Structural organization and thermal behavior of the heteropolynuclear complex [Au2{S2CN(CH3)2}4][ZnCl4] and the heterovalent complex ([Au{S2CN(CH3)2}2][AuCl2]) n obtained in the chemisorption system [Zn2{S2CN(CH3)2}4]-Au3+/2 M HCl

Reactions of freshly precipitated binuclear zinc dimethyldithiocarbamate with [AuCl₄]^? anions in 2 M HCl were studied. The heteropolynuclear complex [Au₂{S₂CN(CH₃)₂}₄][ZnCl₄] (I) and the polymeric heterovalent complex ([Au{S₂CN(CH₃)₂}₂][AuCl₂]) _n (II) were preparatively isolated from the chemisorption system [Zn₂{S₂CN(CH₃)₂}₄]-Au³⁺/2 M HCl. The products were characterized by ¹³C MAS NMR data and by X-ray diffraction determination of crystal and molecular structures. The principal structural units of compounds I and II are the tetragonal planar complex cations [Au{S₂CN(CH₃)₂}₂]⁺ (in which the complex-forming ion coordinates two MDtc ligands in the S,S′-bidentate mode) and the anions, namely, the distorted tetrahedral anion [ZnCl₄]^2? in I and the linear [AuCl₂]^? anion in II. The further structural self-organization of complexes at the supramoleular level occurs through relatively weak secondary bonds Au?S and Au?Cl. The chemisorption capacities of zinc dimethyldithiocarbamate calculated from gold(III)-binding reactions are 644.1 and 1288.2 mg of gold per gram of the sorbent. Simultaneous thermal analysis studies of the thermal behavior of I and II were used to elucidate the conditions of gold recovery.     

Adduct formation of cadmium(II) N,N-cyclo-hexamethylenedithiocarbamate, [Cd2{S2CN(CH2)6}4], with morpholine: Synthesis, molecular structure, and thermal behavior of a crystalline adduct cis-[Cd{NH(CH2)4O}2{S2CN(CH2)6}2]

The reaction of [Cd₂{S₂CN(CH₂)₆}₄] (I) with morpholine gives a crystalline adduct of cadmium N,N-cyclo-hexamethylenedithiocarbamate [Cd{NH(CH₂)₄O}₂{S₂CN(CH₂)₆}₂] (II), whose coordination sphere includes two molecules of the donor base. The structural organization and thermal behavior of II is studied by X-ray diffraction analysis and simultaneous thermal analysis in comparison with the original binuclear cadmium complex I. The central cadmium atom (coordination number 6) coordinates two morpholine molecules and two structurally equivalent S,S’-anisobidentate ligands HmDtc to form a chromophore [CdN₂S₄] with the structure of a distorted octahedron. The thermal destruction of II proceeds in two stages and includes consecutive steps of dissociation of the Cd-N bonds followed by the desorption of morpholine and thermolysis of the dithiocarbamate moiety of the adduct to form CdS as the final product. The structure of binuclear [Cd₂{S₂CN(CH₂)₆}₄] is refined for a correct refinement of the geometric characteristics of compounds I and II.     

Synthesis and Structure of Tetra(para-tolyl)antimony Dicyanodiiodoaurate [p-Tol4Sb][Au(CN)2I2] and Alkyltriphenylphosphonium Dicyanodiiodoaurates [Ph3PAlk][Au(CN)2I2], Alk = Me,CH2CN

Russian Journal of Coordination Chemistry - Red-colored crystalline gold complexes [p-Tol4Sb][Au(CN)2I2] (I), [Ph3PMe][Au(CN)2I2] (II), and [Ph3PCH2CN][Au(CN)2I2] (III) were synthesized by the...     

