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The molecular bis-chelate complex (2-{[(2-hydroxyethyl-κO)amino-κN]methyl}-6-methoxyphenolato-κO)(2-{[(2-hydroxyethyl)imino-κN]methyl}-6-methoxyphenolato-κO)copper(II), [Cu(C10H14NO3)(C10H12NO3)] or [Cu(HL im)(HL am); HL im = C10H14NO3; HL am = C10H12NO3, represents the first compound containing a salicylidene-2-ethanolamine type ligand in both imino HL im (Schiff base) and amino HL am (reduced Schiff base) forms that has been structurally characterized on the basis of X-ray data. Two molecules of the monodeprotonated ligands coordinate the CuII ion in an (N,O phen)-bidentate and an (N,O phen,O alc)-tridentate fashion in the case of the imino and amino forms, respectively. The shape of the CuN2O3 coordination polyhedron is a distorted square-pyramid (geometry index τ5 = 0.26). Intermolecular N—H...O and O—H...O hydrogen bonds, involving H atoms of the amino and hydroxyethyl groups, create a two-dimensional supramolecular array extending parallel to (010).

Please provide a synopsis (of no more than two sentences) for inclusion in the Contents listing of the journal., The title compounds, di-μ-chlorido-bis­({2-[(η-2,3)-(prop-2-en-1-yl)sulfan­yl]pyridine-κN}copper(I)), [Cu2Cl2(C8H9NS)2], and di-μ-bromido-bis­({2-[(η-2,3)-(prop-2-en-1-yl)sulfan­yl]pyridine-κN}copper(I)), [Cu2Br2(C8H9NS)2], were obtained by alternating-current electrochemical synthesis starting from an ethano­lic solution of 2-[(prop-2-en-1-yl)sulfan­yl]pyridine (Psup) and the copper(II) halide. The isostructural crystals are built up from centrosymmetric [Cu2 Hal 2(Psup)2] dimers, which are formed due to the π,σ-chelating behavior of the organic ligand. In the crystals, the dimers are linked by C—H⋯Hal hydrogen bonds as well as by aromatic π–π stacking inter­actions into a three-dimensional network.

The title compound was obtained via the reaction of 1-azido-2,3,4,5,6-penta­fluoro­benzene with 4,4,4-tri­fluoro-1-(p-tol­yl)butane-1,3-dione using tri­ethyl­amine as a base catalyst and solvent. In the crystal, the mol­ecules are linked by C—H⋯F and C—H⋯O hydrogen bonds as well as by aromatic π–π stacking inter­actions into a three-dimensional network., The title compound, C17H7F8N3O, was obtained via the reaction of 1-azido-2,3,4,5,6-penta­fluoro­benzene with 4,4,4-tri­fluoro-1-(p-tol­yl)butane-1,3-dione using tri­ethyl­amine as a base catalyst and solvent. The dihedral angles between the penta­fluoro­phenyl (A), triazole (B) and p-tolyl (C) rings are A/B = 62.3 (2), B/C = 43.9 (3) and A/C = 19.1 (3)°. In the crystal, the mol­ecules are linked by C—H⋯F and C—H⋯O hydrogen bonds as well as by aromatic π–π stacking inter­actions into a three-dimensional network. To further analyse the inter­molecular inter­actions, a Hirshfeld surface analysis was performed.

Electrochemical alternating current synthesis starting from an ethanol solution of CuSO4 · 5H2O and allylamine in the presence of solid sodium azide results in formation of Cu[C3H5NH2]N3. The trigo...

By means of electrochemical alternating current synthesis starting from a methanol solution of CuCl2·2H2O and dabco (dabco = 1,4-diazabicyclo[2.2.2]octane) titrated with HCl, a salt of (H2dabco)Cu2Cl4 composition (I) was obtained. It consists of infinite chains composed from vertex-sharing Cu2Cl2 rhombs and diprotonated (H2dabco)2+ cations. The use of ethanol as a solvent and a higher CuCl2·2H2O : dabco ratio lead to the formation of the (H2dabco)Cu3Cl5 (II) salt. Its inorganic part consists of infinite corrugated ribbons in which each half-loop is closed by an additional chloride bridge. The decrease of the CuCl2·2H2O : dabco ratio leads to the appearance of the compound (H2dabco)5Cu12Cl22·H2O (III), which contains unique anionic 2-D (CuI12Cl22)10− networks. Syntheses carried out in aprotic solvents led to the formation of known (H2dabco)CuCl3 salt. Recrystallization of the compound III from dymethyl sulfoxide (DMSO) unexpectedly led to the appearance of two copper(I) chloride complexes with in situ formed dymethylsulfide (DMS): the already known CuCl·DMS and observed for the first time (CuCl)7(DMS)3 (IV). The latter contains two types of infinite copper–chloride columns, consisting of cubane-like Cu4Cl4 and prismane-like Cu6Cl6 clusters. μ-Sulfur (DMS) bridges connect the above columns to form a 3-D network. Crystallisation from the initial CuCl2·2H2O – dabco – HCl mixture yielded deep-red crystals of the unknown (H2dabco)Cu2IICl6 salt (V) among other products. Its structure consists of infinite cupro(II)-chloride chains and discrete (H2dabco)2+ cations.

