Low-temperature modification of Ba(BF4)2(H2O)3.

The crystal structure of the low-temperature modification of Ba(BF4)2(H2O)3, barium bis(tetra-fluorido-borate) trihydrate, was determined at 150 K. In contrast to the room-temperature modification, which crystallizes in the space group C2221 [a = 7.1763 (6), b = 18.052 (2), c = 7.1631 (6) Å, V = 927.93 (15) Å3 at 300 K, Z = 4; Charkin et al. (2023 ▸). J. Struct. Chem. 64, 253-261], the low-temperature phase is monoclinic, space group P21 [a = 7.0550 (4), b = 7.1706 (3), c = 9.4182 (6) Å, ß = 109.295 (7)o, V = 449.68 (5) Å3, Z = 2]. The structure of the low-temperature modification of Ba(BF4)2(H2O)3 features O-H⋯F and O-H⋯O hydrogen bonding between water mol-ecules and BF4 - anions. One of the coordinating water mol-ecules in the low-temperature modification is disordered over two sets of sites.

Crystal Structures of Xenon(VI) Salts: XeF5Ni(AsF6)3, XeF5AF6 (A = Nb, Ta, Ru, Rh, Ir, Pt, Au), and XeF5A2F11 (A = Nb, Ta).

Experiments on the preparation of the new mixed cations XeF5M(AF6)3 (M = Cu, Ni; A = Cr, Nb, Ta, Ru, Rh, Re, Os, Ir, Pt, Au, As), XeF5M(SbF6)3 (M = Sn, Pb), and XeF5M(BF4)x(SbF6)3-x (x = 1, 2, 3; M = Co, Mn, Ni, Zn) salts were successful only in the preparation of XeF5Ni(AsF6)3. In other cases, mixtures of different products, mostly XeF5AF6 and XeF5A2F11 salts, were obtained. The crystal structures of XeF5Ni(AsF6)3, XeF5TaF6, XeF5RhF6, XeF5IrF6, XeF5Nb2F11, XeF5Ta2F11, and [Ni(XeF2)2](IrF6)2 were determined for the first time on single crystals at 150 K by X-ray diffraction. The crystal structures of XeF5NbF6, XeF5PtF6, XeF5RuF6, XeF5AuF6, and (Xe2F11)2(NiF6) were redetermined by the same method at 150 K. The crystal structure of XeF5RhF6 represents a new structural type in the family of XeF5AF6 salts, which crystallize in four different structural types. The XeF5A2F11 salts (M = Nb, Ta) are not isotypic and both represent a new structure type. They consist of [XeF5]+ cations and dimeric [A2F11]- anions. The crystal structure of [Ni(XeF2)2](IrF6)2 is a first example of a coordination compound in which XeF2 is coordinated to the Ni2+ cation.

Cation Charge as a Tool to Change Dimensionality in Organic-Inorganic Hybrids Based on Copper Thiocyanate Templated by 1,4-Diazabicyclo[2.2.2]octane.

The first three compounds based on a {copper-thiocyanate-dabco} combination, namely, (Hdabco)[Cu2(NCS)3] (1), (H2dabco)[Cu(NCS)3] (2), and [Cu(Hdabco)2(NCS)4]∙2dmso (3), where dabco = 1,4-diazabicyclo[2.2.2]octane were synthesized and characterized by single-crystal XRD, elemental analysis, Raman, and partial IR spectroscopy. In copper(I) derivatives, the influence of the charge of the organic cation on the dimensionality of the crystal structure is observed. Thus, in the case of 1, monoprotonated Hdabco+ cations provide the template for the formation of a polymeric anionic 3D framework {[Cu2(NCS)3]-}n, while in the case of 2, diprotonated H2dabco2+ cations together with discrete [Cu(SCN)3]2- anions generate a simple ionic 0D structure with an island-like crystal lattice. The anionic {[Cu2(SCN)3]-}n framework has infinite square channels of 10 × 10 Å size running along the 001 crystallographic direction. In 3, both the Hdabco+ and thiocyanato units behave as terminal monodentate ligands attached to copper(II) centers via N-donor atoms, forming neutral molecular complexes with an elongated (4+2) octahedral environment. The crystallization molecules of dmso are hydrogen bonded to the protonated parts of the coordinated dabco molecules. A series of by-products Cu(SCN)2(dmso)2 (4), (Hdabco)SCN (5), (H2dabco)(SCN)2 (6), and (H2dabco)(SCN)2∙H2O (7) were identified and characterized.

