Crystal chemical analysis of structures of the unsaturated tetraazamacrocyclic gold(III) complexes

The detailed comparative study is carried out for crystal structure packings of the following gold(III) complexes with unsaturated ligands: [Au(C₁₄H₂₂N₄)]Br (I), [Au(C₁₄H₂₃N₄)](ClO₄)₂ (II), [Au(C₁₄H₂₄N₄)](H₃O)(ClO₄)₄ (III). The determining role in the topological pattern of packings I–III belongs to the compositions and structures of the cations along with the ability of the ions of the complexes to act as donors and acceptors of hydrogen bonds. The 3D packings of complexes I and II containing iminate six-membered rings are determined and stabilized by a wide network of weak hydrogen bonds (C–H…π, C–H…Au, and C–H…Br(O)) and short contacts Au(N)…O (in structure II). The structure of imine complex III is characterized by one-dimensional piles formed due to hydrogen bonds O(w)–H…O and contacts Au…O of the О(2) atom of anion Сl(1)О ₄ ^- with cations (H₃O)⁺ and [Au(C₁₄H₂₄N₄)]³⁺ (CIF files CCDC 251258 (I), 276132 (II), and 287784 (III)).     

Structural features of monomeric octahedral <Emphasis Type="Italic">d</Emphasis><Superscript>2</Superscript>-rhenium(V) monooxo complexes with the oxygen atoms of bidentate chelate (О,S and О,С) acido ligands

Some structural features of 12 mononuclear octahedral d ²-Re(V) monooxo complexes (I–ХII) with the oxygen atoms of bidentate chelate (О,S) acido ligands (Lig) and a similar complex with the oxygen atom of a bidentate chelate (О,С) monoanionic ligand (XIII) have been considered. The O(Lig) atoms are in trans positions to О(oxo) ligands in eleven complexes I–Х and XIII and in cis positions to oxo ligands in two complexes XI and XII. In all the cases, Re–O _trans bonds are longer than Re–O _cis (or Re–O_stand).     

Synthesis and properties of copper(II) complexes with a chiral dioxatetraazamacrocyclic ligand based on a natural monoterpene, (+)-3-carene

The copper(II) compounds [CuL](NO₃)₂ · H₂O (I), [CuL](ClO₄)₂ · H₂O (II), CuLCl₂ · 3H₂O (III), and CuLBr₂ · 4H₂O (IV), where L is a chiral dioxatetraazamacrocyclic ligand based on the natural monoterpene (+)-3-carene, have been synthesized. According to IR and EPR spectroscopy, L acts as a tetradentate chelating ligand coordinated through the N atoms of the NH and C=N groups. The NO ₃ ^? anions in I and the ClO ₄ ^? anions in II are outer-sphere. I and II have a planar coordination core CuN₄, III has a CuN₄ClO coordination core, and IV has a CuN₄Br₂ coordination core.     

(18-Crown-6)(nitrato-<Emphasis Type="Italic">O,O</Emphasis>′)potassium and (18-crown-6)(nitrato-O,O′)potassium<Subscript>(0.91)</Subscript>silver<Subscript>(0.09)</Subscript>: Synthesis and crystal structures

Two complexes with similar compositions are synthesized: (18-crown-6)(nitrato-O,O′)potassium (I) and (18-crown-6)(nitrato-O,O′)potassium_(0.91)silver_(0.09) (II). Their isomorphic orthorhombic crystals (space group P2₁2₁2₁, Z = 4) are studied by X-ray diffraction analysis. Structure I (a = 8.553 Å, b = 11.967 Å, c = 17.871 Å) and structure II (a = 8.540 Å, b = 11.956 Å, c = 17.867 Å) are solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.044 (I) and 0.055 (II) for all 2385 (I) and 2379 (II) measured independent reflections. Complex molecules [K(NO₃)(18-crown-6)] in structure I and [K_0.91Ag_0.09(NO₃)(18-crown-6)] in compound II are of the host-guest type and rather similar in structure. Their 18-crown-6 and NO ₃ ^? ligands are disordered over two orientations. The K⁺ cation in complex I and the mixed cation (K_0.91Ag_0.09)⁺ in complex II reside in the cavity of the disordered 18-crown-6 ligand and is coordinated by its six O atoms and by two disordered O atoms of the NO ₃ ^? . ligand. The coordination polyhedron (CN = 8) of the K⁺ cation in complex I and that of (K_0.91Ag_0.09)⁺ cation in complex II is a distorted hexagonal pyramid with a base of six O atoms of the 18-crown-6 ligand and a split vertex at two O atoms of the NO ₃ ^? ligand.     