The present work is directed toward preparation and structural characterization of two novel Cu(I) arylsulfonate π-complexes with 3-allyl-2-thiohydantoin, namely [Cu 2 ( Hath ) 4 ](C 6 H 5 SO 3 ) 2 ( 1 ) and [Cu 2 ( Hath ) 4 ]( p -CH 3 C 6 H 4 SO 3 ) 2 ·2H 2 O ( 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 [Cu 2 ( 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. [Cu 2 ( 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) A in 1 and 2.7205(9) A in 2 ). This difference was explained by the impact of the system of weak interactions, which are quite different.

By treating gaseous, liquid, or solid fluorides with UV-photolyzed O2/F2 mixtures and by treating solid oxides with UV-photolyzed F2 (or O2/F2 mixtures) in liquid anhydrous HF at ambient temperature, we investigated the possibility of the preparation of O2MIIIF4 (M = B, Fe, Co, Ag), O2MIVF5 (M = Ti, Sn, Pb), (O2)2MIVF6 (M = Ti, Ge, Sn, Pb, Pd, Ni, Mn), O2MIV2F9 (M = Sn), O2MVF6 (M = As, Sb, Au, Pt), O2MV2F11 (M = Pt), O2MVIF7 (M = Se), (O2)2MVIF8 (M = Mo, W), and O2MVIIF8 (M = I). The approach has been successful in the case of previously known O2BF4, O2MF6 (M = As, Sb, Au; Pt), O2GeF5, and (O2)2(Ti7F30). Novel compounds O2GeF5·HF, α-O2Sn2F9 (1-D), and the HF-solvated and nonsolvated forms of β-O2Sn2F9 (2-D) were synthesized and their crystal structures determined using single-crystal X-ray diffraction. The crystal structures of all of these materials arise from the condensation of octahedral MF6 (M = Ge, Sn) units. The anion in the crystal structure of O2GeF5·HF is comprised of infinite ([GeF5]-)∞ chains of GeF6 octahedra that share common vertices. The HF molecules and O2+ cations are located between the chains. The crystal structure of α-O2SnF9 (1-D) is constructed from [O2]+ cations and polymeric ([Sn2F9]-)∞ anions which appear as two parallel infinite chains comprised of SnF6 units, where each SnF6 unit of one chain is connected to a SnF6 unit of the second chain through a shared fluorine vertex. The single-crystal structure determination of [O2][Sn2F9]·0.9HF reveals that it is comprised of two-dimensional ([Sn2F9]-)∞ grids with [O2]+ cations and HF molecules located between them. The 2-D grids have a wavelike conformation. The ([Sn2F9]-)∞ layer contains both six- and seven-coordinated Sn(IV) atoms that are interconnected by bridging fluorine atoms. A new, more complex [O2]+ salt, O2[Hg(HF)]4[SbF6]9, was prepared. In its crystal structure, the Hg atoms bridge to SbF6 units to form a 3-D framework. The O2+ cations are located inside the voids while the HF molecules are bound to Hg atoms through the F atom. Attempts to prepare several chlorine analogues of O2+ fluorine salts (i.e., O2TiCl5 and O2MCl6 (M = Nb, Sb)) failed.

The title compound, C11H9F3N4S, was synthesized from 2-(trifluoromethyl)aniline by a multi-step reaction. It crystallizes in the non-centrosymmetric space groupPna21, with one molecule in the asymmetric unit, and is constructed from a pair of aromatic rings [2-(trifluoromethyl)phenyl and tetrazole], which are twisted by 76.8 (1)° relative to each other because of significant steric hindrance of the trifluoromethyl group at theorthoposition of the benzene ring. In the crystal, very weak C—H...N and C—H...F hydrogen bonds and aromatic π–π stacking interactions link the molecules into a three-dimensional network. To further analyse the intermolecular interactions, a Hirshfeld surface analysis, as well as interaction energy calculations, were performed.

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Chemical reactions between ethane-1,2-diamine [C2H4(NH2)2; ethylenediamine, abbr. en] and 1,3,5-triazine-2,4,6-triamine [C3H6N6; melamine, abbr. mel], with titanium tetrafluoride (TiF4) were carried out in liquid anhydrous hydrogen fluoride (aHF). The latter acted in a dual role: as a reagent and as a solvent. The n(en): n(TiF4) = 2:1, 1:1, 1:3, 1:4, and n(mel): n(TiF4) = 2:1, 1:1, 1:2, 1:3, 1:4 M ratios were studied. Crystallizations of the products from the saturated HF solutions yielded single crystals of [enH2]F2·2HF, previously known [enH2][TiF6] and three new perfluoridotitanate(IV) salts, i.e., [enH2][TiF6]·HF, [enH2]0.5[TiF5] and [melH2][TiF6]·HF. Their crystal structures were determined including the crystal structure of the low-temperature modification of [enH2][TiF6]. The [enH2]0.5[TiF5] phase represents the first example of a structurally characterized perfluoridotitanate(IV) compound with a double charged cation, where instead of the usual octahedral [TiF6]2− monomer, another kind of anion is present, i.e., polymeric chain-like ([TiF5]−)∞ anion. The reactions in en/TiF4/HF and mel/TiF4/aHF systems are not selective enough to enable syntheses of individual [enH2]2+ and [melH2]2+ perfluoridotitanates(IV) in large quantities.

