The reaction of binuclear zinc dipropyldithiocarbamate [Zn 2 {S 2 CN(C 3 H 7 ) 2 } 4 ] with an AuCl 3 /2 М HCl solution is studied. The double ionic complex [Au{S 2 CN(C 3 H 7 ) 2 } 2 ] 2 [ZnCl 4 ] ( I ) is identified as the main species of gold(III) binding in the heterogeneous system under study and is characterized by 13 С and 15 N CP-MAS NMR spectroscopy. Single crystals of heterovalent compound [Au{S 2 CN(C 3 H 7 ) 2 } 2 ] 2 [AuCl 4 ][AuCl 2 ] ( II ) are sampled as a by-product. The crystal and supramolecular structures of complexes I and II are determined by the direct XRD method (CIF files CCDC nos. 2159171 and 2159170, respectively). The self-organization of the complex pseudopolymeric structures of compounds I and II are shown to be due to the binding of ionic structural units by secondary nonvalent interactions Au⋅⋅⋅S and S⋅⋅⋅Cl and hydrogen bonds C–H⋅⋅⋅Cl. The thermal behavior of the complexes is studied by simultaneous thermal analysis (STA), and the quantitative regeneration of bound gold ( I and II ) with the partial transformation of released ZnCl 2 to ZnS ( I ) is found.

The capability of thallium(I) alkylenedithiocarbamates to bind gold(III) from solutions in 2 M HCl was studied. Double complexes [AuS2CN(CH2)52][TlCl4] and [AuS2CN(CH2)62][TlCl4] were preparatively isolated as individual forms of gold(III) fixation to the solid phase. In the crystalline state, the ionic structural units of the complexes are combined together by the secondary Au···S, Tl···S, and S···Cl bonds that results in complicated supramolecular architectures. Thermal behavior of the compounds was studied using the simultaneous thermal analysis technique; reduced elemental gold and thallium(I) chloride were identified as the final thermolysis products.

Chemisorption binding of gold(III) by mercury(II) N,N-diisobutyldithiocarbamate from a solution of H[AuCl4] in 2 M HCl is accompanied by a complete redistribution of ligands between the coordination spheres of metals, which leads to the formation of the [Au(S2CNBui2)2]2[Hg2Cl6] compound belonging to double complex salts. According to X-ray diffraction data, the mutual binding of ionic structural units due to non-valent secondary (Au···S and S···Cl) interactions promotes the formation of a supramolecular 2D pseudopolymer structure of the complex. Thermolysis of this complex was studied by the simultaneous thermal analysis method.

An ionic Au(III)-Zn(II) dithiocarbamato-chlorido compound of [H3O][Au{S2CN(CH2)5}2]3[ZnCl4]2 (1) has been synthesised by the reaction of binuclear zinc(II) pentamethylenedithiocarbamate with a H[AuCl4]/2.0 M HCl solution. The obtained complex was successfully characterised by FT-IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. There are six ionic moieties in the unit cell of 1: (i) three dithiocarbamato-gold(III) cations, one of which is structurally inequivalent to the other two; (ii) two symmetrically related tetrachloridozincate(II) anions and (iii) one hydronium cation that is disordered over four positions with equal occupancies of 0.25. The compound exhibits a rather complicated supramolecular structure, including pseudo-binuclear gold-rich [Au2(S2CNPm)4]2+ cations and {[ZnCl4]2}4– counter anions, which are stabilised by secondary Au···S and Cl···Cl interactions, respectively. In turn, the former pseudo-binuclear formations involving centrosymmetric mononuclear cations of [Au(S2CNPm)2]+ give the pseudo-polymeric cationic chains of (···[Au2(S2CNPm)4]2+···[Au(S2CNPm)2]+···)n; while the latter, pseudo-binuclear zinc(II) anions, {[ZnCl4]2}4–, as the double linkers combine the neighbouring cationic chains yielding a two-dimensional pseudo-polymeric network. The results on the biological activity of 1 in vitro against the non-pathogenic strain Mycolicibacterium smegmatis (MIC 0.05 µg/disc) and virulent strains Mycobacterium tuberculosis H37Rv (0.14–0.19 µg/mL) and CN-40 (0.11–0.14 µg/mL) indicate a high efficiency of the studied Au(III)–Zn(II) compound against mycobacteria.

