Chemisorptive Synthesis,Self-Assembly of Complicated 2D and 3D Supramolecular Architectures (Role of Hydrogen Bonds and Secondary Interactions Au···S and S···Cl), and Thermal Behavior of Pseudo-Polymeric Gold(III)–Mercury(II) Dibutyldithiocarbamato-Chlorido Complexes

Russian Journal of Coordination Chemistry - The interaction of mercury(II) dibutyl dithiocarbamate (BuDtc) with [AuCl4]? anions in 2 M HCl was studied. The heterogeneous reaction of...     

Hexanuclear Silver(I) Hexamethylene Dithiocarbamate Cluster [Ag6{S2CN(CH2)6}6]·2CH2Cl2: Preparation,Molecular Structure (Manifestation of Argentophilic Interaction), and Thermal Behavior

Russian Journal of General Chemistry - A new silver(I) cyclohexamethylene dithiocarbamate has been isolated in the form of a hexanuclear solvated cluster [Ag6{S2CN(CH2)6}6]·2CH2Cl2. Structure...     

Synthesis,Molecular Structure,and Thermal Properties of the Supramolecular Complex [Zn{NH(CH2)4O}{S2CN(C2H5)2}2]2 · CH2N(CH2)4O}2

The supramolecular complex [Zn{NH(CH₂)₄O}{S₂CN(C₂H₅)₂}₂]₂ · CH₂N(CH₂)₄O}₂ (I) has been synthesized and studied by X-ray crystallography and thermal analysis. The noncentrosymmetric complex is composed of two structurally nonequivalent molecules of the adduct of bis(diethyldithiocarbamato)zinc with morpholine, which are linked with the outer-sphere N,N’-dimorpholinomethane molecule through two hydrogen bonds N-H?O. The major differences between the adduct molecules are related to the strength of Zn-N bonds, spatial orientation of the coordinated morpholine heterocyclic rings, and the proportion between the contributions of the trigonal bipyramidal (TBP) and tetragonal pyramidal (TP) components to the geometry of zinc polyhedra. Calculations show that the geometry of the zinc polyhedra is almost halfway between TBP and TP. The thermal destruction of supramolecular compound I is accompanied by desorption of the outer-sphere and coordinated organic molecules. At the final stage, defragmentation of the “dithiocarbamate part” of the complex leads to the formation of ZnS.     

Chemisorption Synthesis of the Ion-Polymeric Heteronuclear Gold(III)–Bismuth(III) Complex ([Au{S2CN(C3H7)2}2]3[Bi2Cl9])n Based on [Bi2{S2CN(C3H7)2}6]: 13C MAS NMR,Supramolecular Structure,and Thermal Behavior

Russian Journal of Coordination Chemistry - Chemisorption synthesis on the basis of the binuclear compound [Bi2{S2CN(C3H7)2}6] (I) and preparative isolation of the ion-polymeric heteronuclear...     

Platinum(II) cyclo-hexamethylenedithiocarbamate complex, [Pt{S2CN(CH2)6}2] and its solvated form, [Pt{S2CN(CH2)6}2] · CHCl3: Crystal and molecular structures, 13C CP/MAS NMR data, and thermal behavior

Platinum(II) cyclo-hexamethylenedithiocarbamate (HmDtc) complex, [Pt{S₂CN(CH₂)₆}₂] (I), and its solvated form, Pt{S₂CN(CH₂)₆}₂] · CHCl₃ (II), are synthesized and characterized by the ¹³C MAS NMR data. The HmDtc ligands in structure I are not equivalent, whereas the solvation of the complex is accompanied by the structural unification of the initially nonequivalent HmDtc ligands. In addition, the spectra are characterized by the ¹³C-¹⁹⁵Pt spin-spin coupling. The noncentrosymmetric molecular structure of compound I determined by X-ray diffraction analysis includes two nonequivalent dithiocarbamate ligands coordinated by the metal in the S,S′-bidentate mode. The central atom forming the [PtS₄] chromophore (intraorbital dsp ²-hybrid state of platinum) shifts from the plane of four sulfur atoms by 0.07 Å in the vertex of the flattened tetragonal pyramid. The seven-membered heterocycles ?N(CH₂)₆ of the HmDtc ligands are oppositely directed in space relative to the [S₄] plane (trans orientation). The thermal behavior of compounds I and II are studied by simultaneous thermal analysis. In both cases, the final product of the multistage thermal destruction of the complexes is reduced metallic platinum.     