The present work is directed toward preparation, structure and optical property characterization of tetrazole-containing Cu(I) compounds. By means of the alternating-current electrochemical techniq...

International audience; A family of eight polymeric manganese(III) complexes with the general formula Mn(HL1,2)2X (H2L1 = 2[(2-hydroxyethyl)iminomethyl]phenol, H2L2 = 2[(2-hydroxyethyl)iminomethyl]-6-methoxy-phenol), while X = Cl (1, 5), Br (2, 6), I (3, 7), NCS (4, 8) for H2L1 and H2L2, respectively were obtained using “the direct synthesis” approach, i.e., the oxidative dissolution of the manganese powder in the presence of a Schiff base (SB), an ammonium salt, and oxygen in the air. Single crystal X-ray diffraction studies for the new complexes 2, 3, 4, and 8 were compared with the previously reported crystallographic data for 1 and 7, showing that all complexes possess a one-dimensional polymeric structure. The main structural units in 1–7 are cationic chains [Mn(HL1,2)2]nn+ and anions X– linked together via electrostatic interactions and hydrogen bonds, while the complex 8 consists of polymeric chains of neutral [Mn(HL2)2(NCS)]n units. The SB ligands are mono-deprotonated as HL–, and coordinated by the metal atoms in a tridentate chelate-bridging fashion generating chains with Mn centers connected by double or single {−N–C–C–O−} bridges for 1–7 and 8, respectively. In 8, bridging and pure chelate modes of HL2– occur. The intrachain MnIII···MnIII distances vary from 5.700(2) Å for 1 to 6.6950(4) Å for 8. A high-field electron paramagnetic resonance study reveals narrow ranges of the zero-field splitting parameters of the spin Hamiltonian, D and E (−3.22 cm–1 to −3.44 cm–1 and −0.16 cm–1 to −0.21 cm cm–1, respectively) and demonstrates a clear correlation between the degree of the structural distortion and the E parameter. The ab-initio CASSCF method was employed to calculate the zero-field splitting parameters. “Broken symmetry” density functional theory calculations were performed to estimate the magnitude of the Mn–Mn exchange interactions.

This work is directed toward the synthesis, structural characterization and NLO properties investigation of the novel copper(I) nitrate π,σ-coordination compound [Cu(Anor)(CH3CN)](NO3) (1) based on 1-allyl-3-norbornan-thiourea (Anor). In the crystal structure of both Anor and 1, the organic part is disordered because of the superposition of (2S)-exo and (2R)-exo enantiomers. The Anor ligand in 1 acts as a bridging ligand, connecting Cu(I) ions into the cationic coordination polymer {[Cu(Anor)(CH3CN)]+}n through η2-allyl group and the thiourea S atom. The H atoms of the –NH– groups in the Anor structure participate in N—H···S hydrogen bonding and form an infinite hydrogen-bonded layer, while the same ligand groups in the organometallic chain of 1 are linked by bifurcated N—H···O bonds to the two O atoms of the same NO3– anion. The second-order nonlinear optical properties for Anor and coordination compound 1 were studied at 1064 nm generated by a nanosecond pulsed Nd:YAG laser. The corresponding values of the average first-order NLO hyperpolarizabilities calculated by the DFT method and the B3LYP functional for the Anor ligand molecule and the cation fragment confirm the experimentally determined much higher second-harmonic generation efficiency for compound 1.

By means of alternating current-electrochemical synthesis novel Cu(I) π-complex of the composition [Cu4(dapt)2Cl4]∙0.38EtOH (dapt – (2Z)-3-allyl-2-(allylimino)-1,3-thiazolidin-4-one was obtained and studied by X-ray single crystal diffraction and IR-spectroscopy. π-Complex crystallizes in the trigonal centrosymmetric space group R‾3 and is built of dimeric tetranuclear [Cu4(dapt)2Cl4] fragments. Disordered solvent molecules are located in the voids of crystal structure. It was shown experimentally a high coherent laser induced second order effects like second harmonic generation. Principal role of the absorption due to 3dCu states is shown.

In the present study, the oxidative dissolution of metallic copper has been explored with the intention to prepare some new complexes with urotropine (hmta) and triethylenediamine (dabco) ligands. All the compounds synthesized were characterized by single-crystal X-ray diffraction and Raman spectroscopy. Reactions performed in a DMSO/CuCl2∙2H2O mixture resulted in [(μ-Cl)2CuI(hdabco+)CuI(μ-Cl)(κS-DMSO)]n and [CuICl(hmta)2] complexes. Their isostructural bromide analogs [(μ-Br)2CuI(hdabco+)CuI(μ-Br)(κS-DMSO)]n and [CuIBr(hmta)2] were prepared by the reaction of elemental copper with respective ligands in a DMSO/CBr4 mixture. Early interrupted reaction of the copper wire with the DMSO/CBr4/dabco solution resulted in an appearance of crystals of the [CuI2Br2(CO)2(dabco)]n carbonyl complex on the copper surface. It arises with the participation of in situ formed carbon monoxide. Despite the identical stoichiometry, the crystal structure of the [Cu2Br2(CO)2(dabco)]n complex is markedly different from t...