Supramolecular Diversity, Theoretical Investigation and Antibacterial Activity of Cu, Co and Cd Complexes Based on the Tridentate N,N,O-Schiff Base Ligand Formed In Situ.

The four new complexes, [Cu(HL1)(L2)Cl] (1), [Cu(HL1)(L1)]∙Cl∙2H2O (2), [Co(L1)2]∙Cl (3) and [Cd(HL1)I2]∙dmso (4), have been prepared by one-pot reactions of the respective chloride or iodide metal salt with a non-aqueous solution of the polydentate Schiff base, HL1, resulted from in situ condensation of benzhydrazide and 2-pyridinecarboxaldehyde, while a ligand HL2, in case of 1, has been formed due to the oxidation of 2-pyridinecarboxaldehyde under reaction conditions. The crystallographic analysis revealed that the molecular building units in 1-4 are linked together into complex structures by hydrogen bonding, resulting in 1D, 2D and 3D supramolecular architectures for 1, 2 and 4, respectively, and the supramolecular trimer for 3. The electronic structures of 1-4 were investigated by the DFT theoretical calculations. The non-covalent interactions in the crystal structures of 1-4 were studied by means of the Hirshfeld surface analysis and the QTAIM theory with a special focus on the C-H⋯Cl bonding. From the DFT/DLPNO-CCSD(T) calculations, using a series of charged model {R3C-H}0⋯Cl- assemblies, we propose linear regressions for assessment of the interaction enthalpy (ΔH, kcal mol-1) and the binding energy (BE, kcal mol-1) between {R3C-H}0 and Cl- sites starting from the electron density at the bond critical point (ρ(rBCP), a.u.): ΔH = -678 × ρ(r) + 3 and BE = -726 × ρ(r) + 4. It was also has been found that compounds 1, 3 and 4 during in vitro screening showed an antibacterial activity toward the nine bacteria species, comprising both Gram-positive and Gram-negative, with MIC values ranging from 156.2 to 625 mg/L. The best results have been obtained against Acinetobacter baumannii MßL.

Novel N-(4-thiocyanatophenyl)-1H-1,2,3-triazole-4-carboxamides exhibit selective cytotoxic activity at nanomolar doses towards human leukemic T-cells.

The N-(4-thiocyanatophenyl)-1H-1,2,3-triazole-4-carboxamides were synthesized via the condensation of variety of 1H-1,2,3-triazole-4-carboxylic acids and 4-thiocyanatoaniline using CDI as amide coupling reagents. According to computer-aided calculations, all synthesized compounds are expected to have acceptable ADME profile for drug design. The antiproliferative potency of derivatives was evaluated towards different cell lines. The specific activity of four N-(4-thiocyanatophenyl)-1H-1,2,3-triazole-4-carboxamides (4a, 4b, 4c, 4f) was comparable to doxorubicin (GI50 = 0.65 µM) at nanomolar level against Jurkat cells in the range of GI50 0.63-0.69 µM. According to the results of toxicity studies of the compounds for HEK293, HaCaT, Balb/c 3T3 cells, compound 4a was selected for further studies as a biocompatible agent with promising anticancer activity in the NCI60 cell lines. A remarkable antiproliferative activity of compound 4a towards leukemia cell lines (SR, MOLT-4; CCRF-CEM; HL-60(TB); K-562; RPMI-8226) was observed and high cytotoxicity towards the CAKI-1 (kidney cancer), LOX IMVI (melanoma) and UO-31 (renal cancer) cells lines was detected. Compound 4a inhibits LOX IMVI cells growth at a GI50 value of 0.15 µM. COMPARE analysis to indicate potential mechanisms of action of novel compound, as well as in silico SwissTargetPrediction and SwissSimilarity were performed. Compound 4a induced morphological changes (apoptotic bodies, membrane blebbing, chromatin condensation), and DNA fragmentation in Jurkat T-cells. It reduced mitochondrial membrane potential and induced DNA damage in Jurkat cells without binding and/or intercalation to DNA molecule.

Thiocyanatoarylation of Methyl Vinyl Ketone under Meerwein Conditions for the Synthesis of 2-Aminothiazole-Based Heterocyclic Systems.