Synthesis and crystal structures of (2.2.2-cryptand)rubidium chloride and bromide hydrates

Two complexes, (2.2.2-cryptand)rubidium chloride and bromide hydrates [Rb(Crypt-222]Hal · 3.5H₂O (Hal = Cl (I) and Br (II)), are synthesized. The structures of isomorphic crystals of compounds I and II are studied by X-ray diffraction analysis. The crystals are trigonal: space group P \(\overline 3 \), Z = 2; I: a = 11.810 Å, c = 11.302 Å; II: a = 11.890 Å, c = 11.402 Å. The structures are solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.060 (I) and 0.077 (II) for 2650 (I) and 2700 (II) independent reflections (CAD-4 automated diffractometer, λMoK _α radiation). In crystals of complexes I and II, the [Rb(Crypt-222)]⁺ cation of the host-guest type lies on the crystallographic axis 3 and has the approximate symmetry D ₃. In complexes I and II, the coordination polyhedron of the Rb⁺ cation is a two-base-centered trigonal prism somewhat distorted to an antiprism. The crystals of compounds I and II contain H-bonded disordered cubes of the water molecules and Cl^? or Br^? anions.     

Mono- and dinuclear vanadium complexes with the pentadentate schiff base 2,6-diacetylpyridine bis(nicotinylhydrazone): Synthesis and structures

A reaction between VOSO₄, 2,6-diacetylpyridine, and nicotinohydrazide in a molar ratio of 1: 1: 2 afforded two complexes differing in both color and crystal shape as well as in chemical composition and molecular structure. The compositions and structures of the vanadium complexes were determined by IR spectroscopy and X-ray diffraction (CIF files CCDC_nos. 1411235 (I) and 1411236 (II)). These complexes can be formulated as [V ₂ ^II (H₂L)₂](NO₃)₄ ? H₂O (I) and [V^IV(=O)(H₂L)(SO₄)] ? 5H₂O (II), where H₂L is 2,6-diacetylpyridine bis(nicotinylhydrazone). Complex I consists of centrosymmetric dinuclear complex cations [V₂(H₂L)₂]⁴⁺, NO ₃ ^- anions, and crystal water molecules in a ratio of 1: 4: 1; complex II is built from molecular V(IV) complexes and crystal water molecules in a ratio of 1: 5. The coordination polyhedron of the metal atom in I is a tetragonal pyramid made up of the electron-donating atoms N₃O₂ of two ligands H₂L. The coordination polyhedron of the metal atom in II is a pentagonal bipyramid made up of the electron-donating atoms N₃O₂ of one neutral five-coordinate ligand H₂L and two O atoms coming from the oxo ligand and the SO ₄ ^2- anion coordinated in a monodentate fashion.     

Synthesis and crystal structure of 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane sulfate tetrahydrate

A hydrated salt of 2.2.2-cryptand and sulfuric acid [H₂(Crypt-222)]²⁺ · SO ₄ ^2? · 4H₂O(I) was prepared and studied by X-ray diffraction. The structure of I (space group C2/c, a = 22.823, b = 9.610, c = 26.150 Å, β = 107.71°, Z = 8) was solved by the direct method and refined by full-matrix least-squares in the anisotropic approximation to R = 0.056 for 4032 independent reflections (CAD4 automated diffractometer, λMoK _α radiation). In the structure of I, the 2.2.2-cryptand dication (with approximate C ₂ symmetry) has a rare exo-exo conformation where two H atoms at two N atoms are directed away from the cavity. The tetrahedral SO ₄ ^2? anion is disordered over two orientations. In two water molecules, the H atoms are disordered, while in the other two water molecules all atoms are disordered. The crystal structure of I has an extensive three-dimensional system of ion-ion (intermolecular) hydrogen bonds in which infinite chains of alternating SO ₄ ^2? anions and 2.2.2-dications can be distinguished.     