A distinction in the behaviour of several hydrazines as N-nucleophiles in the recently developed one-pot method for pyrimidine core annulation via 1H-tetrazole ring cleavage was examined. The product structures, 2,3-diamino- or hydrazino derivatives of thieno[3,2-d]pyrimidin-4(3H)-ones, thieno[2,3-d]pyrimidin-4(3H)-ones and [1]benzofuro[3,2-d]pyrimidin-4(3H)-one, were elucidated based on NMR and single crystal X-ray analysis.

The digestion of the natural mineral ilmenite, FeTiO3, in hydrofluoric acid results in the formation of mixed-valency hydrated iron fluoridotitanate. High quality single crystals of the compound were obtained and their crystal structures at room temperature (RT, 296 K, trigonal, R 3 ¯ , Z = 3) and at 233 K, which is below the ferroelastic phase transition (271.5–275.5 K (LT), monoclinic P21/c or triclinic P 1 ¯ , Z = 2) were determined by X-ray diffraction. Both iron and titanium are present in a mixed-valency state. The cationic sublattice is characterized by the presence of hydrated [Fe(H2O)6]2+, [Fe(H2O)5F]2+, and [Ti(H2O)5F]2+ octahedra, while only [TiF6]2– octahedra form the anionic sublattice with partial isomorphous substitution of hydroxide ions for fluoride. The overall formula of the compound studied was determined to be {[Fe(H2O)6]1–x–y[Fe(H2O)5F]x[Ti(H2O)5F]y}[Ti(OH)zF6–z] (x, y ≤ 0.1; z ≤ 0.5). Its thermal behavior is characterized by two-stage dehydration followed by pyrohydrolysis with the HF evolution in accordance with the existence of three crystallographically distinct O–H•••F hydrogen bonds.

For the first time, natural product Cytisine was successfully used as a reagent for thermal-activated transannulation of 1H-tetrazoles and a series of cytisine-thienopyrimidinone conjugates were obtained in high yields (85-95%). Structures of conjugates were analysed by 1H and 13C NMR. Moreover, the structure of compound 3c was also proven by a single crystal X-ray diffraction analysis and intermolecular interactions were studied by the Hirshfeld surface analysis. The molecular docking studies and primary anticancer activity screening of selected synthesised conjugates have been performed.

New multifunctional 1,2,4-triazole based allyl-derivative as the ligand L (3-allylsulfanyl-4-allyl-5-phenyl-4H-1,2,4-triazole) revealed an ability to form stable binuclear copper(I) π-complexes. A series of related Cu(I) halides π-complexes, [Cu2(L)2X2] (X = Cl, 1a; Br, 1b; I, 1c), [Cu2(L)2I2]2 (1c’), [Cu2(L)2(CuCl2)2] (2), [Cu2(L)2Cu2Br4] (3) was obtained by alternating-current electrochemical synthesis, starting from acetonitrile solutions of the ligand L and CuX2 (in the case of 1a, 1b, 2, 3) or I2 (1c, 1c’). This is the first notice of using iodine being reduced at copper electrodes under alternating current in the presence of a ligand for copper(I) iodide complexes synthesis. The crystal structures were determined by means of single crystal X-ray diffraction. The organic ligand acts as multidentate chelating σ,π-donor using triazole (tr) and η2-allyl moieties, resulting in a formation of the dimeric {Cu2N4} core with a trigonal-pyramidal (2 N, C C + X) environment of the Cu cation. Packing polymorphism was revealed for the iodine complex. In the case of 2 and 3 the Cu centers participate in a formation of both – metal-organic cations and copper(I) halide anions. In structure 3, the copper(I)-halide subunit is organized in the Cu2(μ2-Br)2Br2 cluster that links organometallic moieties leading to a 1D ladder fragment. High inertia of complexes in acetonitrile solutions enabled a comparative evaluation of a strength of the Cu(I)–(C C) interaction by means of 1H NMR spectra. NMR spectroscopic studies are consistent with the structural analysis.

3,5-Diamino-1,2,4-triazolium fluoride-hydrogen-difluoride (HL)(H 2 L)(HF 2 ) 2 F ( I ) and heptafluorotantalate (H 2 L)TaF 7 ( III ) have been crystallized from 66% aqueous solution of hydrogen fluoride. Fluoride-trihydrogen-tetrafluoride (H 2 L)(H 3 F 4 )F ( II ) has been crystallized from anhydrous hydrogen fluoride (L – 3,5-diamino-1,2,4-triazole). Single-crystal X-ray structure determination has shown the presence of doubly protonated H 2 L 2+ cations in each structure. In structures of I and II salts doubly protonated H 2 L 2+ units are associated with F − anions via strong hydrogen bonds, and charge balance is provided by HF 2 − and H 3 F 4 − anions respectively. The N H⋯F and N H⋯N hydrogen bonds play an important role in the formation of 3-D structures of all compounds.