Synthesis and Structure of Acetonitrile Solvates of Copper(II) Monofluoroacetate and Silver(I) Trifluoroacetate, [Cu2(CH2FCOO)4· 2CH3CN](CH3CN) and Ag3(CF3COO)3(CH3CN)2

Compounds [Cu₂(CH₂FCOO)₄· 2CH₃CN](CH₃CN) (I) and Ag₃(CF₃COO)₃(CH₃CN)₂(II) were synthesized and studied by X-ray structural analysis. Crystals Iare monoclinic, space group C2/c, a= 27.854(6), b= 8.286(2), c= 19.428(4) Å, = 106.82(3)°, V= 4292(2) ų, Z= 8, R ₁= 0.0426; crystals IIare triclinic, space group , a= 8.676(2), b= 9.819(2), c= 11.961(2) Å, = 95.27(3), = 109.59(3)°, = 104.60(3)°, V= 911.4(3) ų, Z= 2, R ₁= 0.0252. Structure Iis composed of the structural units (lanterns) typical of copper(II) carboxylates. The presence of an additional acetonitrile molecule noncoordinated by the copper atoms makes it possible to consider compound Ias a lattice clathrate. Structure IIhas no analogs among the silver carboxylates. It simultaneously contains silver atoms with coordination numbers varying from 2 to 4.     

Synthesis,Characterization and Thermal Behavior of Complexes of Cu(II), Zn(II) and Cd(II) with S,S′-Methylenebis(Cysteine)

Synthesis and characterization, including data on thermal decomposition, are reported for the complexes of S,S'-methylenebis(cysteine) (djenkolic acid) with copper(II), zinc(II) and cadmium(II): CuC₇H₁₂N₂O₄S₂ [I]; ZnC₇H₁₂N₂O₄S₂ [II] and CdC₇H₁₂N₂O₄S₂ [III]. X-ray diffraction showed that the compounds are isostructural and belong to a monoclinic system. According to IR spectra, COO, NH₂ groups and bridging sulfur atoms are the main coordination sites.     

Chemisorption of the [AuCl4]− anion by cadmium cyclo-pentamethylenedithiocarbamate and the resulting bound-gold(III) species: The supramolecular structure and thermal behavior of the polynuclear complexes ([Au{S2CN(CH2)5}2]2[CdCl4]) n and ([Au{S2CN(CH2)5}Cl2]) n

The interaction between cadmium cyclo-pentamethylenedithiocarbamate (chemisorbent Ia) and the [AuCl₄]^? anion in 2 M HCl has been investigated. The state of the chemisorbent in contact with AuCl₃ solutions has been probed by ¹¹³Cd MAS NMR spectroscopy. The heterogeneous reactions in the system, including gold(III) chemisorption from the solution and partial ion exchange, yield the gold(III)-cadmium heteropolynuclear complex ([Au{S₂CN(CH₂)₅}₂]₂[CdCl₄]) _n (I) and the polynuclear mixed-ligand complex ([Au{S₂CN(CH₂)₅}Cl₂]) _n (II). The crystal and molecular structures of these compounds have been determined by X-ray crystallography. The main structural units of the compounds are the complex cation [Au{S₂CN(CH₂)₅}₂]⁺, [CdCl₄]^2? anion (in I), and Au{S₂CN(CH₂)₅}Cl₂ molecule (in II). The further structural self-organization of the complexes at the supramolecular level is due to secondary Au...S and Au...Au bonds. [Au₂{S₂CN(CH₂)₅}₄]²⁺ dinuclear cations form in the structure of I, which then polymerize into ([Au₂{S₂CN(CH₂)₅}₄]²⁺) _n chains. In the structure of II, adjacent Au{S₂CN(CH₂)₅}Cl₂ molecules join by forming pairs of asymmetric secondary Au...S bonds, producing polymer chains with alternating antiparallel monomer units. The chemisorption capacity values calculated for cadmium cyclo-pentamethylenedithiocarbamate from gold(III) binding reactions are 455 and 910 mg of gold per gram of sorbent. The gold recovery conditions have been determined by investigating the thermal behavior of I and II by synchronous thermal analysis. The multistep thermal destruction of ionic complex I includes the thermolysis of its carbamate moiety and [CdCl₄]_2? (which liberates gold metal and cadmium chloride and yield some amount of CdS) and CdCl₂ and CdS evaporation. The thermolysis of II proceeds via the formation of Au₂S and AuCl as intermediate compounds. In both cases, the ultimate pyrolysis product is elemental gold.     