Topological insights in polynuclear Ni/Na coordination clusters derived from a schiff base ligand

This article presents the syntheses, crystal structures, topological features and magnetic properties of two Ni^II/Na^I coordination clusters formulated [Ni ₃ ^II Na(L1)₃(HL1)(MeOH)₂] (1) and [Ni ₆ ^II Na(L1)₅(CO₃)(MeO)(MeOH)₃(H₂O)₃]·4(MeOH) 2(H₂O) [2 4(MeOH) 2(H₂O)] where H₂L1 is the semi-rigid Schiff base ligand (E)-2-(2-hydroxy-3-methoxybenzylideneamino)-phenol). Compound 1 possesses a rare Ni ₃ ^II Na^I cubane (3M4-1) topology, and compound 2 is the first example in polynuclear Ni/Na chemistry that exhibits a 2,3,4M7-1 topology.     

Polyoxometalate-based supramolecular hybrids composed of Cu/2, 2′-dimethyl-4, 4′-bithiazole fragments extended via non-bonding S···O interactions

Four polyoxometalate-based complexes, namely [Cu^I(dm4bt)₂]₃[PMo₁₂O₄₀] (1), H₂[Cu^I(dm4bt)₂]₂{[Cu ₂ ^I (dm4bt)₃]₂[SiW₁₂O₄₀]}[SiW₁₂O₄₀] (2), [Cu^I(dm4bt)₂]₅ {[Cu^I(dm4bt)][P₂W₁₈O₆₂]} (3) and {Cu ₂ ^II (dm4bt)₂[Mo₆O₂₀]} (4) (dm4bt = 2,2′-dimethyl-4,4′-bithiazole), were synthesized hydrothermally from copper nitrate and various polyoxoanions. X-ray crystal structural analysis reveals that all four complexes have supramolecular structures, in which the dm4bt ligands coordinate with the Cu atoms to give different Cu/dm4bt fragments, which are further connected into supramolecular structures via non-bonding S···O interactions between Cu/dm4bt fragments and polyoxoanions. The crystal structures also reveal the crucial role of S···O interactions in the packing structures of complexes 1–4. The electrochemical and electrocatalytic properties of 1–3 with respect to bromate reduction were investigated.     

Effect of the air humidity on the proton conductivity of some aminobenzenesulfonic acids

Effects of environment conditions (humidity and temperature) on the proton conductivity of aminobenzenesulfonic acids: 2-amino-(orthanilic) acid (I), 3-amino-(metanilic) acid (II), 4-amino-(sulfanilic) acid (III), their general formula NH₂C₆H₄SO₃H, and 3-amino-4-hydroxobenzenesulfonic acid (IV) [NH₂(OH)C₆H₃SO₃H), as well as (for sake of comparison) inorganic aminosulfonic acid [sulphamic acid (NH₂SO₃H)] (V) are studied. All above-listed compounds are zwitter-ions: they contain a fragment NH ₃ ⁺ SO ₃ ^? . The presence of this structural fragment affects the thermal stability of the compounds; according to the mass-spectrometry analysis data, the decomposition of the SO₃-fragment begins at the following temperatures: (I) ?339, (II) ?370, (III) ?320, (IV) ?278, and (V) ?220°C. It is shown that the increase of the environment relative humidity up to 95% results in the increase of the aminobenzenesulfonic acids proton conductivity from 10^?9–10^?8 to 10^?5 S cm^?1; sulphamic acid, to 10^?4 S cm^?1. At that, the amount of adsorbed water does not exceed 0.2 moles per 1 sulfo group in all cases. The conductance activation energy equals 0.2 eV at a relative humidity of 95%.     