Reactions between XeF2, MnF3 and UV-irradiated elemental F2 in anhydrous HF have yielded [XeF5]2[MnF6] and XeF5MnF5; meanwhile, [XeF5]4[Mn8F36] has been observed as a minor phase upon the crystallization of the product obtained by fluorination of an n(XeF2)/n(MnF3) = 1:3 mixture in the presence of an UV source. The crystal structure of [XeF5]2[MnF6] is isotypic with the known [XeF5]2[PdF6]. Its asymmetric structural unit consists of two crystallographically unique [XeF5]+ cations and a [MnF6]2– anion. The single-crystal structure determination of XeF6·2MnF4 reveals that it is better formulated as [XeF5]4[Mn8F36]. Discrete octameric [Mn8F36]4– anions are built from eight MnF6 octahedra, each sharing three vertices, in the shape of a ring, which is different from the previously known cubic [Ti8F36]4– anion. The main structural feature of the anionic part of the crystal structure of [XeF5][MnF5] (determined from both X-ray single-crystal and synchrotron X-ray powder diffraction data) is infinite zigzag chains of distorted MnF6 octahedra that share cis vertices. [XeF5][MnF5] is paramagnetic in the 296–200 K temperature range, with a Curie constant of C = 1.87 emu K mol–1 (µeff = 3.87 µB) and a Curie–Weiss temperature of θ = –9.3 K. Below 100 K, there is weak antiferromagnetic coupling between the MnIV ions, with a coupling constant of J = –1.3 cm–1. Raman spectra showed that [XeF5]2[MnF6] decomposes at ambient temperature in a He–Ne laser beam (power > 1.7 mW) to [XeF5][MnF5], with further decomposition to MnF3.

The fluoropolymers as FEP and PFA are widely used materials for making reaction vessels applied to experiments involving liquid anyhdrous HF, elemental F2 and various inorganic fluorides and fluoro-organic compounds. However, due to their permeability to gases and liquids, crystals of unexpected compounds can be sometimes grown during extended durations of the crystallizations. One of such examples is the growth of single crystals of (H3O)2Ce(BF4)5, which were grown unintentionally from the CeF3/BF3/aHF solution after five months of crystallization. Reaction between the La2O3 and excess of BF3 in anhydrous HF yielded a similar compound, i.e., (H3O)2La(BF4)5 upon crystallization. The attempts to prepare single crystals of analogous compounds of Nd and Sm failed. (H3O)2Ce(BF4)5 crystallizes in the monoclinic P21/n space group (No. 14) with a = 11.9160(14) A, b = 9.1551(12) A, c = 14.5290(14) A, β = 94.929(5)°, V = 1579.1(3) A3, and Z = 4 at 200 K. The crystal structure of (H3O)2La(BF4)5 is isotypic with cerium compound. Corresponding unit cell is monoclinic, P21/n space group (No.14), with a = 12.004(10) A, b = 9.197(2) A, c = 14.577(7) A, β = 94.459(9)°, V = 1604.5(17) A3 and Z = 4 at 100 K. The crystal structures of (H3O)2Ln(BF4)5 (Ln = La, Ce) consist of slabs formed from the Ln3+ cations interconnected with the [BF4]−anions. The oxonium cations are located in the space between the slabs. Ln3+ cations are nine-fold coordinated with a tricapped trigonal prismatic arrangement of F ligands.

The reaction of hydrazinium difluoride and TaF 5 in 66% hydrofluoric acid water solution resulted in the formation of rather unusual (N 2 H 6 ) 3 TaF 8 TaF 7 HF 2 compound. Similar procedure started from a TaF 5 NaF mixture performed in 35% HF water solution resulted in the formation of a Na 7 TaF 8 (TaF 7 ) 2 compound. Synthesis, crystal structures and Raman spectra of these new compounds are reported in this communication. The main feature of both compounds is the presence of discrete TaF 8 3− and TaF 7 2− anions in their crystal structures, which was also confirmed by Raman spectroscopy.

By means of alternating current-electrochemical synthesis starting from a mixture of 2-imino-3-(prop-2-en-1-yl)-1,3-thiazolidin-4-one (3-allylpseudothiohydantoin, napt) and 2-allylamino-1,3-thiazol-4(5H)-one (allylaminopseudothiohydantoin, aapt) hydrochlorides and corresponding copper(II) salts five new π-complexes, [Cu(napt)Cl] (1), [Cu2(aapt)2Cl]NO3 (2), [Cu2(aapt)2Cl]BF4 (3), [Cu2(aapt)2Cl]ClO4 (4) and [Cu2(aapt)2Cl]2SiF6·2H2O (5), were obtained and studied by X-ray single crystal diffraction and IR-spectroscopy. Napt and aapt molecules are selectively coordinated to Cu+ depending on the anion type. In crystals of 1 and 5, the organic ligands are attached to the metal in a chelating N,(C=C)-bidentate mode. The aapt molecule in 2-4 acts as a tridentate chelating ligand, being coordinated to the copper(I) ion through the heterocyclic N atom, carbonyl O atom, and C=C bond of allyl group, forming an original cationic [Cu2(aapt)2Cl]+ fragment with both a bridging Cl– ion and O atom of the C=O group....