Trinuclear {M1}CN{M2}2 complexes (M1 = Cr(III), Fe(III), Co(III); M2 = Cu(II), Ni(II), Mn(II)). Are single molecule magnets predictable?

The reaction of the hexacyanometalates K3[M(1)(CN)6] (M(1) = Cr(III), Fe(III), Co(III)) with the bispidine complexes [M(2)(L(1))(X)](n+) and [M(2)(L(2))(X)](n+) (M(2) = Mn(II), Ni(II), Cu(II); L(1) = 3-methyl-9-oxo-2,4-di-(2-pyridyl)-7-(2-pyridylmethyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylic acid dimethyl ester; L(2) = 3-methyl-9-oxo-7-(2-pyridylmethyl)-2,4-di-(2-quinolyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylic acid dimethyl ester; X = anion or solvent) in water-methanol mixtures affords trinuclear complexes with cis- or trans-arrangement of the bispidine-capped divalent metal centers around the hexacyanometalate. X-ray structural analyses of five members of this family of complexes (cis-Fe[CuL(2)]2, trans-Fe[CuL(1)]2, cis-Co[CuL(2)]2, trans-Cr[MnL(1)]2, trans-Fe[MnL(1)]2) and the magnetic data of the entire series are reported. The magnetic data of the cyanide bridged, ferromagnetically coupled cis- and trans-Fe[ML]2 compounds (M = Ni(II), Cu(II)) with S = 3/2 (Cu(II)) and S = 5/2 (Ni(II)) ground states are analyzed with an extended Heisenberg Hamiltonian which accounts for anisotropy and zero-field splitting, and the data of the Cu(II) systems, for which structures are available, are thoroughly analyzed in terms of an orbital-dependent Heisenberg Hamiltonian, in which both spin-orbit coupling and low-symmetry ligand fields are taken into account. It is shown that the absence of single-molecule magnetic behavior in all spin clusters reported here is due to a large angular distortion of the [Fe(CN)6](3-) center and the concomitant quenching of orbital angular momentum of the Fe(III) ((2)T2g) ground state.     

Binding of Gold(III) from Solutions by Tetranuclear Lead(II) Dipropyldithiocarbamate [Pb4{S2CN(C3H7)2}8] and Chemisorption Synthesis of the Double Ionic Polymer Complex ([Au{S2CN(C3H7)2}2][PbCl3] · 0.5CH3–C6H5)n: Heteronuclear ( 13 C, 15 N) CP-MAS NMR,Structural Organization,and Construction Principles of Cationic and Anionic Polymer Chains

Russian Journal of Coordination Chemistry - Solid-state 13C and 15N CP-MAS NMR data adequately reflected the presence of four nonequivalent PrDtc ligands in the tetranuclear lead(II)...     

Formation of the ionic gold(III) complex [Au3{S2CN(CH2)4O}6][Au2Cl8][AuCl4] in chemisorption systems [M{S2CN(CH2)4O}2] n -[AuCl4]−/2 M HCl (M = Cd, Zn): Supramolecular structure and thermal behavior

The interaction of freshly precipitated cadmium and zinc morpholinedithiocarbamates with solutions of AuCl₃ in 2 M HCl is studied. In both cases, the heterogeneous reactions of gold(III) binding from solutions lead to the formation of the ionic gold(III) complex [Au₃{S₂CN(CH₂)₄O}₆][Au₂Cl₈][AuCl₄] (I), whose molecular and supramolecular structures are determined by X-ray diffraction analysis. Compound I includes centrosymmetric and noncentrosymmetric cations [Au{S₂CN(CH₂)₄O}₂]⁺ in a ratio of 1: 2. According to the manifested structural differences, the complex cations are related as conformers (cations A are Au(1) and cations B are Au(2)). At the supramolecular level, the isomeric cations form linear trinuclear structural fragments [Au₃{S₂CN(CH₂)₄O}₆]³⁺ [A...B...A] due to secondary bonds Au...S of 3.6364 Å. The anionic part of compound I is presented by [AuCl₄]^? and centrosymmetric binuclear [Au₂Cl₈]^2?, whose formation involved secondary bonds Au...Cl of 3.486 and 3.985 Å. The ultimate chemisorption capacity of cadmium and zinc morpholinedithiocarbamates calculated from the binding of gold(III) is 901.7 and 1010.4 mg of Au³⁺ per 1 g of the sorbent, respectively (i.e., each miononuclear fragment of the chemisorption complexes [M{S₂CN(CH₂)₄O}₂] participates in binding of two gold atoms). To establish the conditions for the isolation of bound gold, the thermal properties of compound I are studied by simultaneous thermal analysis. The thermal destruction process includes the thermolysis of the dithiocarbamate part of the complex and anions [AuCl₄]^? and [Au₂Cl₈]^2? with the reduction of gold to the metal, being the only final product of the thermal transformations of compound I.     