Uranyl Methacrylate Complexes with Carbamide and Methylcarbamide: Synthesis and Structure

The synthesis and X-ray diffraction and IR spectroscopic study of (UO₂)₂(mac)₄(L)₃ · H₂O crystals, where mac^– is the methacrylate ion C₃H₅COO^– and L is carbamide (I) or methylcarbamide (II), have been performed. Complexes I and II have a homotypic structure: crystals contain two kinds of mononuclear uranium-containing complexes, i.e., cationic [UO₂(mac)(L)₃]⁺ and anionic [UO₂(mac)₃]^–. The crystallographic formula of complexes in structures I and II is AB⁰¹M ₃ ¹ + AB ₃ ⁰¹ (A =UO₂²⁺ B⁰¹ = mac^–, M¹ = L). The uranium-containing complexes in structures I and II are linked into a framework by means of electrostatic interactions and a system of hydrogen bonds. Despite the similar compositions and structures of the uranium-containing complexes, their packings into a three-dimensional framework appreciably differ from each other.     

Cobalt(II) and copper(II) complexes with chiral pyrazolylquinoline,a derivative of terpenoid (+)-3-carene. Catalytic activity in ethylene polymerization reaction

Coordination compounds [CoLCl₂] (I), [CuLCl(NO₃)] (II), CuL(NO₃)₂ (III), and CuLCl₂ (IV) (where L is a chiral pyrazolylquinoline—a derivative of terpenoid (+)-3-carene) were synthesized. X-ray diffraction data showed that crystal structures I and II are built of mononuclear acentric molecules. In the molecule of complex I, the Co₂₊ ion coordinates two N atoms of bidentate cycle-forming ligand L and two Cl atoms. The coordination polyhedron of Cl₂N₂ is a distorted tetrahedron. For complex I, μ_eff = 4.50 μ_B, which corresponds to a high-spin configuration d ⁷. In the molecules of II(1), II(2) (which are diastereoisomers of complex II), each Cu²⁺ ion coordinates two N atoms of bidentate cycle-forming ligand L, the Cl atom, and two O atoms of bidentate cyclic NO ₃ ^? ion. The ClN₂O₂ coordination polyhedra are tetragonal pyramids with different degrees of distortion. The structure of complex II consists of supramolecular clusters, i.e., isolated chains incorporating the molecules of II(1) and II(2). The values of μ_eff for II–IV correspond to the d ⁹ configuration. The results of EPR and IR study suggest that complex III contains the O₄N₂ polyhedron, whereas complex IV contains the Cl₂N₂ polyhedron. Complexes I and IV were found to show a high catalytic activity in ethylene polymerization reaction.     

Syntheses and crystal structures of hydrated complexes of strontium and barium bromides with 18-crown-6

Two complexes, namely, triaqua(18-crown-6)strontium dibromide monohydrate (I) and diaquabromo(18-crown-6)barium bromide (II), are synthesized. Their crystal structures are determined by X-ray diffraction analyses. For complex I, space group C2/c, a = 17.547 Å, b = 10.246 Å, c = 14.786 Å, β = 123.08°, Z = 4. For complex II, space group Pnma, a = 17.753 Å, b = 17.465 Å, c = 6.629 Å, Z = 4. The structures are solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.056 (I) and 0.042 (II) for 2696 (I) and 2440 (II) independent reflections (CAD-4 automated diffractometer, λMoK _α radiation). Both complex cations—randomly disordered [Sr(18C6)(H₂O)₃]²⁺ in complex I and [BaBr(18C6)(H₂O)₂]⁺ in complex II—are of the host-guest type. The Sr²⁺ (Ba²⁺) cation resides in the cavity of the 18-crown-6 ligand and coordinated by all six O atoms. In the structures complexes I and II, the coordination polyhedra of the Sr²⁺ and Ba²⁺ cations (coordination number 9) can be described as distorted hexagonal bipyramids with one apex at the O atom of the water molecule in complex I or at the Br^? ligand in complex II and the other split apex at the O atoms of two water molecules.     