The interaction of zinc(II) di-iso-butyldithiocarbamate with [AuCl4]— anions in 2M HCl is studied. The result of chemisorption binding of gold(III) from a solution to the solid phase is the formation of double ionic complexes of the compositions [Au{S2CN(iso-C4H9)2}2]2[Zn2Cl6] (1) and [Au{S2CN(iso-C4H9)2}2][Zn{S2CN(iso-C4H9)2}Cl2] (2). The chemical identification of preparatively isolated crystalline compounds was performed by 13C CP-MAS NMR spectroscopy. According to single crystal X-ray diffraction data, structural units of complex 1 are a binuclear zinc anion and non-equivalent complex [Au{S2CN(iso-C4H9)2}2]+ cations: centrosymmetric A with the Au(1) atom and С – Au(3) and non-centrosymmetric В – Au(2). With the participation of secondary Cl⋯S bonds (3.2407 Å and 3.2756 Å), В cations and anions form supramolecular ionic pairs. The structure of 2 in turn involves the centrosymmetric gold(III) cation whose counterion is a mixed-ligand dithiocarbamato-chlorido anion of zinc(II). Pairs of non-equivalent secondary Cl⋯S bonds (3.2337 Å and 3.3151 Å) combine the ionic structural units of 2 into zigzag-like pseudo-polymeric chains along which the alternation of complex cations and anions is noted. Thermolysis of complexes in cationic and anionic parts is accompanied by the quantitative regeneration of bound gold along with the formation of ZnCl2 and ZnS.

Изучено взаимодействие ди-изо-бутилдитиокарбамата цинка с анионами [AuCl4]- в 2M HCl. Результатом хемосорбционного связывания золота(III) из раствора в твердую фазу является образование двойных ионных комплексов состава [Au{S2CN(iso-C4H9)2}2]2[Zn2Cl6] (1) и [Au{S2CN(iso-C4H9)2}2][Zn{S2CN(iso-C4H9)2}Cl2] (2). Химическая идентификация препаративно выделенных кристаллических соединений выполнена методом CP-MAS ЯМР 13C. Согласно РСА, структурные единицы комплекса 1 — биядерный анион цинка и неэквивалентные комплексные катионы золота(III) [Au{S2CN(iso-C4H9)2}2]+: центросимметричные A с атомом Au1 и С — Au3 и нецентросимметричный В — Au2. При участии вторичных связей Cl⋯S (3.2407 Å и 3.2756 Å) катионы В и анионы формируют супрамолекулярные ионные пары. Структура 2, в свою очередь, включает центросимметричный катион золота(III), противоионом которого является разнолигандный дитиокарбаматно-хлоридный анион цинка. Пары неэквивалентных вторичных связей Cl⋯S (3.2337 Å и 3.3151 Å) объединяют ионные структурные единицы 2 в зигзагообразные псевдополимерные цепи, по длине которых отмечается чередование комплексных катионов и анионов. Термолиз комплексов в части катионов и анионов сопровождается количественной регенерацией связанного золота, а также формированием ZnCl2 и ZnS.

The interaction of mercury(II) dibutyl dithiocarbamate (BuDtc) with [AuCl4]− anions in 2 M HCl was studied. The heterogeneous reaction of chemisorption binding of gold(III) from the solution leads to heteronuclear Au(III)–Hg(II) pseudo-polymeric complexes of the ionic type: ([Au{S2CN(C4H9)2}2]2[Hg2Cl6])n (I) and ([(C4H9)2NH2]0.5[Au{S2CN(C4H9)2}2]1.5[Hg2Cl6])n (II), whose crystal and supramolecular structures were determined by X-ray diffraction analysis (CIF files CCDC nos. 1965151 (I) and 1965152 (II)). The cationic part of each compound is represented by two structurally nonequivalent complex ions [Au{S2CN(C4H9)2}2]+ (A and B) being conformers. The structure of compound II additionally contains the dibutylammonium cation. In both cases, binuclear [Hg2Cl6]2– is a counterion (centrosymmetric in the structure of compound I and noncentrosymmetric in the structure of compound II). Owing to the secondary interactions Au···S and S···Cl (as well as hydrogen bonds N–H···Cl in compound II), all ionic structural units participate in the construction of pseudo-polymeric cationic and cation-anionic chains, which are combined into a complicatedly organized 2D supramolecular network (in I) or 3D framework (in II). The thermal behavior of compounds I and II was studied by simultaneous thermal analysis. The thermolysis of the complexes is accompanied by the quantitative regeneration of bound gold, liberation of HgCl2, and partial transformation of the latter into HgS.