The [Ag(H2O)2]SbF6, is triclinic, P1̅ (No. 2), with a=6.6419(3) Å, b=7.6327(3) Å, c=11.1338(3) Å, α=95.492(3)°, β=96.994(3)°, γ=113.535(4)°, V=507.13(4) Å3 at 150 K, and Z=3. There are two crystallographically non-equivalent Ag+ cations. The Ag1 is coordinated by two water molecules with Ag–OH2 distances equal to 2.271(2) Å forming in that way a discrete linear [Ag(H2O)2]+ cation. Additionaly, it forms two short Ag···F contacts (2.630(2) Å), resulting in AgO2F2 plaquette, and four long ones (2×3.001(2) Å and 2×3.095(2) Å) with fluorine atoms located below and above the AgO2F2 plaquette. The H2O molecules bridge Ag2 atoms into {–[Ag(μ-OH2)2]–}n infinite chains, with Ag–O distances of 2.367(2)–2.466(2) Å. The [Pd(H2O)4](SbF6)2·4H2O is monoclinic, P2 1 /a (No.14), with a=8.172(2) Å, b=13.202(3) Å, c=8.188(3) Å, β=115.10(1)o, V=799.9(4) Å3 at 200 K, and Z=2. Its crystal structure can be described as an alternation of layers of [Pd(H2O)4]2+ cations (interconnected by H2O molecules) and [SbF6]− anions. It represents the first example where [Pd(H2O)4]2+ has been structurally determined in the solid state. Four oxygen atoms provided by H2O molecules are in almost ideal square-planar arrangement with Pd–O bond lengths 2×2.004(5) Å and 2×2.022(6) Å. The [Cd(H2O)6](SbF6)2, is orthorhombic, Pnnm (No.58), with a=5.5331(2) Å, b=14.5206(4) Å, c=8.9051(3) Å, V=715.47(4) Å3 at 200 K, and Z=2. It consists of [Cd(H2O)6]2+ cations and [SbF6]− anions.

The reactions between the MO (M = Be, Mg, Ca, Sr, Ti, V, Nb, Mn, Ni, Cu, Pd, Zn, Hg, Sn, Pb) and SbF 5 in liquid aHF were investigated. Reactions with the MO (M = Mg, Ni, Cu and Zn) yielded H 3 OM(SbF 6 ) 3 compounds. Both BeO and PdO didn’t show any sign of reactivity meanwhile MO (M = V, Nb, Ti) gave products with M in oxidation state higher than two. The rest of the MO (M = Ca, Sr, Mn, Hg, Sn, Pb) formed mixtures of M(SbF 6 ) 2 , H 3 OSbF 6 and/or H 3 OSb 2 F 11 . Reactions between H 3 OSbF 6 and M(SbF 6 ) 2 (M = Fe, Co, Ni) also gave H 3 OM(SbF 6 ) 3 compounds, meanwhile similar attempts with H 3 OSbF 6 and M(SbF 6 ) 2 (M = Ca, Mn, Pd, Ag, Cd, Sn) to prepare [H 3 O] + /M 2+ /[SbF 6 ] − salts failled. However, slow crystallizations of H 3 OSbF 6 and M(SbF 6 ) 2 (M = Mn, Pd, Cd) mixtures resulted in the single crystal growth of new (H 3 O) 3 M(SbF 6 ) 5 phases which crystal structures are not isotypic. Similar procedure with H 3 OSbF 6 /Cr(SbF 6 ) 2 mixture resulted in few light orange crystals of (H 3 O) 3 [Cr IV (SbF 6 ) 6 ](Sb 2 F 11 )·HF. Its crystal structure determination showed the presence of discrete [Cr IV (SbF 6 ) 6 ] 2− units where each of Cr atoms is found in a homoleptic coordination of six SbF 6 groups.

2-Bromo-2-chloro-3-arylpropanenitriles can be prepared by Meerwein reaction from 2-chloroacrylonitrile and various aryldiazonium salts under copper(II) bromide catalysis. They proved to be stable compounds which form 2-chlorocinnnamonitriles upon treatment with bases. Reaction of the title compounds with substituted thioglycolates gave substituted 3-aminothiophenes which have not yet been accessible by other routes. Three-component reactions with the title compound, sodium sulfide and bromonitromethane, chloroacetonitrile, or ethyl 4-chloroacetoacetate gave 2-nitro- and 2-cyano-substituted 3-aminothiophenes, and thienopyridinediones in high yields and in one single step, respectively.