Synthesis,crystal structure,and luminescent properties of silver complexes with 2-methylquinoline

The complexes [AgL₂(NO₃)] (I) and [AgL₂(CH₃SO₃)] · H₂O (II) (L is 2-methylquinoline, C₁₀H₉N) have been synthesized and structurally characterized by single-crystal X-ray diffraction. Crystals of I are monoclinic, space group P2₁/n, a = 9.296(1) Å, b = 13.495(1) Å, c = 14.931(1) Å, β = 95.06(1)°, V = 1865.8(3) ų, ρ_calc = 1.624 g/cm³, Z = 4. Crystals of II are monoclinic, space group P2₁/n, a = 13.147(1) Å, b = 11.767(1) Å, c = 13.814(1) Å, β = 96.06(1)°, V = 2124.3(3) ų, ρ_calc = 1.599 g/cm³, Z = 4. Compounds I and II are composed of discrete complexes of similar structure but with different orientation of the methyl groups of ligand L (trans and cis arrangement, respectively). Both anions, NO ₃ ^- and CH₃SO ₃ ^- function as a chelating weakly bound ligand for the Ag⁺ ion. The presence of water molecules in II is favorable for the formation of dimeric supramolecular moieties between the centrosymmetrically arranged Ag⁺ complexes with 2-methylquinoline. The luminescence spectra of solid complexes I and II showed a bathochromic shift as compared to the spectrum of L in acetonitrile. Complexes I and II have been characterized by ¹H and ¹³C{H} NMR spectra in CD₃CN.     

(18-Crown-6)sodium tribromide and (18-crown-6)potassium triiodide (with an admixture of bromodiiodide): Synthesis and crystal structure

Two crystalline host-guest complexes are synthesized and studied using X-ray diffraction analysis: (18-crown-6)sodium tribromide [Na(18-crown-6)]⁺ · Br ₃ ^? (I) and (18-crown-6)potassium tribromide (with an admixture of bromodiiodide) [K(18-crown-6)]⁺ · (Br_0.25I_2.75)^? (II). The structures of compound I (space group P2₁/_{n, a} = 8.957 Å, b = 8.288 Å, c = 14.054 Å, β = 104.80°, Z = 2) and compound II (space group Cc, a = 8.417 Å, b = 15.147 Å, c = 17.445 Å, β = 99.01°, Z = 4) are solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.098 (I) and 0.036 (II) for all 2311 (I) and 2678 (II) independent measured reflections on a CAD-4 automated diffractometer (λMoK _α). Similar crystalline complexes I and II exist as infinite chains of alternating complex cations and trihalide anions linked to each other through weak Na-Br or K-I coordination bonds. In [Na(18-crown-6)]⁺ and [K(18-crown-6)]⁺ complex cations, the Na⁺ or K⁺ cation (coordination number is eight) is located in the center of the cavity of the 18-crown-6 ligand and coordinated by the six O atoms and two terminal Br or I atoms of two trihalide anions lying on opposite sides of the rms plane of the crown ligand.     

Synthesis,luminescent sensing based on a three-fold interpenetrating network with flexible carboxylates

A Zn-based complexes with chemical formulae {[Zn(L)_0.5(4,4'-Bipy)] · 2H₂O} (I) (H₄L = 5,5'-(1,4-phenylene-bis(methylene))bis(oxy) diisophthalic acid), has been synthesized and structurally characterized. Single-crystal X-ray crystallography (CIF file CCDC no. 1465538) reveals that compound I shows a three-dimensional three-fold interpenetrating network simplified by a bbf topology (vertex symbol (6⁶)₂(6⁴.8²)). Complex I can work as highly sensitive sensors to Cu²⁺, CrO ₄ ^2- and explosive by luminescent quenching.     

Thermal properties of dimethylgold(III) 8-hydroxyquinolinate and 8-mercaptoquinolinate

