact, but further heating results in the rupture of the host lattice. The compounds were capable in the solid state of sorbing other organic molecules once they had been heated to the temperature required for almost complete loss of guest molecule i.e. n→o.     

Hydration reaction of Hofmann's benzene clathrate,diamminenickel(II) tetracyanonickelate(II)-benzene-(1/2), suspended in aqueous media

Hofmann's benzene clathrate Ni(NH₃)₂Ni(CN)₄·2C₆H₆ suspended in ammoniacal, neutral, and acidic aqueous media undergoes the replacement reactions of the guest C₆H₆ and the ligating NH₃ molecules with molecules of water to give Ni(NH₃)₂Ni(CN)₄·?1H₂O, Ni(H₂O)₂Ni(CN)₄·nH₂O(0<n<2), and Ni(H₂O)₂Ni(CN)₄·4～5H₂O, respectively. The integrity of the host metal complex sheet structure is conserved with little change during the replacement reactions.     

Clathrate and inclusion compounds: Part V. An infrared and Raman study of the decomposition of the Hofmann aniline clathrates M(NH3)2Ni(CN)4.2C6H5NH2 {M = Cd(II) and Ni(II)}

The time-dependent changes which are observed in the infrared and Raman spectra of samples of the two Hofmann aniline clathrates M(NH₃)₂Ni(CN)₄.an₂ {M = Cd(II), Ni(II), an = C₆H₅NH₂} indicate the occurrence of a solid state ligand replacement reaction in which the aniline guest molecule replaces the coordinated ammonia to give Man₂Ni(CN)₄ as the final product. The rate of replacement is greater for the cadmium than for the nickel clathrate, and for both clathrates evacuation of the sample greatly increases the rate of replacement. The Man₂Ni(CN)₄ complexes can themselves act as host lattices forming clathrates containing guest molecules such as aniline.     

Infrared Spectroscopic Study on the Hofmann Td-Type Clathrates: Mn(NH3)2M(CN)4·2 C6H5NH2 (M = Zn, Cd or Hg)

Infrared spectra of Mn(NH₃)₂M(CN)₄·2C₆H₅NH₂ (M = Zn, Cd or Hg) are reported. The spectral data suggest that these compounds are similar in structure to Hofmann-T_d-type clathrates.     

Infrared Spectroscopic Study on the Hofmann-dadn-type and the Td-dahxn-type clathrates

Infrared spectra of M(1,10-diaminodecane)Ni(CN)₄ · 1,5 G (M=Co, Ni or Cd; G=o-xylene, m-xylene, p-xylene) and Cd(l,6-diaminohexane)M(CN)₄ · C₆H₆ (M=Cd or Hg) clathrates are reported. The 1,10-diaminodecane and 1,6-diaminohexane molecules in the host permit the inclusion of bulky guest molecules. The spectral data of clathrates were compared with those of the corresponding host. The spectral features suggest that these compounds are similar in structure to other Hofmann-type and Hofmann-T_d type clathrates, respectively.     

Vibrational spectroscopic studies of some dimethylpyrazine cadmium (II) tetracyanonickelate benzene clathrates: [Cd(C6H8N2)Ni(CN)4]·C6H6

Two new cadmium dimethylpyrazine (2,3-dimethylpyrazine or 2,5-dimethylpyrazine) tetracyanonickelate benzene clathrates, [Cd(C₆H₈N₂)Ni(CN)₄]·C₆H₆, have been prepared in powder form and characterized by FT-IR spectroscopy, Raman spectroscopy, X-ray diffraction, thermal analyses and elemental analyses. Vibrational assignments are proposed for the bands of the host lattice and guest molecule. It is shown that the spectra are consistent with a proposed crystal structure for these compounds derived from X-ray diffraction measurements. The C, H, N, Cd and Ni analyses were carried out for all the compounds. Thermal behaviors of these compounds are followed using TG and DTA techniques. The FT-IR, Raman spectroscopic, XRD, thermal and elemental analyses results propose that these compounds are similar in structure to the Hofmann-type clathrates. Their structure consists of planar polymeric layers, {M–Ni(CN)₄}_∞, formed from Ni(CN)₄ anions coordinated to the bridging 2,3- or 2,5-dimethylpyrazine molecules bound directly to the cadmium. The cadmium atoms are bound to four N atoms of the CN ions and, the Ni atoms are surrounded by four C atoms of the CN groups in a square-planar layer.     

