Interaction of Fe(III) pivalate, barium(II) nitrate, and 2,2′-bipyridine (bpy) in acetonitrile leads to the formation of the ionic heteronuclear complex [Fe(bpy) 3 ] 2 [Ba(NO 3 ) 6 ] ( 1 ). The structure of the complex is determined by X-ray diffraction (XRD). According to the XRD data, each [Ba(NO 3 ) 6 ] 4– anion in the packing of 1 is surrounded by twelve [Fe(bpy) 3 ] 2+ cations, and its additional stabilization due to non-covalent interactions leads to the formation of a strong supramolecular framework. Thermal behavior of 1 is studied by simultaneous thermal analysis (STA).

Взаимодействие пивалата FeIII, нитрата бария(II) и 2,2`-бипиридина (bpy) в ацетонитриле приводит к формированию ионного гетероядерного комплекса [Fe(bpy)3]2[Ba(NO3)6] (1), структура которого была определена методом рентгеноструктурного анализа (РСА). По данным РСА в упаковке 1 каждый анион [Ba(NO3)6]4- окружен двенадцатью катионами [Fe(bpy)3]2+, а дополнительная стабилизация при участии нековалентных взаимодействий приводит к образованию прочного надмолекулярного каркаса. Термическое поведение 1 исследовано методом синхронного термического анализа (СТА).

Pseudobinuclear, [Bi(S2CNiPr2)3]2 (I), and 1D pseudopolymeric, [Bi(S2CNiPr2)2][Bi(S2CNiPr2)Cl3] (II), bismuth(III) complexes have been synthesized and structurally characterized. Secondary Bi⋅⋅⋅S, Bi⋅⋅⋅Cl, and S⋅⋅⋅Cl bonds combine mononuclear structural units of the complexes, playing a key role in self-assembly of their supramolecular structures. The thermal behavior of the compounds has been studied by simultaneous thermal analysis under an argon atmosphere. It has been determined by energy dispersive X-ray microanalysis and scanning electron microscopy that the residual substances after thermolysis of I/II are microcrystalline Bi2S3/Bi2S3, BiCl3.

Two new dialkyldithiocarbamato platinum(II) complexes of [Pt(S2CNR)(2)], R = iso-C3H7 (1) and iso-C4H9 (2), have been prepared and characterised using C-13 CP-MAS NMR. The crystal and molecular structures of the isolated compounds were established by single-crystal X-ray diffraction. The unit cell of 1 contains four centrosymmetric discrete molecules of [Pt{S2CN(iso-C3H7)(2)}(2)], of which the pairs are structurally inequivalent to each other (hereafter denoted as molecules 1a and 1b). At the supramolecular level, due to numerous intermolecular C-H center dot center dot center dot S hydrogen bonds, the la molecules form linear polymeric ribbons, whose interaction with the 1b molecules results in a two-dimensional polymeric network. In the structure of 2, the construction of supramolecular zigzag chains by non-centrosymmetric molecules of [Pt{S2CN(iso-C4H9)(2)}(2)] is determined by intermolecular C-H center dot center dot center dot Pt anagostic interactions. The thermal behaviour of crystalline compounds 1 and 2 was studied by simultaneous thermal analysis (STA), a combination of the TG and DSC techniques, under an argon atmosphere. In both cases, platinum(II) sulfide (PtS) was identified as the main end-product upon thermal decomposition of the complexes at 600 degrees C. (C) 2019 Elsevier Ltd. All rights reserved.