4-Methyl-1,2,3,5-dithiadiazoliumsalze Die Kristallstrukturen von (CH3CN2S2)5[CoCl4]Cl3 und (CH3CN2S2)Cl

4-Methyl-1,2,3,5-dithiadiazolium Salts. Crystal Structures of(CH₃CN₂S₂)₅[CoCl₄]Cl₃ and (CH₃CN₂S₂)Cl 4-Methyl-1,2,3,5-dithiadiazolium tetrachlorocobaltate trichloride, (CH₃CN₂S₂)₅[CoCl₄]Cl₃, was obtained by reaction of trithiazyl chloride, (NSCl)₃, with CoCl₂ in acetonitrile; it forms brown, moisture sensitive crystals. With tetraphenylarsonium chloride in CH₂Cl₂ it yields yellow crystalline (CH₃CN₂S₂)Cl and (AsPh₄)₂CoCl₄. The IR spectra of the title compounds are reported and assigned. Theit crystal structures were determined by X-ray diffraction. Crystal data: (CH₃CN₂S₂)₅[CoCl₄]Cl₃, orthorhombic, P2₁2₁2₁, Z = 4, a = 830, b = 1603, c = 2443 pm at 180 K (structure determination with 1787 observed independent reflexions, R = 0.070); (CH₃CN₂S₂)Cl, triclinic, P2₁2₁2₁, Z = 4, a = 749, b = 819, c = 1015 pm, α = 84.9, β = 67.4, γ = 84.6° at 296 K (2653 reflexions, R = 0.040). Both compounds are ionic, having chloride and distorted tetrahedral CoCl₄^2? anions and planar 4-methyl-1,2,3,5-dithiadiazolium cations which nearly fulfill C_2v symmetry. The (CH₃CN₂S₂)₅[CoCl₄]Cl₃ structure contains five symmetry independent cations, (CH₃CN₂Cl has two symmetry independent cations, all being nearly equal. No nitrogen atom but all sulfur atoms of the cations have contact with three to five chlorine atoms, and as a rule there is one chloride ion which is coplanar with the cation and exhibits rather short distances to both S atoms (288 to 309 pm); therefore, the positive charge of the cations must be concentrated on the sulfur atoms.     

Pentafluorophenyl(dithiocarbamate)gold(III) complexes. Crystal and molecular structure of (C6F5)2Au{S2CN(CH2Ph)2}

Addition of dialkyldithiocarbamate ligands to solutions of Au(C₆F₅)₃(tht) gives either monomeric Q[Au(C₆F₅)₃(η¹-S₂CNR₂)] (Q = N(PPh₃)₂ or NBu₄; R = Me, Et, CH₂Ph) or binuclear dithiocarbamate-bridged complexes. NBu₄(μ-S₂CNR₂){Au(C₆F₅)₃}₂]. When binuclear [Au(μ-Cl)(C₆F₅)₂]₂ is used as gold source, neutral mononuclear complexes [Au(C₆F₅) ₂(η²-S₂CNR₂)] are obtained. The structure of [Au(C₆F₅)₂{η²-S₂CN(CH₂Ph)₂}] has been determined by X-ray diffraction.     

Reaction of S2CC(PPh3)2 with Silver Salts Containing Weakly Coordinating Anions; Preparation and Crystal Structures of [Ag6{S2CC(PPh3)2}4][BF4]6 · 9.75CH2CL2 and [Ag4{S2CC(PPh3)2}4][Al{OC(CF3)3}4]4 · 4.25C2H4Cl2

The betain‐like carbodiphosphorane CS₂ adduct S₂CC(PPh₃)₂ ( 1 ) reacts with Ag(I) salts which contain weakly coordinating anions such as [BF₄]^? or [Al{OC(CF₃)₃}₄]^? to produce the cluster compounds [Ag₆{S₂CC(PPh₃)₂}₄][BF₄]₆ ( 2 ) and [Ag₄{S₂CC(PPh₃)₂}₄][Al{OC(CF₃)₃}₄]₄ ( 3 ), respectively, as orange yellow crystals containing solvent molecules. In the solid state the Ag₄ unit in 3 forms a tetrahedron, and in the Ag₆ core of 2 two of the opposite edges of the tetrahedron are bridged by Ag⁺ ions. The clusters are held together by argentophilic interactions, and each sulfur atom of 1 is coordinated to four (as in 2 ) or three (as in 3 ) silver atoms. The compounds are characterized by IR and ³¹P NMR spectroscopic studies and by X‐ray diffraction analyses.     