Fixation mode of gold(III) in [Cd{S2CN(CH2)4O}2] n -[AuCl4]−/2 M HCl chemisorption system: Preparation, supramolecular self-organization and thermal behavior of the heteropolynuclear complex ([Au{S2CN(CH2)4O}2]2[CdCl4] · H2O) n

A capability of freshly deposited cadmium complex with cyclic morpholinodithiocarbamate ligand (MfDtc) to bind gold(III) from 2 M HCl solutions was studied. The individual form of bound gold (III) isolated from solution was found to be the hydrated heteropolynuclear complex of ionic type ([Au{S₂CN(CH₂)₄O}₂]₂[CdCl₄] · H₂O) _n (I). Molecular and supramolecular structure of preparatively isolated compound I was established by X-ray diffraction study, the structure includes four (1: 1: 1: 1) structurally nonequivalent centrosymmetric complex cations [Au{S₂CN(CH₂)₄O}₂]⁺ which relate to each other in agreement with appeared structural differences as conformers: A, B, C, and D cations with Au(1), Au(2), Au(3), and Au(4), respectively. At the supramolecular level, the isomeric complex cations undergo structural self-organization to form independent polymeric chains of two types: (-A-C-) _n and (-B-D-) _n on account of pairs of unsymmetrical secondary Au…S bonds (3.463, 3.496, and 3.627, 3.669 Å). Distorted tetrahedral [CdCl₄]^2? anions are located in the space between these chains. The chemisorption capacity of cadmium morpholinodithiocarbamate calculated from gold(III) binding is 450.8 mg Au³⁺ per 1 g of sorbent (i.e., each mononuclear fragment of the chemisorbent complex [Cd{S₂CN(CH₂)₄O}₂] binds one gold atom. The conditions of recovery of bound gold were found in the study of thermal behavior of I by simultaneous thermal analysis (STA). The multistep process of thermal destruction includes complex dehydration, thermolysis of its dithiocarbamate fragment and [CdCl₄]^2? to release gold metal, cadmium chloride, and partially CdS.     

Ionic Platinum(II)–Imidobis(diphenylthiophosphinato) Complexes: Preparation,Structure, and Thermal Behavior

The PPh₂P(S)NHP(S)PPh₂ (dppaS₂) ligand reacts with the starting complexes PtCl₂(L-L) (L-L = Ph₂PCH₂PPh₂), (dppm), Ph₂PCH₂CH₂PPh₂ (dppe), Ph₂PCH₂CH₂CH₂PPh₂ (dppp), and NaClO₄·H₂O. Final products are monomeric complexes, and their formulas are [Pt(L-L)(dppaS₂-H)] [(L-L = dppm(1), dppe(2), dppp(3)]. All of these have been characterized by ¹H, ¹³C^,31{P¹H} NMR, FTIR, and elemental analysis. These complexes were also examined by TGA, DTA, and DSC analysis. Complexes 2 and 3 were crystallographically characterized.     

Rearrangement of the {Mo6S8}cluster fragment to {Mo4S4} and a New {Mo6S6} Cluster Nucleus: Crystal Structure of K6[Mo4S4(CN)12]·10H2O and (18-Crown-6K)8[Mo6S6(CN)16]·17.5H2O

Two new compounds containing molybdenum thiocyanide cluster anions, K₆[Mo₄S₄(CN)₁₂]·10H₂O (1) and (18-crown-6K)₈[Mo₆S₆(CN)₁₆]·17.5H₂O (2), were synthesized and investigated by X-ray structure analysis. Crystal data: a=11.8430(17), b=11.8430(17), c=35.170(7) , V=4932.8(14) ³, space group I4₁/a, Z=4, d_calc=1.563 g/cm³ for 1; a=28.7513(5), b=18.4190(3), c=20.7586(4) , =118.5982(7)°, V=9651.9(3) ³, space group C2/m, Z=4, d_calc =1.563 g/cm³ for 2. The [Mo₄S₄(CN)₁₂]^6- cluster anion in 1 has an ordinary structure typical of cubane transition metal complexes. In the structure of the [Mo₆S₆(CN)₁₆]^8- anion of 2, two crystallographically independent molybdenum atoms form a Mo₆ metallocluster, represented as two edge-sharing tetrahedra.     