Solid-state 13C and 15N CP-MAS NMR data adequately reflected the presence of four nonequivalent PrDtc ligands in the tetranuclear lead(II) N,N-dipropyldithiocarbamate (PrDtc), [Pb4{S2CN(C3H7)2}8] (I); the spin–spin coupling constants 3J(15N–207Pb) for the ligands were estimated. It was shown by 13C MAS NMR that the chemisorption binding of AuCl3 from a solution in 2M HCl using lead(II) dipropyldithiocarbamate is accompanied by complete redistribution of the PrDtc ligands from Pb(II) to Au(III) coordination sphere; this gives the double complex of [Au{S2CN(C3H7)2}2][PbCl3] (II). Upon crystallization from an acetone–toluene mixture (3 : 1), this complex was isolated as the solvated form ([Au{S2CN(C3H7)2}2][PbCl3] ⋅ 1/2CH3C6H5)n (IIa), which was characterized by X-ray diffraction (CIF file CCDC no. 1978947). The cationic part of the complex is represented by non-centrosymmetric gold(III) complex ions, [Au{S2CN(C3H7)2}2]+, which are combined by pairs of nonequivalent Au···S secondary bonds, thus forming supramolecular pseudo-polymer chain ([Au{S2CN(C3H7)2}2]+)n. The 1D polymeric trichloroplumbate(II) anion, {[Pb(μ2-Cl)3]–}n, acts as the counter-ion. The C–H···Cl hydrogen bonds between the anionic and cationic chains lead to formation of channels in the crystal lattice, which are occupied by solvating toluene molecules.

Chemisorption synthesis on the basis of the binuclear compound [Bi2{S2CN(C3H7)2}6] (I) and preparative isolation of the ion-polymeric heteronuclear gold(III)–bismuth(III) complex ([Au{S2CN(C3H7)2}2]3[Bi2Cl9])n (II) are carried out. Compounds I and II are characterized in comparison by IR spectroscopy and 13C CP-MAS NMR. According to the X-ray diffraction analysis data (CIF file CCDC no. 1407705), the cationic moiety of compound II exhibits an unusually complicated supramolecular structure including six isomeric noncentrosymmetric complex cations [Au{S2CN(C3H7)2}2]+ (hereinafter A–F) and two binuclear anions [Bi2Cl9]3– as conformers. The isomeric gold(III) cations perform various structural functions. Owing to pair secondary interactions Au···S, cations B, C, E, and F form centrosymmetric ([E···E], [F···F]) and noncentrosymmetric ([B···C]) binuclear aggregates [Au2{S2CN(C3H7)2}4]2+, whereas cations A and D are not involved in dimerization. The strongest secondary Au···S bonds are formed between the binuclear and mononuclear cations, resulting in the formation of supramolecular cation-cationic polymer chains of two types: (⋅⋅⋅A⋅⋅⋅[B⋅⋅⋅C]⋅⋅⋅A⋅⋅⋅[B⋅⋅⋅C]⋅⋅⋅)n and (D⋅⋅⋅[E⋅⋅⋅E]⋅⋅⋅D⋅⋅⋅[F⋅⋅⋅F]⋅⋅⋅])n. In both chains, the gold atoms of the binuclear cations are characterized by a distorted octahedral coordination [S6], whereas in the mononuclear cations the gold atoms retain the square environment [S4]. The cation-anionic interactions are provided by secondary bonds Cl⋅⋅⋅S involving the terminal chlorine atoms of isomeric [Bi2Cl9]3– and the sulfur atoms of the binuclear cations [Au2{S2CN(C3H7)2}4]2+. The character of the thermal behavior of compounds I and II is studied by simultaneous thermal analysis with the identification of intermediate and final products of the thermal transformations. The thermolysis of compound I at 193–320°C is accompanied by the formation of Bi2S3 with an impurity of reduced metallic bismuth particles. The final products of the thermal transformations of compound II are reduced elemental gold and Bi2O3, and the thermal transformation intermediates are BiCl3 and Bi2S3.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