Die Kristallstrukturen von {Li3(12-Krone-4)2[HC(CN)2]3}, {Na(15-Krone-5)-[HC(CN)2]} und {Na[N(nBu)4][HC(CN)2]2 · THF}

The Crystal Structures of {Li₃(12-crown-4)₂[HC(CN)₂]₃}, {Na(15-crown-5)[HC(CN)₂]}, and {NaN(nBu)₄[HC(CN)₂]₂ · THF} The preparation and the crystal structures of the title compounds 1 — 3 are described. 1 forms a polymeric chain structure, in which one of the lithium ions is linked by Li…NCC(H)CN… bridges. The remaining lithium ions form (12-crown-4)Li[NCC(H)CN] units, which are coordinated by one of the nitrogen atoms of the dicyanomethanide ions with the lithium ions of the chain. 2 forms an ion pair, in which the sodium ion is coordinated by the five oxygen atoms of the crown ether molecule and by one nitrogen atom of the dicyanomethanide ion. 3 has a threedimensional network, in which the sodium ions are coordinated in a distorted tetrahedral manner by the nitrogen atoms of the dicyanomethanide ions. In the cavities of the network the tetrabutylammonium ions and the THF molecules are found.     

Binding forms of gold(III) from solutions by cadmium diethyl dithiocarbamate: Thermal behavior and role of secondary interactions in the supramolecular self-assembly of polymeric complexes ([Au{S2CN(C2H5)2}2][AuCl4]) n and [Au{S2CN(C2H5)2}Cl2] n

The chemisorption interaction between the binuclear cadmium diethyl dithiocarbamate (EDtc), [Cd₂{S₂CN(C₂H₅)₂}₄], (chemisorbent I) and AuCl₃ solutions in 2 M HCl results in the formation of polymeric gold(III) complexes: ([Au{S₂CN(C₂H₅)₂}₂][AuCl₄]) _n (II) and [Au{S₂CN(C₂H₅)₂}Cl₂] _n (III) with the same Au : EDtc : Cl ratio (1 : 1 : 2). The alternating centrosymmetric cations and anions of complex II are structurally self-assembled to form linear polymeric chains: the gold atom in [Au{S₂CN(C₂H₅)₂}₂]⁺ forms secondary Au(1)?Cl(1) bonds (3.7784 Å) with two neighboring [AuCl₄]^? anions. This binding is additionally strengthened by secondary S(1)?Cl(1) interactions (3.4993 Å). The mixed-ligand complex III comprises two structurally non-equivalent molecules [Au{S₂CN(C₂H₅)₂}Cl₂]: A—Au(1) and B—Au(2), each being in contact with two nearest neighbors through pairs of unsymmetrical secondary bonds: Au(1)?S(1)^a/b 3.4361/3.6329; and Au(2)?S(4)^c/d 3.4340/3.6398 Å. At the supramolecular level, this gives rise to independent zigzag-like polymeric chains, (?A?A?A?) _n and (?B?B?B?) _n along which antiparallel isomeric molecules of III alternate. The chemisorption capacity of cadmium diethyl dithiocarbamate calculated from the gold(III) binding reaction is 963.2 mg of gold per 1 g of the sorbent. The recovery conditions for the bound gold were elucidated by simultaneous thermal analysis of II and III. The DSC curves reflect different sets of heat effects, because thermolysis occurs for complex molecules (III) or for cations and anions (II). Nevertheless, the patterns of experimental TG curves are similar despite different structures of the complexes. The final product of thermal transformations is reduced gold.     

Synthesis, structure, and magnetic properties of [(CH3CN)5V-O-V(CH3CN)5][BF4]4

The reaction of vanadium(III) acetylacetonate with HBF4 in acetonitrile yields [(CH3CN)5V-O-V(CH3CN)5][BF4]4, a material that serves as a convenient precursor to other [V-O-V]4+ species such as [(bipy)2(CH3CN)V-O-V(CH3CN)(bipy)2][BF4]4 (bipy=2,2'-bipyridine). Single-crystal X-ray diffraction shows that the V-O-V linkage of [(CH3CN)5V-O-V(CH3CN)5]4+ is linear. An Evans method measurement of the solution-phase magnetic susceptibility indicates strong ferromagnetic coupling between the vanadium centers. Magnetic susceptibility (chi) and magnetization (M(H)) data for a powdered sample and for a single crystal oriented with its V-O-V axis parallel to the applied field were measured over 1.8-300 K. The results suggest that the V(III) centers are ferromagnetically coupled with J approximately 72 K (approximately 50 cm(-1)) yielding a ground state with a total spin Stotal=2. Theoretical fit to the M(H) plot for the single crystal yielded g||=2.01+/-0.01 and the zero-field splitting parameter D=0.60+/-0.04 K (0.42+/-0.03 cm(-1)). EPR measurements at 34 and 101.6 GHz are consistent with the Stotal=2 ground state and yield g||=1.9825, g perpendicular=1.9725 and D=0.57+/-0.03 K.     