The use of the boron-doped diamond electrode as a sufficiently stable electrode for electrochemical measurements/synthesis in liquid anhydrous hydrogen fluoride medium is reported. Electrooxidation of silver(I) has been studied in this solvent by using classical transient electrochemical methods and impedance spectroscopy. It has been found that faradaic currents related to silver(I) oxidation and the fluorine evolution reaction are reasonably separated at the potential scale, which allows efficient electrosynthesis of AgII F2 , a powerful oxidizer. Impedance spectroscopy measurements provide insight into complex mechanism of AgF2 formation. The procedure for electrosynthesis is provided for the first time in both galvanostatic and potentiostatic condition.

A study of the reactions between the various starting molar ratios of H3OAsF6, and in situ prepared M(AsF6)2 (M = Mg, Ca, Sr, Ba) and Mn(AsF6)2 in liquid anhydrous hydrogen fluoride (aHF) acidified with AsF5 resulted in three novel oxonium salts, i.e. (H3O)3M(HF)Mn(AsF6)7 (M = Ca, Sr) and (H3O)5BaMn(AsF6)9. Reactions between in situ prepared AAsF6 (A = K, NH4), M(AsF6)2 (M = Ca, Sr, Ba) and M’(AsF6)2 (M’ = Mn, Mg, Ni, Co, Zn) in aHF acidified with AsF5 gave mixtures of various products upon crystallization. An attempt to grow single crystals of K3Ba(HF)Mn(AsF6)7 resulted in (H3O/K)3Ba(HF)Mn(AsF6)7 instead, due to moisture penetrating through the reaction vessel walls during long lasting crystallization. The crystal structures of A3M(HF)Mn(AsF6)7 (A = H3O for M = Ca and Sr; A = H3O/K for M = Ba) salts are isotypical and crystallize in the monoclinic space group P21/n (No. 14). The crystal structures consist of a complex three-dimensional framework formed from M2+ (M = Ca, Sr, Ba) and Mn2+ cations interconnected with [AsF6]– anions. The HF molecules are bound directly to alkaline earth metals via the fluorine atom. Single charged cations are located within the cavities. The Mn atoms are found in an octahedral coordination of six fluorine atoms. The Ca atoms are coordinated by eight fluorine atoms, while this number increases to nine for the Sr and Ba atoms.

The reactions between group 12 metals and the acidic TaF 5 were studied in the anhydrous HF (aHF) solvent. We were able to prepare and characterize the first compounds containing metal M 2+ cations and undecafluoridodimetallate anions – M(Ta 2 F 11 ) 2 (M = Cd, Hg) without the additional cations, anions or ligands included in the crystal structure. They both crystallize in P -1 space group with cell parameters a = 9.1571(4) A, b = 9.8750(3) A, c = 10.9400(7) A, α = 94.389(4)°, β = 113.124(5)°, γ = 101.142(3)°, V = 879.81(8) A 3 , Z = 2, T = 150 K (Cd(Ta 2 F 11 ) 2 ) and a = 9.1381(5) A, b = 9.8613(6) A, c = 11.4470(7) A, α = 114.086(6)°, β = 102.290(5)°, γ = 100.398(5)°, V = 877.84(11) A 3 , Z = 2, T = 150 K (Hg(Ta 2 F 11 ) 2 ). Metal cations connected through two anions form chains along b axis. M(HF) 2 (TaF 6 ) 2 . nHF (M = Cd, Hg) compounds were also prepared in the MF 2 /TaF 5 (M = Cd, Hg) system and their crystal structures were determined.

The reactions between XeF5SbF6 and M(SbF6)2 (M2+ = Ni, Mg, Zn, Co, Mn, Pd) in anhydrous HF (aHF) in a 1:1 molar ratio yielded XeF5M(SbF6)3 upon crystallization. All six structures were characterized at 150 K by single-crystal X-ray diffraction. For Mn, there is a phase transition at around 235 K, and for Pd between 260 and 296 K. Similar attempts to prepare new [XeF5]+/M2+ mixed-cation salts with M2+ = Ca, Sr, Ba, Cr, Fe, Ag, Cd, and Hg were only successful for Hg, for which (XeF5)3[Hg(HF)]2(SbF6)7 was obtained. The crystal structures of XeF5M(SbF6)3 (M2+ = Mg, Co, Ni, Zn) and the low-temperature phase α-XeF5Mn(SbF6)3 are isotypic with the known XeF5Cu(SbF6)3. The main features of the crystal structures of β-XeF5Mn(SbF6)3 and β-XeF5Pd(SbF6)3 are similar to those of the other XeF5M(SbF6)3 compounds, that is, a 3D framework consisting of rings of MF6 octahedra that share the apexes with SbF6 octahedra, forming cavities within which the [XeF5]+ cations are located. At 296 K, the disordered [XeF5]+ cations in β-XeF5Pd(SbF6)3 are ordered in the α-phase (260 K). The crystal structure of (XeF5)3[Hg(HF)]2(SbF6)7 consists of columns of [Hg(HF)]2+ cations bridged by SbF6 units. The charge balance is maintained by the [XeF5]+ cations, which form secondary contacts with the F atoms of the SbF6 groups.

