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The present work is directed toward preparation and structural characterization of two novel Cu(I) arylsulfonate π-complexes with 3-allyl-2-thiohydantoin, namely [Cu2(Hath)4](C6H5SO3)2 (1) and [Cu2(Hath)4](p-CH3C6H4SO3)2·2H2O (2) (Hath = 3-allyl-2-thiohydantoin), obtained by the means of alternating current electrochemical synthesis and studied with X-ray diffraction method. In both structures, the inner coordination sphere is represented by the cationic dimer [Cu2(Hath)4]2+ with one crystallographically independent copper(I) atom which has a trigonal pyramidal coordination environment formed by three Hath thiogroup S atoms and double C=C bond of its allyl group. [Cu2(Hath)4]2+ fragments in both coordination compounds are very similar, despite some divergences such as a big difference in Cu−S distance to the apical S atom (3.0374(8) Å in 1 and 2.7205(9) Å in 2). This difference was explained by the impact of the system of weak interactions, which are quite different.

Novel tetrachloridoruthenium(III) complex Na[trans-RuCl4(DMSO)(PyrDiaz)] (3) with pyridine-tethered diazenedicarboxamide PyrDiaz ligand (PyrDiaz = N1-(4-isopropylphenyl)-N2-(pyridin-2-ylmethyl)diazene-1,2-dicarboxamide) was synthesized by direct coupling of PyrDiaz with sodium trans-bis(dimethyl sulfoxide)tetrachloridoruthenate(III) (Na-[trans-Ru(DMSO)2Cl4]). Compound 3 is the analogue of the antimetastatic Ru(III) complex NAMI-A and NAMI-Pyr. Single crystal X-ray diffraction analysis revealed that the compound 3 is a polymeric complex with the ruthenium and sodium centres.

Four copper(I) π-complexes: [Cu(Hapn)NO3]NO3 (1), [Cu(Hapn)(H2O)2]SiF6 (2), [Cu(Hapn)(H2O)BF4]BF4·H2O (3) and [Cu(Hapn)(NH2SO3)2] (4) were prepared using alternating-current electrochemical technique, starting from alcohol solutions of 3-(prop-2-en-1-ylamino)propanenitrile (apn) titrated with appropriate acid and copper(II) salts (Cu(NO3)2∙3H2O, CuSiF6∙4H2O, Cu(BF4)2∙6H2O or Cu(NH2SO3)2∙xH2O, respectively). Obtained compounds were characterized by single-crystal X-ray diffraction and partially by IR spectroscopy. In the structures of complexes 1, 2 and 4 Cu(I) cation possesses a tetrahedral environment formed by the C=C bond of one organic cation Hapn, the N atom of ciano group from another Hapnmoiety, and two O atoms (from NO3– anions in 1, from H2O molecules in 2) or N atoms (NH2SO3– anions in 4). In compound 3 strongly pronounced trigonal-pyramidal coordination environment of Cu(I) is formed by a mid-point of C=C-bond of one Hapncation, nitrogen atom (of cyano group) of another Hapn unit, O atom of H2O molecule in the basal plane, and F atom of BF4– anion at the apical position.

Salts containing [Xe2F3]+ cations and [MF6]- anions (M = Ru, Ir) were synthesized by the oxidation of metal with excess of XeF2 in anhydrous hydrogen fluoride (aHF) as a solvent. Single crystals of [Xe2F3][RuF6]∙XeF2, [Xe2F3][RuF6] and [Xe2F3][IrF6] were grown by slow evaporation of the solvent. [Xe2F3][RuF6]∙XeF2 crystallizes in a triclinic P-1 space group (a = 8.3362(1) Å, b = 8.8197(2) Å, c = 9.3026(4) Å; α = 68.27(1) °, β = 63.45(1) °, γ = 82.02 °, V = 568.09(9) Å3 (Z = 2)). Discrete [Xe2F3]+, XeF2 and [RuF6]- units are found in the asymmetric unit. [Xe2F3][RuF6] and [Xe2F3][IrF6] compounds are isostructural and crystalize in a monoclinic C/c space group (a = 14.481(3) Å (Ru); 14.544(3) Å (Ir); b = 8.0837(8) Å (Ru), 8.0808(7) Å (Ir), c = 10.952(2) Å (Ru), 11.014(2) Å (Ir); β = 136.825(6) ° (Ru), 139.954(7) °,V = 877.2(3) Å3 (Ru), 883.6(3) Å3 (Ir); Z = 4). The asymmetric unit in the [Xe2F3][MF6] (M = Ru, Ir) consists of one [Xe2F3]+ and one [MF6]- unit.

By means of the alternating current electrochemical technique two new [Cu(2-Apyt)NO3] (1) and [Cu(2-Apyt)(H2O)](BF4) (2) π-compounds have been obtained starting from the mixture of 1-allyl-5-(2-pyridyl)-2H-tetrazole (1-Apyt) and 2-allyl-5-(2-pyridyl)-2H-tetrazole (2-Apyt) and corresponding copper(II) salts, and structurally studied. Selective towards 2-allyl- isomer complexation results in a formation of 2-Apyt complexes. Copper(I) ion in both 1 and 2 complexes is coordinated by allylic C=C bond, one pyridyl and one tetrazole N atoms. In both structures Cu+ center adopts distorted tetrahedral surrounding, being additionally coordinated by oxygen of NO3- in 1 and H2O moiety in 2. Coordination of bridging nitrate anion causes the dimeric [Cu(2-Apyt)NO3]2 fragment formation, while participation of H2O in metal coordination leads to infinite {[Cu(2-Apyt)(H2O)]2+}n chain construction. To analyze interactions between the particles in 1 and 2 Hirshfeld surface analysis was performed.