Novel pseudo-polymeric complexes of gold(III)-mercury(II) with cyclic alkylene dithiocarbamate ligands: ([Au{S 2 CN(CH 2 ) 6 } 2 ][HgCl 3 ]) n , ([Au{S 2 CN(CH 2 ) 6 } 2 ] 2 [HgCl 4 ]·H 2 O) n , and ([Au{S 2 CN(CH 2 ) 4 O} 2 ] 2 [Hg 2 Cl 6 ]) n have been obtained and structurally characterized. The sophisticated supramolecular structure of the obtained compounds is realized due to secondary non-valent Au⋯S interactions and includes mononuclear and binuclear cations and anions as structural units as well as cationic and anionic polymer chains. The thermal behavior of the obtained complexes has been studied by means of simultaneous thermal analysis. The products of thermal transformations of the complexes are reduced elemental gold and HgCl 2 .

A new representative of mercury(II) dithiocarbamate complexes, crystalline bis(morpholinedithiocarbamato- S , S ')mercury(II) with the pseudo-1D-polymeric structure, is preparatively synthesized. The structure is characterized by 13 С and 15 N MAS NMR spectroscopy and X-ray diffraction analysis (CIF file CCDC no. 1821609). Pairs of symmetric secondary Hg⋅⋅⋅S bonds (3.400 Å) combine mononuclear [Hg{S 2 CN(CH 2 ) 4 O} 2 ] molecules, including planar polygons [HgS 4 ], into a linear pseudo-polymeric chain. The study of the thermal behavior shows that the two-stage mass loss detected by thermogravimetry is due to the thermal destruction of the complex with the formation of HgS and its subsequent sublimation.

A new representative of mercury(II) dithiocarbamate complexes, crystalline bis(morpholinedithiocarbamato-S,S')mercury(II) with the pseudo-1D-polymeric structure, is preparatively synthesized. The structure is characterized by 13С and 15N MAS NMR spectroscopy and X-ray diffraction analysis (CIF file CCDC no. 1821609). Pairs of symmetric secondary Hg⋅⋅⋅S bonds (3.400 Å) combine mononuclear [Hg{S2CN(CH2)4O}2] molecules, including planar polygons [HgS4], into a linear pseudo-polymeric chain. The study of the thermal behavior shows that the two-stage mass loss detected by thermogravimetry is due to the thermal destruction of the complex with the formation of HgS and its subsequent sublimation.

New heteroleptic mercury( ii ) complexes [Hg 4 (S 2 CNPr 2 ) 6 (NO 3 ) 2 ] ( 1 ) and [Hg 4 (S 2 CNPr 2 ) 4 Cl 4 ] ( 2 ) were synthesized and characterized by single-crystal X-ray dif raction and 13 C and 15 N MAS NMR spectroscopy. In these complexes, the metal atoms are linked in pairs by bridging dipropyldithiocarbamate ligands (Pr 2 Dtc) to form tetranuclear cations and molecules. The further structural organization of compound 1 to the polymeric chains [Hg 4 (S 2 CNPr 2 ) 6 (NO 3 ) 2 ] n occurs due to the linking of [Hg 4 (S 2 CNPr 2 ) 6 ] 2+ cations by pairs of bridging nitrate groups. The formation of the supramolecular polymeric structure of 2 is determined by pairwise secondary Hg⋯Cl bonds between the cyclic [Hg 4 (S 2 CNPr 2 ) 4 Cl 4 ] molecules, in which the central eight-membered metallocycle [Hg 4 S 4 ] adopts a distorted chair conformation. The thermal behavior of compounds 1 and 2 was studied by simultaneous thermal analysis.

The chemisorption binding of gold(III) by freshly precipitated binuclear zinc dithiocarbamates [Zn 2 (S 2 CNR 2 ) 4 ] from solutions in 2 M HCl makes it possible to obtain heteroligand complexes [Au(S 2 CNR 2 )Cl 2 ]: R = CH 3 ( I ), iso -C 3 H 7 ( II ); R 2 = (CH 2 ) 6 ( III ). The structural organization of complexes I , II , and III is determined by X-ray diffraction analysis (CIF files CCDC no. 1813107, 1813369, and 1813108, respectively). The distorted square–planar structure of the cis -[AuS 2 Cl 2 ] chromophores shows the low-spin dsp 2 -hybrid state of the central gold atom. Pairwise secondary interactions Au⋅⋅⋅S between the adjacent molecules in complexes I and III result in the building of zigzag polymer chains (⋅⋅⋅[Au{S 2 CN(CH 3 ) 2 }Cl 2 ]⋅⋅⋅) n and binuclear aggregates [Au{S 2 CN(CH 2 ) 6 }Cl 2 ] 2 at the supramolecular level. Complex II is presented by discrete molecules [Au{S 2 CN( iso -C 3 H 7 ) 2 }Cl 2 ]. According to the simultaneous thermal analysis data, the single final product of the thermolysis of compounds I–III is reduced elemental gold.