Synthesis of homoleptic tris(organo-chelate)iridium(III) complexes by spontaneous ortho-metallation of electronrich olefin-derived N,N′-diarylcarbene ligands and the X-ray structures of fac-[Ir{CN(C6H4Me-p) (CH2)2NC6H3Me-p}3] and mer-Ir{CN(C6H4Me-p)(CH2)2NC6H3Me-p}2 {CN(C6H4Me-p)(CH2)2NC6H4Me-p}Cl (a product of HCl cleavage)

Treatment of [{Ir(COD)(μ-Cl)}₂] with excess of the electron-rich olefin [$\text{CN(Ar)(CH}{}_2\text{)}{}_2\text{N}$Ar]₂ (abbreviated as (L^Ar)₂, Ar = C₆H₄Me-p or C₆H₄OMe-p) affords the ortho-metallated tricycle [$\text{Ir(L}{}^{\mathrm{A}}\text{r}$)₃], which for Ar = C₆H₄Me-p (Ia) with HCL yields [$\text{Ir(L}{}^{\mathrm{A}}\text{r}$)₂(L^Ar)]Cl (IV); X-ray data show that in IV there is an unexpectedly close Ir?C(o-aryl) contact (2;52(1) Å) involving the “free” L^Ar which compares with an IrC(o-aryl) distance of 2.09(3) Å in Ia or 2.07(3) Å in the ortho-metallated L^Ar ligand of complex IV.     

Zur solvensfreien Darstellung von Tetramethylammoniumsalzen: Synthese und Charakterisierung von [N(CH3)4]2[C2O4], [N(CH3)4][CO3(CH3)], [N(CH3)4][NO2], [N(CH3)4][CO2H] und [N(CH3)4][O2C(CH2)2CO2(CH3)]

Solvent-free Synthesis of Tetramethylammonium Salts: Synthesis and Characterization of [N(CH₃)₄]₂[C₂O₄], [N(CH₃)₄][CO₃CH₃], [N(CH₃)₄][NO₂], [N(CH₃)₄][CO₂H], and [N(CH₃)₄][O₂C(CH₂)₂CO₂CH₃] A general procedure to synthesize tetramethylammonium salts is presented. Several tetramethylammonium salts were prepared in a crystalline state by solvent-free reaction of trimethylamine and different methyl compounds at mild conditions: [N(CH₃)₄]₂[C₂O₄] (cubic; a = 1 114.8(3) pm), [N(CH₃)₄][CO₃CH₃] (P2₁/n; a = 813.64(3), b = 953.36(3), c = 1 131.3(4) pm, β = 90.03(1)°), [N(CH₃)₄][NO₂] (Pmmn; a = 821.2(4), b = 746.5(3), c = 551.5(2) pm), [N(CH₃)₄][CO₂H] (Pmmn; a = 792.8(7), b = 791.7(3), c = 563.3(4) pm) and [N(CH₃)₄][O₂C(CH₂)₂CO₂CH₃] (P2₁; a = 731.1(2), b = 826.4(3), c = 1 025.2(3) pm, β = 110.1(1)°). The tetramethylammonium salts were characterized by IR-spectroscopy and X-ray diffraction. The crystal structures of the methylcarbonate and the nitrite are described.     

