New crystalline pseudo-polymer complex [AuS2CN(CH2)62]4[Ag5Cl9] (I) was obtained by binding gold(III) with silver(I) hexamethylenedithiocarbamate from an AuCl3/2.5 M NaCl solution. Complex I was isolated in a preparative yield and structurally characterized. The X-ray diffraction (XRD) data (CIF file CCDC no. 2205197) show that the isomeric cations of [AuS2CN(CH2)62]+ (A : 2B : C) and complicated pentanuclear anion [Ag5Cl9]4– are the main structural units of the compound. The supramolecular self-organization of the ionic structural units in complex I occurs due to multiple secondary interactions Cl···S and Ag···S, hydrogen bonds C–H···Cl, and anagostic interactions C–H···Ag, resulting in the formation of the 3D pseudo-polymer framework. The thermal behavior of complex I is studied by simultaneous thermal analysis to find that the thermolysis of the double Au(III)–Ag(I) compound is accompanied by the quantitative regeneration of the bound metals under comparatively mild conditions.

New crystalline pseudo-polymer complex [Au{S2CN(CH2)6}2]4[Ag5Cl9] (I) was prepared by inding gold(III) with silver(I) dithiocarbamate from an AuCl3/2.5 M NaCl solution. Complex I is isolated in a preparative yield and structurally characterized. The X-ray diffraction (XRD) data (CIF file CCDC no. 2205197) show that the isomeric cations [Au{S2CN(CH2)6}2]+ (A : 2B : C) and complicated pentanuclear anion [Ag5Cl9]4– are the main structural units of the compound. The supramolecular self-organization of the ionic structural units in complex I occurs due to multiple secondary interactions Cl···S and Ag···S, hydrogen bonds C–H···Cl, and anagostic interactions C–H···Ag leading to the formation of the 3D pseudo-polymer framework. The thermal behavior of complex I is studied by simultaneous thermal analysis to find that the thermolysis of the double Au(III)—Ag(I) compound is accompanied by the quantitative regeneration of the bound metals under comparatively mild conditions.

New crystalline pseudo-polymer complex [Au{S2CN(CH2)(6)}(2)](4)[Ag5Cl9] (I) was obtained by binding gold(III) with silver(I) hexamethylenedithiocarbamate from an AuCl3/2.5 M NaCl solution. Complex I was isolated in a preparative yield and structurally characterized. The X-ray diffraction (XRD) data (CIF file CCDC no. 2205197) show that the isomeric cations of [Au{S2CN(CH2)(6)}(2)](+) (A : 2B : C) and complicated pentanuclear anion [Ag5Cl9](4-) are the main structural units of the compound. The supramolecular self-organization of the ionic structural units in complex I occurs due to multiple secondary interactions ClS and AgS, hydrogen bonds C-HCl, and anagostic interactions C-HAg, resulting in the formation of the 3D pseudo-polymer framework. The thermal behavior of complex I is studied by simultaneous thermal analysis to find that the thermolysis of the double Au(III)-Ag(I) compound is accompanied by the quantitative regeneration of the bound metals under comparatively mild conditions.

New crystalline pseudo-polymer complex [Au{S2CN(CH2)6}2]4[Ag5Cl9] (I) was prepared by inding gold(III) with silver(I) dithiocarbamate from an AuCl3/2.5 M NaCl solution. Complex I is isolated in a preparative yield and structurally characterized. The X-ray diffraction (XRD) data (CIF file CCDC no. 2205197) show that the isomeric cations [Au{S2CN(CH2)6}2]+ (A : 2B : C) and complicated pentanuclear anion [Ag5Cl9]4– are the main structural units of the compound. The supramolecular self-organization of the ionic structural units in complex I occurs due to multiple secondary interactions Cl···S and Ag···S, hydrogen bonds C–H···Cl, and anagostic interactions C–H···Ag leading to the formation of the 3D pseudo-polymer framework. The thermal behavior of complex I is studied by simultaneous thermal analysis to find that the thermolysis of the double Au(III)—Ag(I) compound is accompanied by the quantitative regeneration of the bound metals under comparatively mild conditions.

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.

The reaction of a solution of H[AuCl4] with 1,10-phenanthroline (Phen) in acetonitrile gave the complex (H2Phen)[AuCl4]Cl (I). According to X-ray diffraction data (CCDC no. 2165199), Phen exists in I as an unusual doubly protonated (cationic) form (H2Phen)2+. Binding of ionic structural units ([AuCl4]–, Cl–, and (H2Phen)2+) by D–H···Cl hydrogen bonds (D = N, C) gives rise to supramolecular 2D pseudo-polymer layers. The biological activity of I was measured for human ovarian carcinoma cells (SKOV3). Using MTT assay results, the half-maximal inhibitory concentration was calculated, demonstrating high selectivity of I to cancer cells in combination with low toxicity towards normal fibroblasts.