Dimethylgold(III) complexes with 8-hydroxyquinoline Me₂Au(Ox) (I) and 8-mercaptoquinoline Me₂Au(Tox) (II) were synthesized and studied. Complex II obtained for the first time was identified from the elemental analysis, IR, ¹H NMR, and mass spectrometry data. The thermal properties of complexes I, II in condensed state were investigated by thermography. The temperature dependences of the saturated vapor pressure over crystals were measured by the Knudsen effusion method with mass spectrometric recording of the gas phase composition and the thermodynamic characteristics of the sublimation process were determined: for I, log P[Torr] = (14.6 ± 0.3) ? (6.34 ± 0.10) × 10³/(T, K), Δ H _subl ^o = 121.2 ± 1.9 kJ^?1, Δ S _subl ^o = 224.1 ± 4.6 J mol^?1 K^?1 (the temperature interval under study 80–115°C); for II, log P [Torr] = (13.3 ± 0.2) ? (6.30 ± 0.09) × 10³/(T, K), Δ H _subl ^o = 120.5 ± 1.7 kJmol^?1, ΔS _subl ^o = 199.3 ± 3.0 J mol^?1 K^?1 (86–145°C).     

Structural Features of [{MoO<Subscript>2</Subscript>(L<Subscript>bi</Subscript>)}<Subscript>2</Subscript>(μ-O)] Based Oxomolybdenum(VI) Complexes with Five-Coordinate Molybdenum(VI)

Structural features of eight binuclear complexes with the general formula [{MoO₂(L _bi ⁿ )}₂(μ-O)] (I–VIII) (L_bi is a bidentate chelate ligand, n = 1–8), in which the coordination number of Mo atoms is five, are considered. The parameter τ = (A–B)/60, where A and B are the greatest bond angles among the ten bond angles at the Mo atoms in coordination pentahedra, can be used as a criterion characterizing the coordination polyhedron of the molybdenum atom in complexes I–VIII. The parameter τ is zero for an ideal square pyramid and unity for an ideal trigonal bipyramid.     

Crystal Structure and Properties of Levofloxacinium 2-Thiobarbiturate Trihydrate

The structure of levofloxacinium 2-thiobarbiturate trihydrate LevoH ₂ ⁺ Htba^–·3H₂O (I) (LevoH is levofloxacin, H₂tba is 2-thiobarbituric acid) is determined (CIF file CCDC No. 1547466); its thermal decomposition and IR spectrum are studied. The crystals of I are triclinic: a = 8.670(1) Å, b = 9.605(1) Å, c = 15.786(2) Å, α = 89.144(5)°, β = 88.279(5)°, γ = 76.068(5)°, V = 1275.4(3) ų, space group P1, Z = 2. The unit cell of I contains two LevoH ₂ ⁺ ions, two Htba^– ions, and six H₂O molecules. The absolute structure of the crystal and the configuration of the chiral center in a levofloxacin molecule S are determined. Experiments for generating the second optical harmonics gave a positive result. Intermolecular hydrogen bonds (HBs) N–H···O and O–H···O in I form a bilayer system along the ab diagonal with hydrophilic moieties within a layer and hydrophobic moieties directed outward. The structure is stabilized by multiple HBs and the π–π interaction between the Htba–and LevoH ₂ ⁺ ions and between the LevoH ₂ ⁺ ions.     

Synthesis and crystal structures of binuclear complexes of cobalt(II) and cadmium(II) diisobutyldithiophosphinates with hexamethylenetetramine

Heteroligand complexes [Co₂(HMTA)(iso-Bu₂PS₂)₄] (I) (μ_eff = 4.67 μB) and [Cd₂(HMTA)(iso-Bu₂PS₂)₄] (II) have been synthesized. Single crystals of compounds I and II have been obtained. The crystals are monoclinic: a = 32.622(2) Å, b = 9.4891(6) Å, c = 21.7570(13) Å, β = 125.774(1)^o, V = 5464.3(6) Å,³, Z = 4, ρ_calcd = 1.331 g/cm³ for I; a = 34.6092(7) Å, b = 9.5595(2) Å, c = 22.3473(5) Å, β = 127.144(1)^o, V = 5893.5(2) Å, Z = 4, ρ_calcd = 1.355 g/cm³ for II; space group for both complexes C2/c. Structures I and II are based on discrete binuclear molecules. The coordination polyhedra of the Co and Cd atoms are distorted tetragonal pyramids NS₄, with the bases formed by four S atoms of two bidentate chelating ligand iso-Bu₂PS ₂ ^? and the axial vertices occupied by N atoms of bidentate bridging HMTA ligand. The character of interaction of the molecules in structures I and II is considered.