4-Aryl-3-thiocyanatobutan-2-ones were prepared by Meerwein reactions from methyl vinyl ketone and aryldiazonium salts under copper(II) catalysis in 35-75% yields. α-Thiocyanato ketones regioselectively react with 1-methyl-3-aminopyrazole forming N-(3-pyrazolyl)-substituted 2-aminothiazoles in 80-91% yields. An ester group in position 3 of the pyrazole induced a regioselective ring-closure reaction followed by an intramolecular cyclization, which gave first representatives of a new heterocyclic system, pyrazolo[4,3-e]thiazolo[3,2-a]pyrimidine, in 74-93% yields. In addition, the preparations of 5-benzyl-4-methylthiazol-2-ones in 84-93% yields are described.

Crystal Growth from Anhydrous HF Solutions of M2+ (M = Ca, Sr, Ba) and [AuF6]-, Not Only Simple M(AuF6)2 Salts.

Crystal growth from anhydrous HF solutions of M2+ (M = Ca, Sr, Ba) and [AuF6]- (molar ratio 1:2) gave [Ca(HF)2](AuF6)2, [Sr(HF)](AuF6)2, and Ba[Ba(HF)]6(AuF6)14. [Ca(HF)2](AuF6)2 exhibits a layered structure in which [Ca(HF)2]2+ cations are connected by AuF6 units, while the crystal structure of Ba[Ba(HF)]6(AuF6)14 exhibits a complex three-dimensional (3-D) network consisting of Ba2+ and [Ba(HF)2]2+ cations bridged by AuF6 groups. These results indicate that the previously reported M(AuF6)2 (M = Ca, Sr, Ba) compounds, prepared in the anhydrous HF, do not in fact correspond to this chemical formula. When the initial M2+/[AuF6]- ratio was 1:1, single crystals of [M(HF)](H3F4)(AuF6) were grown for M = Sr. The crystal structure consists of a 3-D framework formed by [Sr(HF)]2+ cations associated with [AuF6]- and [H3F4]- anions. The latter exhibits a Z-shaped conformation, which has not been observed before. Single crystals of M(BF4)(AuF6) (M = Sr, Ba) were grown when a small amount of BF3 was present during crystallization. Sr(BF4)(AuF6) crystallizes in two modifications. A high-temperature α-phase (293 K) crystallized in an orthorhombic unit cell, and a low-temperature ß-phase (150 K) crystallized in a monoclinic unit cell. For Ba(BF4)(AuF6), only an orthorhombic modification was observed in the range 80-230 K. An attempt to grow crystals of Ca(BF4)(AuF6) failed. Instead, crystals of [Ca(HF)](BF4)2 were grown and the crystal structure was determined. During prolonged crystallization of [AuF]6- salts, moisture can penetrate through the walls of the crystallization vessel. This can lead to partial reduction of Au(V) to A(III) and the formation of [AuF4]- byproducts, as shown by the single-crystal growth of [Ba(HF)]4(AuF4)(AuF6)7. Its crystal structure consists of [Ba(HF)]2+ cations connected by AuF6 octahedra and square-planar AuF4 units. The crystal structure of the minor product [O2]2[Sr(HF)]5[AuF6]12·HF was also determined.

Oxidation of Iodine to Dihaloiodate(I) Salts of Amines With Hydrogen Peroxides and Their Crystal Structures.

Herein we report a general preparation of dihaloiodate salts of heterocyclic amines (tertiary and quaternary) with sterically accessible and hindered nitrogen atom. A number of such compounds were prepared from preformed HICl2 or HIBr2 formed in situ by the reaction of corresponding hydrogen halide, iodine and H2O2. The salts of 1,4-diazabicyclo[2.2.2]octane (DABCO) and its methylated derivatives, 1,3,5,7-tetraazaadamantane (HMTA), diazabicycloundecene (DBU) and 2,4,6-tri-tert-butylpyridine (TBP) were obtained in excellent yields and their structure was determined by NMR and Raman spectroscopy and single crystal X-ray diffraction. Non-hindered bases such as DABCO, HMTA and DBU formed IX2 - salts, which further decomposed to complexes with interhalogen compounds due to formation of N…X halogen bonds. The dihaloiodiate(I) salts of sterically hindered 2,4,6-tri-tert-butylpyridine were stable. Its dichlorobromate(I) salt was also prepared via a different synthetic method using N-chlorosuccinimide as oxidant.