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.     

Infrared spectroscopic studies of some piperidine metal(II) clathrates: M(C5H11N)2Ni(CN)4·G (M = Co,Ni; G = m-xylene,p-xylene or o-xylene; M = Ni; G = dioxane)

IR spectra of M(C₅H₁₁N)₂Ni(CN)₄·G (M=Co, Ni; G=o-, m- or p-xylene; M=Ni; G=dioxane) are reported. These clathrates are analogues to the previously reported classical Hofmann-type clathrates.     

Mixed and partial oxidation states. Photoelectron spectroscopic evidence

X-ray photoelectron spectra of the single valence platinum complexes K₂[Pt(CN)₄] · 3H₂O(1),K₂[Pt(CN)₄]Cl_0.3 · n H₂O(2) and K₂[Pt(CN)₄]Cl₂ · 3H₂O(3) and the mixed valence compound [Pt^II(C₂H₅NH₂)₄]Cl₄ · [Pt^IV (C₂H₅NH₂)₄Cl₂] · 4H₂O(4) have been measured. It is found that one can distinguish clearly between mixed and single valence compounds by electron spectroscopy. The Pt spectrum of (4) is a superposition of a Pt^II and Pt_IV spectrum. The chemical shift between (1) and (3) is normal, however (2) shows an anomalous low binding energy for the Pt 4f electrons. The importance of using reliable reference peaks for obtaining absolute binding energies is emphasized.     

Die Elektronen- und Infrarotspektren von Hydraten und Clathraten des Nickelcyanids

The infrared and diffuse reflectance spectra in the visible and ultraviolet region of the following compounds have been measured: Ni(CN)₂, 2 H₂O, Ni(CN)₂, 1½ H₂O, Ni(CN)₂, NH₃, ¼ H₂O, Ni(CN)₂, NH₃, R (R = C₆H₆, C₆H₅NH₂, C₆H₅OH). The structural units of these compounds are shown to be the square planar [NiC₄] and the pseudo-octahedral [NiN₄L₂]-group (L = H₂O, NH₃) with Ni-C-N-Ni-bridges. Additional water is present as zeolitic water. The magnetic data give a 1:1 relation of the paramagnetic pseudo-octahedral to the diamagnetic square planar co-ordination polyhedra. The nitrogen of the cyanide ion is close to ammonia in the spectrochemical as well as in the nephelauxetic series, the values of Dq and B being ?1000 and ?900 cm^?1 respectively. The absorption bands of the aromatic molecules in the clathrates are shifted towards lower wave numbers compared to the corresponding solution spectra.     

Crystal structures ofcatena-[diligatocadmium(II) tetra-μ-cyanocadmate(II)] host clathrates: Diamminecadmium(II) tetracyanocadmate(II)-benzene(1/2), diamminecadmium(II) tetracyanocadmate(II)-aniline(1/2), ethylenediaminecadmium(II) tetracyanocadmate(II)-aniline(1/2), and a novel type bis(aniline)cadmium(II) tetracyanocadmate(II)-aniline(2/1)

The crystal structures of the four title clathrate compounds Cd(NH₃)₂Cd(CN)₄ · 2C₆H₆,I, Cd(NH₃)₂Cd(CN)₄ · 2C₆H₅NH₂,II, Cd(NH₂CH₂CH₂NH₂)Cd(CN)₄ · 2 C₆H₅NH₂,III, and Cd(C₆H₅NH₂)₂Cd(CN)₄ · 0.5C₆H₅NH₂,IV, have been analyzed by single crystal X-ray diffraction methods. CompoundI crystallizes in the monoclinic space groupC2/c,a = 12.063(2),b = 12.174(2),c = 14.621(1) Å,β = 90.976(9)°,Z = 4,R = 0.042 for 2388 reflections;II: monoclinic C₂/c,a = 12.1951(9),b = 12.078(1),c = 14.6921(7) Å,β = 93.436(5)°,Z = 4,R = 0.039 for 2374 reflections;III: monoclinicCc,a = 11.027(1),b = 12.0767(9),c = 15.837(1) Å,β = 92.059(9)°,Z = 4,R = 0.041 for 2883 reflections; andIV: monoclinicP2₁/n,a = 15.169(2),b = 16.019(2),c = 8.866(1) Å,β = 95.73(1)°,Z = 4,R = 0.052 for 3612 reflections. The three-dimensionalcatena-[diamminecadmium(II) tetra-μ-cyanocadmate(II)] hosts ofI andII are substantially isostructural to that of the already known Hofmann-Td-type Cd(NH₃)₂Hg(CN)₄ · 2C₆H₆. The three-dimensional en-Td-typecatena-[catena-μ-ethylenediaminecadmium(II) tetra-μ-cyanocadmate(II)] host ofIII, reinforced by the catena-μ-en linking between the octahedral Cd atoms, accommodates the aniline as the guest with a monoclinic distortion from the tetragonal symmetry of the previously reported en-Td-type benzene clathrate. InIV dual behavior of aniline, one as the unidentate ligand in the three-dimensional host and the other as the guest in the cage-like cavity, has been demonstrated.     