Synthesis, Chemical Characterization, and Molecular Structure of Au8{Fe(CO)4}4(dppe)2 and Au6Cu2{Fe(CO)4}4(dppe)2

The new Au₈{Fe(CO)₄}₄(P^P)₂ and Au₆Cu₂{Fe(CO)₄}₄(P^P)₂ (P^P=dppm, dppe) neutral cluster compounds were isolated in good yields by condensation of the [Au₃{Fe(CO)₄}₂(P^P)]^- anions with Au(SEt₂)Cl and CuCl, respectively, and have been characterized by IR, NMR and microanalyses. The molecular structures of Au₈{Fe(CO)₄}₄(dppe)₂ and Au₆Cu₂{Fe(CO)₄}₄(dppe)₂ have been determined by X-ray diffraction studies. Both molecules adopt a stereogeometry of the heavy atoms consisting of a triangulated and corrugated ribbon twisted around the elongation direction. Contrary to the expectations the latter displays the two copper atoms in the sites of highest connectivity. This implies that site exchange between copper and gold occurs during the synthesis.     

A Tri-Coordinate-Magnesium Silylamide Complex: {[(CH3)3Si]2N}2MgO(CH2CH2)2OMg{N[Si(CH3)3]2}2

The reaction of diethylmagnesium dioxane adduct solution with 1,1,1,3,3,3-hexamethyldisilazan ((CH₃)₃SiNHSi(CH₃)₃) gives {[(CH₃)₃Si]₂N}₂MgO(CH₂CH₂)₂OMg{N[Si(CH₃)₃]₂}₂ (1); this alkoxomagnesium silylamide in the solid state contains unprecedented three-coordinate magnesium and oxygen atoms.     

Synthesis and Structure of a Three‐dimensional Organically Templated Zinc Ethylenediphosphonate, [NH3(CH2)2NH3][Zn3{O3P(CH2)2}4]

A hydrothermal reaction of a mixture of ZnO, HCl, ethylenediphosphonic acid, ethylenediamine, acetic acid in a water, THF mixture gave rise to a new three‐dimensional zinc ethylenediphosphonate, [NH₃(CH₂)₂NH₃][Zn₃{O₃P(CH₂)₂}₄], I . The structure, determined by single crystal X‐ray diffraction, (monoclinic, space group = C2/c, a = 16.9948(14), b = 6.7383(6), c = 16.8886(14)Å, β = 1113.568(1)°, V = 1772.7(3)ų, Z = 4, R₁ = 0.0227, wR₂ = 0.0601), consists of a network of strictly alternating ZnO₄ and PO₃C tetrahedral units linked through their vertices forming the three‐dimensional structure. The amine molecules occupy the middle of the 8‐membered channels and interact with the framework through the hydrogen bonds. Unlike other zinc diphosphonates, I appear to have close similarity to zinc phosphate structures reported in the literature. To our knowledge, this is the first three‐dimensional zinc diphosphonate prepared in the presence of an organic amine molecule.     

Synthese und Strukturuntersuchungen von Iodocupraten(I). XV Iodocuprate(I) mit solvatisierten Kationen: [Li(CH3CN)4][Cu2I3] und [Mg{(CH3)2CO}6][Cu2I4]

Synthesis and Structure Investigations of Iodocuprates(I). XV Iodocuprate(I) with Solvated Cations: [Li(CH₃CN)₄] [Cu₂I₃] and [Mg{(CH₃)₂CO}₆][Cu₂I₄] [Li(CH₃CN)₄][Cu₂I₃] 1 and [Mg((CH₃)₂CO)₆][Cu₂I₄] 2 were prepared by reactions of CuI with LiI in acetonitrile and of CuI with MgI₂ in acetone. 1 crystallizes orthorhombic, Pnma, a = 552.7(2), b = 1258.8(8), c = 2516(1) pm, z = 4. [Li(CH₃CN)₄]⁺ cations are located between rod packings of CuI₄ tetrahedra double chains [(CuI_2/2I_2/4)₂]^? parallel to the axis. Short intermolecular anion/cation contacts were observed. The crystal structure of 2 (monoclinic, P2₁/n, a = 1840(2), b = 1059.2(2), c = 1879(2)pm, β = 112.94(4)°, z = 4) is built up by [Mg((CH₃)₂CO)₆]²⁺ cations forming a simple hexagonal sphere packing. The binuclear anions [Cu₂I₄]^2? occupy holes in the trigonal prismatic channels formed by the cations.