Synthesis, crystal structure and Hirshfeld surface analysis of (4-methyl-phen-yl)[1-(penta-fluoro-phen-yl)-5-(tri-fluoro-meth-yl)-1H-1,2,3-triazol-4-yl]methanone.

The title compound, C17H7F8N3O, was obtained via the reaction of 1-azido-2,3,4,5,6-penta-fluoro-benzene with 4,4,4-tri-fluoro-1-(p-tol-yl)butane-1,3-dione using tri-ethyl-amine as a base catalyst and solvent. The dihedral angles between the penta-fluoro-phenyl (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 mol-ecules are linked by C-H⋯F and C-H⋯O hydrogen bonds as well as by aromatic π-π stacking inter-actions into a three-dimensional network. To further analyse the inter-molecular inter-actions, a Hirshfeld surface analysis was performed.

Syntheses and crystal structures of two copper(I)-halide π,σ-coordination compounds based on 2-[(prop-2-en-1-yl)sulfan-yl]pyridine.

The title compounds, di-µ-chlorido-bis-({2-[(η-2,3)-(prop-2-en-1-yl)sulfan-yl]pyridine-κN}copper(I)), [Cu2Cl2(C8H9NS)2], and di-µ-bromido-bis-({2-[(η-2,3)-(prop-2-en-1-yl)sulfan-yl]pyridine-κN}copper(I)), [Cu2Br2(C8H9NS)2], were obtained by alternating-current electrochemical synthesis starting from an ethano-lic solution of 2-[(prop-2-en-1-yl)sulfan-yl]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 inter-actions into a three-dimensional network.

A bis-chelate o-vanillin-2-ethano-lamine copper(II) complex bearing both imine and amine forms of the ligand.

The mol-ecular bis-chelate complex (2-{[(2-hy-droxy-ethyl-κO)amino-κN]meth-yl}-6-meth-oxy-phenolato-κO)(2-{[(2-hy-droxy-eth-yl)imino-κN]meth-yl}-6-meth-oxy-phenolato-κO)copper(II), [Cu(C10H14NO3)(C10H12NO3)] or [Cu(HL im)(HL am); HL im = C10H14NO3; HL am = C10H12NO3, represents the first compound containing a salicyl-idene-2-ethano-lamine 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 mol-ecules 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). Inter-molecular N-H⋯O and O-H⋯O hydrogen bonds, involving H atoms of the amino and hy-droxy-ethyl groups, create a two-dimensional supra-molecular array extending parallel to (010).

Syntheses of Dioxygenyl Salts by Photochemical Reactions in Liquid Anhydrous Hydrogen Fluoride: X-ray Crystal Structures of α- and ß-O2Sn2F9, O2Sn2F9·0.9HF, O2GeF5·HF, and O2[Hg(HF)]4(SbF6)9.

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 ß-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.

Cu(I) Arylsulfonate D€-Complexes with 3-Allyl-2-thiohydantoin: The Role of the Weak Interactions in Structural Organization.

The present work is directed toward preparation and structural characterization of two novel Cu(I) arylsulfonate ?-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) ? in 1 and 2.7205(9) ? in 2). This difference was explained by the impact of the system of weak interactions, which are quite different.

Crystal structure, Hirshfeld surface analysis and computational studies of 5-[(prop-2-en-1-yl)sulfan-yl]-1-[2-(tri-fluoro-meth-yl)phen-yl]-1H-tetra-zole.

The title compound, C11H9F3N4S, was synthesized from 2-(tri-fluoro-meth-yl)aniline by a multi-step reaction. It crystallizes in the non-centrosymmetric space group Pna21, with one mol-ecule in the asymmetric unit, and is constructed from a pair of aromatic rings [2-(tri-fluoro-meth-yl)phenyl and tetra-zole], which are twisted by 76.8 (1)° relative to each other because of significant steric hindrance of the tri-fluoro-methyl group at the ortho position of the benzene ring. In the crystal, very weak C-H⋯N and C-H⋯F hydrogen bonds and aromatic π-π stacking inter-actions link the mol-ecules into a three-dimensional network. To further analyse the inter-molecular inter-actions, a Hirshfeld surface analysis, as well as inter-action energy calculations, were performed.

Preparative Electrosynthesis of Strong Oxidizers at Boron-Doped Diamond Electrode in Anhydrous HF.