Coordination compounds of cobalt, nickel, copper and zinc with thiosemicarbazone and 3-phenylpropenal semicarbazone

Hydrates of 3-phenylpropenal thiosemicarbazone (HL·H₂O) and semicarbazone (HL′·H₂O) react in methanol with cobalt, nickel, copper, and zinc chlorides, nitrates, and acetates to form coordination compounds MX₂·2HL·nSolv [M = Co, Ni, Cu, Zn; X = Cl, NO₃; HL = C₆H₅CH=CH-CH=N-NHC(O)NH₂; n = 0–3; Solv = H₂O, CH₃OH], CuX₂·HL·nH₂O [M = Ni, Cu; n = 0, 1], ML₂·nH₂O and ML′·nH₂O [M = Co, Ni, Zn; HL′ = C₆H₅CH=CH-CH=N-NHC(O)NH₂; n = 0–3]. In the presence of amines (A = C₅H₅N, 2-CH₃C₅H₄N, 3-CH₃C₅H₄N, and 4-CH₃C₅H₄N) these reactions yield the complexes Cu(A)LCl·CH₃OH and M(A)LX·nH₂O [M = Cu, Ni; X = Cl, NO₃; n = 0–2]. The copper complexes with the amine ligands are of polynuclear structure, and other complexes are monomeric. Carbazones (HL and HL′) are included in the complexes as bidentate N,S-and N,O-ligands. The thermolysis of the complexes involves the stages of removing solvent crystallization molecules (70–90°C), deaquation (150–170°C), and full thermal decomposition (500–580°C).     

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.     

Synthesis,spectroscopic, thermal,crystal structure properties and characterization of new Hofmann-type-like clathrates with 4-aminopyridine and water

In this study, synthesis of two new heteronuclear tetracyanonickelate(II) clathrates based on 4-aminopyridine (4AP) and guest water (H₂O) molecule and investigation of their structural properties were reported. These clathrates were characterized by using vibration spectroscopy, elemental, thermal analysis and single crystal X-ray diffraction (SC-XRD) techniques. Examining the elemental and spectral data of these clathrates, it was observed that the formulas [Zn(II)(4AP)₂Ni(µ-CN)₂(CN)₂]·6H₂O and [Cu(II)(4AP)₄Ni(µ-CN)₂(CN)₂]·H₂O were defined their structures. General information about the structural properties of these clathrates in single crystal form has been obtained by considering the changes in the characteristic peaks of the cyanide group and the 4AP that formed them. The thermal behaviors of these clathrates were obtained by examining the temperature-dependent changes of their masses. The magnetic susceptibilities of these clathrates in single crystal form were measured with a Gouy balance. According to the data obtained using SC-XRD technique, the heterometallic [Zn(II)(4AP)₂Ni(µ-CN)₂(CN)₂]·6H₂O compound has Cmcm and the heterometallic [Cu(II)(4AP)₄Ni(µ-CN)₂(CN)₂]·H₂O compound has crystal structures in the C2 / c space group.     

Synthese von Tetracyanoniccolat-clathraten mit Benzol Kurze Mitteilung

Zusammenfassung Durch Ersetzung des Cadmiums im Clathrat Cden[Ni(CN)₄]·2C₆H₆ wurden drei Verbindungen des TypsM(en) _m[Ni(CN)₄]·nC₆H₆ (M ²⁺=Ni, Cu, Zn;m=2–3;n=0.14–0.28) hergestellt und charakterisiert.

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Synthesis of ethylendiamine-(metal II)-tetracyanoniccolate dibenzene clathrate compounds

Replacing cadmium ion in Cden[Ni(CN)₄]·2C₆H₆ clathrate compound three compounds ofM(en) _m[Ni(CN)₄]·nC₆H₆ type (M ²⁺=Ni, Cu, Zn;m=2–3;n=0.14–0.28) were prepared and characterized.