A reaction of freshly precipitated bismuth(III) N,N-dipropyldithiocarbamate (PDtc) with AuCl3 solution in 2 M HCl was studied. A heteropolynuclear gold(III)-bismuth complex of ionic type [Au{S2CN(C3H7)2}2]3[Bi3Cl12] (I) was isolated by crystallization of products of the heterogeneous reaction from acetone-chloroform (1: 1) solution. Crystal and supramolecular structure of compound I established by X-ray diffraction study includes structurally nonequivalent complex cations [Au{S2CN(C3H7)2}2]+ related to each other as conformers (hereinafter cations A, B, C, and D) in 1: 1: 2: 2 ratio. Due to secondary Au⋯S bonds (3.386–3.617 Å), the isomeric cations form trinuclear species of two types: [C⋯A⋯C] and [D⋯B⋯D] that differ in the character of intercationic binding and Au-Au distances. Relatively weak aurophilic Au⋯Au bonds (3.4704(3) Å) unite the neighboring cationic triads into zigzag polymeric chains of type (⋯[C⋯A⋯C]⋯[D⋯B⋯D]⋯) n oriented along the crystallographic axis b. The spatial isolation of neighboring chains is provided by discrete trinuclear anions [Bi3Cl12]3− where metal atoms bind four bridging (μ2 and μ3) chlorine atoms, while each bismuth atom forms distorted octahedral chromophore [BiCl6]. The complex tribismuth anion in the structure I is the first example of [Bi3Cl12]3− anion of angle rather than linear structure: Bi(1)Bi(2)Bi(3) angle is 72.358°. The thermal behavior of compound I was studied by simultaneous thermal analysis. The multistage process of thermal destruction includes the thermolysis of dithiocarbamate portion of the complex and [Bi3Cl12]3− accompanied by reduction of gold(III) to metal and release of BiCl3 (followed by its evaporation) and partial formation of Bi2S3. In the temperature range 680–760°C, bismuth sulfide undergoes oxidation to (BiO)2SO4, which decomposes above 760°C to give Bi2O3. Residue after thermolysis of compound I is gold metal and bismuth(III) oxide.

The reaction of binuclear bismuth(III) N,N-dipropyldithiocarbamate [Bi2{S2CN(C3H7)2}6] with a solution of AuCl3 in 2 M HCl was studied. Crystallization of the heterogeneous reaction products from an acetone solution afforded the polymeric solvated heteropolynuclear gold(III)–bismuth complex, ([Au{S2CN(C3H7)2}2]3[Bi2Cl9] · 1/2CO(CH3)2 · 1/2HCl)n (I). According to X-ray diffraction data (CIF file CCDC no. 1050766), the structure of I comprises four isomeric [Au{S2CN(C3H7)2}2]+ cations in 1: 1: 2: 2 ratio, namely: cation “A” with the Au(1) atom, cation “B” with the Au(2) atom, cation “C” with the Au(3) atom, and cation “D” with the Au(4) atom, and the discrete binuclear [Bi2Cl9]3– anions. The isomeric gold(III) complex cations are involved in the construction of two types of cationic triads, [“C”···“A”···“C”] and [“D”···“B”···“D”], through secondary bonds and short Au···S contacts. The cation types differ by both the nature of binding and the Au–Au distances. The weak aurophilic binding between the cationic triads (Au···Au 3.5416(2) Å) gives rise to zigzag-like polymeric chains (···[“C”···“A”···“C”]···[“D”···“B”···“D”]···)n extended along the y axis. In turn, the [Bi2Cl9]3– anions located on one side of polymer chains are held by the secondary Cl···S bonds. The outer-sphere CO(CH3)2 and HCl solvate molecules joined by hydrogen bonds are located in the space between bismuth anions. The thermal behavior of I was studied by simultaneous thermal analysis. The thermal destruction of the complex includes desolvation and thermolysis of the dithiocarbamate moiety and [Bi2Cl9]3– with liberation of gold metal and bismuth chloride (which is subsequently evaporated) and partial formation of Bi2S3. In the temperature range of 712–828°C, bismuth sulfide is oxidized to (BiO)2SO4, which decomposes above 828°C to give Bi2O3. Bismuth(III) oxide and reduced gold are the final products of thermal transformations.