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.

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 tetra-chloridozincate(II) anions and (iii) one hydronium cation that is disordered over four positions with equal oc-cupancies 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 sec-ondary 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 mu g/disc) and virulent strains Mycobacterium tuberculosis H37Rv (0.14-0.19 mu g/mL) and CN-40 (0.11-0.14 mu g/mL) indicate a high efficiency of the studied Au(III)-Zn(II) compound against mycobacteria.

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.

The capability of silver(I) cyclo- hexamethylenedithiocarbamate to concentrate gold(III) from solutions characterized by a high level of salinity (5.15 M NaCl) into the solid phase has been established. The double chloroform-solvated Au(III)–Ag(I) complex [Au{S 2 CN(CH 2 ) 6 } 2 ] 2 [AgCl 2 ]Cl·2CHCl 3 ( I ) was preparatively isolated as an individual form of binding of [AuCl 4 ] – anions. The composition of the ionic structural units of compound I indicates that gold(III) binding from a solution to the solid phase is accompanied by the complete redistribution of the HmDtc ligands between the coordination spheres of Ag(I) and Au(III). Complex I characterized by IR spectroscopy, simultaneous thermal analysis, and X-ray structure analysis (CIF file CCDC no. 2051654) exhibits the supramolecular structure containing two oppositely charged pseudo-polymeric subsystems. Complex cations [Au{S 2 CN(CH 2 ) 6 } 2 ] + and anions [AgCl 2 ] – (in a ratio of 2 : 1) form a complicatedly organized cation-anionic pseudo-polymeric ribbon ({[Au(HmDtc) 2 ]⋅⋅⋅[AgCl 2 ]⋅⋅⋅[Au(HmDtc) 2 ]} + ) n due to secondary interactions Ag⋅⋅⋅S (3.2613 Å) and Au⋅⋅⋅Cl (3.2765 Å). The pseudo-polymeric ribbon consists of two rows of cations and a row of anions. The outer-sphere chloride ions combine the solvate chloroform molecules by two equivalent hydrogen bonds Cl⋅⋅⋅H–C yielding anion-molecular triads [Cl 3 CH⋅⋅⋅Cl⋅⋅⋅HCCl 3 ] – , which are involved in the formation of the supramolecular ribbon due to the secondary Cl⋅⋅⋅Cl interactions (3.4058 Å) between the nonequivalent chlorine atoms of the nearest solvate molecules. The study of the thermal behavior of complex I makes it possible to determine the character of thermolysis and conditions for the quantitative regeneration of bound gold.

Two new crystalline dithiocarbamato-chlorido complexes of mercury(II), [Hg-2{S2CN(C4H9)(2)}(2)Cl-2] (1) and [Hg-4{S2CN(iso-C4H9)(2)}(6)][Hg2Cl6] (2), have been prepared and chemically identified by solution (H-1, C-13) NMR and solid-state (C-13, N-15) CP-MAS NMR and FT-IR spectroscopy. The crystal, molecular and supramolecular structures of these compounds were established using single-crystal X-ray diffraction (XRD) analysis. The obtained complexes reveal two principally different types of structural organisation. In the structure of the former neutral complex, there are two isomeric doubly-bridged binuclear molecules [Hg-2(S2CNBu2)(2)Cl-2] ('A' and 'B'), whereas the latter compound comprises two ionic structural moieties: the tetranuclear cation [Hg-4(S2CNiBu2)(6)](2+) and the binuclear anion [Hg2Cl6](2-). In both ionic units, pairs of iBu(2)Dtc or chloride ligands, which perform a bridging structural function, combine with neighbouring mercury atoms. In turn, intermolecular/interionic secondary interactions Hg center dot center dot center dot S/Hg center dot center dot center dot Cl are involved in the formation of supramolecular structures of complexes 1/2, yielding pseudo-polymeric chains of (center dot center dot center dot'A'center dot center dot center dot'B'center dot center dot center dot)(n)/(center dot center dot center dot[Hg-4(S2CNiBu2)(6)]center dot center dot center dot[Hg2Cl6]center dot center dot center dot)(n), which exhibit alternation of isomeric molecules of 1/ionic moieties of 2 along their lengths. Despite the significant structural difference between the above complexes, we established, using simultaneous thermal analysis (STA), that both exhibit very similar thermal behaviour. Moreover, during the thermal transformations of both compounds 1 and 2, the same two substances are generated: HgCl2 and HgS.

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.