     

Study of the solubility of components in the system Mg(ClO3)2-2NH2C2H4OH · H3C6H5O7-H2O

The solubility of components in the system Mg(ClO₃)₂-2NH₂C₂H₄OH · H₃C₆H₅O₇-H₂O was studied from the complete freezing temperature ?59.4°C to 20.0°C. A polythermal solubility diagram was constructed, in which the crystallization fields were determined for ice, Mg(ClO₃)₂ · 16H₂O, Mg(ClO₃)₂ · 12H₂O, Mg(ClO₃)₂ · 6H₂O, 2NH₂C₂H₄OH · H₃C₆H₅O₇ · H₂O, 2NH₂C₂H₄OH · H₃C₆H₅O₇, and two new compounds, [(HOC(CH₂COOH)₂COO)₂Mg · 2H₂O] and [HOC(CH₂COO)₂MgCOOH · 2H₂O], which were identified by chemical and physicochemical analysis methods.     

Synthesis,Characterization and Thermal Decompositions Studies of Some Malates Coordination CompoundsI. iron nickel compounds

The thermal behaviour of three coordination compounds, potential precursors of nickel ferrite [Fe₂Ni(C₄H₄O₅)_2.5(OH)₂]NO₃·5H₂O,[Fe₂Ni(C₄H₈O₃N₂)₄](NO₃)₈·24H₂O and (NH₄)[Fe₂Ni(C₄H₄O₅)₃(OH)₃]·3H₂O has been investigated to evaluate their suitability as precursors for nickel ferrite. For a complete and reliable assignment of the thermal transformations, the isolable solid intermediates and end products were characterized by IR, X-ray diffraction and Mössbauer investigations. A decomposition scheme is proposed.     

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.     

An infrared spectroscopic study of dianiline-metal(ii) tetracyanometalate complexes

The results of an IR spectroscopie study are presented for six new dianiline metal tetracyanometalate complexes, M(an)₂M'(CN)₄ (M = Mn, Fe, Co or Cu and M'= Ni; M = Ni or Cd and M' = Pt; an = aniline). Their structure consists of polymeric layers of (M-M'(CN)₄)∞ with the aniline molecules bound directly to metal (M). For these series of isomorphous complexes there is a correlation between the shifts of some aniline bands on coordination and the strength of metal-nitrogen bonding measured by the v(M-N) value. Low temperature (83 K) data are also reported and it is noted that whilst the aniline ring and CH mode frequencies are virtually insensitive to temperature, the NH₂ wagging, NH₂ rocking and the metal-ligand stretching v(M-N) frequencies increase with decreasing temperature, whilst the v(NH₂) modes decrease with decreasing temperature. The vibrational frequencies of the M'(CN)₄ group are also temperature dependent and increase in value upon cooling the sample to 83 K. The changes are thought to be due to a slight contraction in the cavity size with decreasing temperature. The relationship between these complexes and Hofmann-type aniline clathrates, M(NH₃)₂M'(CN)₄ · 2 an, is indicated.     

Cyano-bridged complexes based on re tetrahedral cluster anions, Ni2+ cations, and polydentate amines

Interaction of the tetrahedral chalcocyanide cluster anionic complexes of Re, K₄[Re₄Q₄(CN)₁₂] (Q=S, Se, Te), with Ni²⁺ cationic complexes with polydentate amines, such as ethylenediamine (En), diethylenetriamine (Dien), or triethylenetetraamine (Trien) was used to synthesize six novel complexes: [Ni(NH₃)₄(En)][{Ni(NH₃)(En)₂}Re₄Te₄(CN)₁₂] · 2H₂O, [{Ni(En)₂}₂Re₄Se₄(CN)₁₂] · 3.5H₂O, [Ni(NH₃)₃(Dien)]₂[Re₄Se₄(CN)₁₂] · 5.5H₂O, [{Ni(NH₃)₂(Dien)}₂Re₄Te₄(CN)₁₂] · 2.5H₂O. [Ni(NH₃)₂(Trien)][{Ni(NH₃)(Trien)}Re₄Se₄(CN)₁₂] · 2.5H₂O, [{Ni(Trien)}₂Re₄S₄(CN)₁₂] · 3H₂O. The complexes were studied by single-crystal X-ray diffraction analysis.