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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.

This work is focused on the synthesis and structure characterization of the novel Cu(I) π-complex [Cu2(Thiaz1)2(ClO4)2] (1) with 2-allylamino-5-methyl-1,3,4-thiadiazole (Thiaz1) ligand. The crystals of the compound were obtained by means of the alternating-current electrochemical technique and studied using single crystal X-ray diffraction. The crystal structure of the complex 1 is constructed from the centrosymmetric dimers, in which two copper(I) ions are coordinated by two Thiaz1 molecules through thiadiazole N atoms and allylic C=C bond. Energy framework computational analysis for structure 1 has been 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...

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

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 (GI

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 copper(II) atom in the mol­ecular title complex has a distorted square-pyramidal coordination environment by three O and two N atoms from a bidentate and a tridentate ligand., 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).

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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...

6-Amino-3-(prop-2-en-1-yl)-9H-purin-3-ium tetracopper(I) hexabromide [(C5H5N5(C3H5))2Cu4Br6] (1) is synthesized in this paper. The title compound is characterized by Raman spectroscopy and single crystal X-ray diffraction: monoclinic, Sp.gr. P21/c, Z = 2, unit cell dimensions: a = 8.6870(3), b = 9.7447(2), c = 16.4418(4) Å, β = 100.681(3)°, V = 1367.72(7) Å3 at 150 K. The peculiarities of the metal coordination and distribution of weak interactions are analyzed. The significant role of hydrogen bonds in the construction of 1 crystal structure is shown.

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.

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., Reactions between fluorides and/or oxides and UV-irradiated F2 and/or F2/O2 mixtures were carried out in anhydrous hydrogen fluoride at ambient temperature to prepare O2+ salts. The crystal structures of O2GeF5·HF and O2GeF5 consist of infinite polymeric ([GeF5]−)∞ anions. The O2Sn2F9 salt exhibits polymorphism consisting of a 1-D phase built from double chainlike ([Sn2F9]−)∞ anions and a 2-D phase built from layerlike anions. The latter also exists as a solvated form O2Sn2F9·nHF. The crystal structure of O2[Hg(HF)]4(SbF6)9 is isotypic to that of H3O[Cd(HF)]4(SbF6)9. The Hg atoms are bridged by SbF6 groups forming a 3-D framework with O2+ cations located inside the voids. The HF molecules are bound to Hg atoms through the F atom.

For the first time, 5-formyl-1-(pyridin-3-yl)-1H-1,2,3-triazole-4-carboxylate was synthesized via a two-step scheme. The molecular structure of the compound was determined by a single-crystal X-ray diffraction analysis. The Hirshfeld surface analysis was used to study various intermolecular interactions. The crystalline structure is marked by the presence of three types of π-interactions (n→π*, lp···π, and π···π) between the -C(H)=O group and triazole rings. The compound is a versatile polyfunctional building block for construction of annulated 1,2,3-triazoles.

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.