[Cu2(amdt)2]SiF6·C6H6 and [Cu2(amdt)2(H2O)2]SiF6·CH3CN·2H2O (amdt = 2-allylamino-5- methyl-1,3,4-thiadiazole) were obtained by alternating-current electrochemical synthesis, starting from water–acetonitrile–benzene mixtures containing 2-allylamino-5-methyl-1,3,4- thiadiazole and CuSiF6·4H2O. The electrochemical reduction of the saturated copper hexafluorosilicate water solution beneath the neatly poured layer of acetonitrile-benzene amdt solution resulted in the formation of crystalline [Cu2(amdt)2]SiF6·C6H6. The initial stirring of the same mixture before subjecting it to the electrochemical reduction resulted in the formation of [Cu2(amdt)2(H2O)2]SiF6·CH3CN·2H2O. A sluggish hydrolysis of the acetonitrile over 2 years in a closed test tube with [Cu2(amdt)2]SiF6·C6H6 crystals in a mother liquor resulted in the formation of [Cu2L2(H2O)2]SiF6·CH3CONH2·2H2O. All the compounds were studied using X-ray single-crystal diffraction and Raman spectroscopy. The molecular structures and the Raman spectra of the compounds were discussed on the basis of computational modeling with the DFT/B3LYP/cc-pVDZ method. peerReviewed

Reactions between XeF2, TiF4 and UV-irradiated elemental F2 in anhydrous HF yielded XeF5TiF5 (XeF6·TiF4), [XeF5]5[Ti10F45] (XeF6·2TiF4), and [XeF5][Ti3F13] (XeF6·3TiF4) upon crystallization. [XeF5]5[Ti10F45] crystallizes in two crystal modifications at low (α-phase, 150 K) and ambient (β-phase, 296 K) temperatures. The crystal structure determination of [XeF5]5[Ti10F45] reveals the largest known discrete decameric [Ti10F45]5− anion built from ten TiF6 octahedra, sharing vertices, in the shape of a double-star. [XeF5]+ cations are completely ordered in the α-phase, while one of three crystallographically unique [XeF5]+ cations is two-fold disordered in the β-phase. The anionic part of [XeF5][Ti3F13] is built from tetrameric Ti4F20 and octameric Ti8F36 units sharing vertices and alternatively linked into ([Ti3F13]−)∞ columns. The charge balance is maintained by [XeF5]+ cations which form secondary Xe⋯F contacts with fluorine atoms of ([Ti3F13]−)∞ groups. The main structural feature of XeF5TiF5 is an infinite chain of distorted TiF6 octahedra joined by cis vertices.

The crystal structures of RbSb2F11, TlSb2F11, O2Sb2F11 and β-NH4Sb2F11 salts are isotypical and crystallize in the orthorhombic space group Cmc21 (No. 36). Crystal data of rubidium salt: a = 19.9981(3) A, b = 11.5093(2) A, c = 12.9623(2) A, V = 2983.46(8) A3, and Z = 12 at 150 K. Unit cell parameters of corresponding thallium salt: a = 19.9876(5) A, b = 11.5400(3) A, c = 13.0267(3) A, V = 3004.70(13) A3 and Z = 12 at 150 K. Reaction between NH4F and excess of SbF5 in anhydrous HF resulted in the single-crystal growth of β-NH4Sb2F11: a = 20.0406(7) A, b = 11.5534(4) A, c = 13.0796(4) A, V = 3028.42(18) A3, and Z = 12 at 296 K. The XRD experiments on NH4Sb2F11 at 240 and 150 K revealed another modification (α-NH4Sb2F11), which crystallizes in a (pseudo-hexagonal) monoclinic cell, space group P21, a = 11.5045(6) A, b = 13.0437(3) A, c = 11.5264(6) A, β = 119.818(7)°, V = 1500.67(15) A3, and Z = 6 at 240 K. Reaction between the O2SbF6 and SbF5 in anhydrous HF yielded O2Sb2F11 upon crystallization with a = 19.8472(5) A, b = 11.1172(3) A, c = 12.8259(3) A, V = 2829.97(12) A3, and Z = 12 at 150 K. The crystal structures of ASb2F11 (A = Rb+, Tl+, O2+, NH4+) salts consist of dimeric Sb2F11− anions with partially disordered terminal fluorine atoms. Negative charge of the anions is compensated by single charged cations. Crystal structure of α-NH4Sb2F11 demonstrates similar motif as in β-phase but with slightly re-arranged N―H… F hydrogen bonds. In the 100−296 K range, only rhombohedral phase was observed for NH4SbF6 (rhombohedral space group R 3 ¯ , No. 148) with a = b = 7.5961(9) A, c = 7.7176(9) A, α = β = 90°, γ = 120°, V = 385.65(12) A3, and Z = 3 at 150 K).

The crystals of tetrahydrated bis(ethylenediamine)copper(II) sulfate, [CuII(SO4)(en)2]∙4H2O or [CuII(en)2(H2O)2][CuII(OSO3)2(en)2]∙6H2O were prepared and characterized using single crystal X-ray diffraction and Raman spectroscopy. The magnetic susceptibility measurements of the aforementioned compound were also performed using a polycrystalline sample, which was found possessing maximum of susceptibility at 7 K.