Double Pseudo-Polymeric Gold(III)-Mercury(II) Complexes [Au(S2CNR2)2]nX [R2 = (CH2)6, (CH2)4O] Containing ([HgCl3]−)n, [HgCl4]2− and [Hg2Cl6]2− Anions: Chemisorption Synthesis,Principles of Supramolecular Self-Assembly,and Thermal Behavior

Russian Journal of General Chemistry - Novel pseudo-polymeric complexes of gold(III)-mercury(II) with cyclic alkylene dithiocarbamate ligands: ([Au{S2CN(CH2)6}2][HgCl3])n,...     

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.     

From an {Fe4S4}-cluster to {Fe2S2}- and {Fe3S}-carbonyls. Crystal structure of [Fe3S(CO)9]2−

We report the electrochemical and chemical synthesis of the first isolable iron carbonyls obtained directly from an {Fe₄S₄}-cluster and carbon monoxide: the structure of one product of chemical reduction, [Fe₃S(CO)₉]²⁻, had been determined by X-ray crystallography.     

Synthesis of cobalt(II), nickel(II) and copper(II) complexes with 2-(2-hydroxyphenyliminomethyl)-1-(4-methyl-phenylsulfonamido)benzene and crystal structures of {bis(methanol)[2-(2′-N-tosylaminophenyl)iminomethyl]phenolato}nickel(II) and {bis(2,2′-bipyridine)[2-(2′-N-tosylaminophenyl)iminomethyl]phenolato}copper(II)

Electrochemical oxidation of metal anodes (cobalt, copper and nickel) in acetonitrile solutions of 2-(2-hydroxyphenyliminomethyl)-1-(4-methyl-phenylsulfonamido)benzene (H₂L) gave [CoL], [CuL] and [NiL] complexes. When 1,10-phenanthroline (phen) or 2,2′-bipyridine (bipy) was added to the electrolytic cell, the mixed complexes [MLL′] (M=Co, Cu, L′=bipy or M=Ni, L′=phen) were obtained. A binuclear compound of composition [Ni₂L₂(MeOH)₄] (1) was synthesized by reaction of the ligand H₂L and nickel(II) acetate in methanol. X-ray structure determination showed the compound to be binuclear, with each nickel atom coordinated to two nitrogen and two bridging phenol oxygen atoms of two dianionic ligands and two methanol molecules, in an octahedral environment. The crystal structure of [CuLbipy] (2) was determined by X-ray diffraction; with the copper atom in a distorted bipyramidal environment defined by the two bipyridine nitrogen atoms and by the phenolic oxygen and the nitrogen atoms of the dianionic ligand. The electronic and vibrational spectral data of the complexes are discussed and related to the structure.     

New Supramolecular Complex Assembled through Hydrogen Bonds. Crystal Structure of Co(PMBP-tsc)_2 ·2DMF·2H_2O

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Synthesis and Crystal Structure of a Novel Heptanuclear Ruthenium- and Sodium-containing Polyoxomolybdate [ {Na(H2O)3}2{Ru(dmso)3}2(MoO4)3]·3H2O

The title compound, [{Na(H2O)3}2{Ru(dmso)3}2(MoO4)3]·3H2O, has been obstructure was determined by single-crystal X-ray diffraction method. The crystal crystallizes in the triclinic system, space group P1 with a = 12.3333(3), b = 12.6289(3), c = 32.0284(14)(A), α =79.873(7), β = 87.549(9), y = 64.500(4)°, V = 4429.5(2) (A)3, Z = 4, Mr = 1358.85, Dc = 2.038g/cm3, F(000) = 2696 and μ = 1.874 mm-1. The compound contains a novel pentanuclear triangle bipyramidal core, [{ Ru(dmso)3 } 2(MoO4)3]2-, which consists of two { Ru(dmso)3 } 2+ fragments and three {μ2-MoO4}2- units. Furthermore, the dmso ligands bridge the pentanuclear [Ru2Mo3] core and two [Na(H2O)3]+ fragments together, forming a neutral heptanuclear ruthenium- and sodiumcontaining polyoxomolybdate.