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.

Increasing Structural Dimensionality of Alkali Metal Fluoridotitanates(IV).

Reactions between AF (A = Li, Na, K, Rb, Cs) and TiF4 (with starting n(AF):n(TiF4) molar ratios in the range from 3:1 to 1:3) in anhydrous hydrogen fluoride yield [TiF6]2-, [TiF5]-, [Ti4F19]3-, [Ti2F9]-, and [Ti6F27]3- salts. With the exception of the A2TiF6 compounds, which consist of A+ cations and octahedral [TiF6]2- anions, all of these materials arise from the condensation of TiF6 units. The anionic part in the crystal structures of A[TiF5] (A = K, Cs) and A[TiF5]·HF (A = Na, K, Rb) is composed of infinite ([TiF5]-)∞ chains built of TiF6 octahedra sharing joint vertices. Each structure shows a slightly different geometry of the ([TiF5]-)∞ chains. The crystal structure of Na[Ti2F9]·HF is constructed from polymeric ([Ti2F9]-)∞ anions that appear as two parallel infinite zigzag chains comprising TiF6 units, where each TiF6 unit of one chain is connected to a TiF6 unit of the other chain through a shared fluorine vertex. Slow decomposition of single crystals of K4[Ti8F36]·8HF and Rb4[Ti8F36]·6HF ( Shlyapnikov , I. M. ; et al. Chem. Commun. 2013 , 49 , 2703 ) leads to the formation of [Ti2F9]- (Rb) and [Ti6F27]3- (K, Rb) salts. The former displays the same ([Ti2F9]-)∞ double chain as in Na[Ti2F9]·HF, while the anionic part in the latter, ([Ti6F27]3-)∞, represents the first example of a three-dimensional network built of TiF6 octahedra. The ([Ti6F27]3-)∞ anion was also found in [H3O]3[Ti6F27]. The crystal structure determination of Cs3[Ti4F19] revealed a new type of polymeric fluoridotitanate(IV) anion, ([Ti4F19]3-)∞. Similar to the ([Ti2F9]-)∞ anion, it is also built of zigzag double chains comprising TiF6 units. However, in the former there are fewer connections between TiF6 units of two neighboring chains than in the latter.

Synthesis and Structure of [Cu(Hapn)]NO3]NO3, [Cu(Hapn)(H2O)2]SiF6, [Cu(Hapn)(H2O)BF4]BF4 · H2O and [Cu(Hapn)(NH2SO3)2] π-complexes (apn = 3-(prop-2-en-1-ylamino)propanenitrile).

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 cyano group from another Hapn moiety, 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 Hapn cation, 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.

Synthesis and X-ray Structural Analysis of the Ruthenium(III) Complex Na[trans-RuCl4(DMSO) (PyrDiaz)], the Diazene Derivative of Antitumor NAMI-Pyr.

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.

Canted Antiferromagnetism in Two-Dimensional Silver(II) Bis[pentafluoridooxidotungstate(VI)].

By slow reaction between colorless AgIW2O2F9 and elemental F2 in liquid anhydrous HF, violet platelike single crystals of Ag(WOF5)2 were grown. The crystal structure of Ag(WOF5)2 consists of layers built from Ag2+ cations bridged by [WOF5]- anions and not, as previously assumed, from infinite [AgII-F]+∞ chains and [W2O2F9]- anions. A majority (97%) of the disordered AgII cations are found with square-planar coordination of F/O ligands within the same layer, and they form additional long contacts with O/F atoms originating from the neighboring layers. The remaining 3% the of Ag(II) ions are coordinated only by F atoms in a square-planar fashion. The magnetic moments of Ag2+ from the same layer are almost perfectly antiferromagnetically aligned. Weak ferromagnetic interlayer interactions cause a small tilt (∼1.5°) of the magnetic moments, resulting in canted antiferromagnetism. Because of the lowering of the symmetry of [WOF5]- in the solid state, the vibrational spectra show more bands than expected for regular C4v symmetry. The electronic spectrum of Ag(WOF5)2 is reported and analyzed.

Oxidation of Ruthenium and Iridium Metal by XeF2 and Crystal Structure Determination of [Xe2F3][RuF6]·XeF2 and [Xe2F3][MF6] (M = Ru, Ir).

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)°, ß = 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 crystallize in a monoclinic Cc 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); ß = 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.