(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 and study of sodium vanadomanganate

Sodium 13-vanadomanganate Na₇[MnV₁₃O₃₈]·5H₂O (I) has been synthesized and studied by mass spectrometry, thermogravimetry, IR spectroscopy, and X-ray powder diffraction analysis. The crystals of compound I are monoclinic: a = 11.487 Å, b = 7.613 Å, c = 11.359 Å, β = 114.15°, V = 906.52 ų, ρ_calcd = 2.73 g/cm³, Z = 1.     

A new 1D chiral metal-organic coordination polymer constructed by Cu(II) with L-3-Cyanophenylalanine

A new 1D chiral metal-organic coordination polymer [Cu(Cphe)₂] · 3H₂O (I) (HCphe = L-3-Cyanophenylalanine) has been synthesized in an aqueous solution and characterized by elemental analysis, thermogravimetric analysis (TGA), X-ray powder diffraction (XRPD), infrared spectroscopy (IR) and single crystal X-ray diffraction. The X-ray diffraction analysis reveals that I crystallizes in the monoclinic space group P2₁. The adjacent copper(II) atoms are linked by Cphe ligands to form a 1D zigzag chain, which is further connected via strong hydrogen bonds to form a 3D supramolecular framework. The unit cell parameters for I are: a = 12.0201(8), b = 6.1495(4), c = 14.8576(10) Å, β = 94.1720(10)°, V = 1095.00(13) ų, and Z = 2.     

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.     

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.     

Syntheses and crystal structures of (2.2.2-cryptand)potassium chloride and (2.2.2-cryptand)ammonium bromide<Subscript>(0.75)</Subscript>chloride<Subscript>(0.25)</Subscript> hydrates

Two new complexes were synthesized, namely, 7: 2 (2.2.2-cryptand)potassium chloride and (2.2.2-cryptand)ammonium bromide_(0.75)chloride_(0.25) hydrates: [M(Crypt-222)]⁺ · Hal^? · 3.5H₂O, where M = K, Hal = Cl (I) and M = NH₄, Hal = Br_0.75Cl_0.25 (II). The structures of two isomorphous crystals were studied by X-ray diffraction analysis. Trigonal (space group P \(\bar 3\), Z = 2) structures I (a = 11.763 Å, c = 11.262 Å) and II (a = 11.945 Å, c = 11.337 Å) were solved by direct methods and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.057 (I) and 0.065 (II) for all 2626 (I) and 1654 (II) independent measured reflections (CAD-4 automated diffractometer, λMoK _α). In structures I and II, the host-guest [M(Crypt-222)]⁺ complex cation lies on the threefold crystallographic axis and has the approximate D ₃ symmetry. In complex I, the coordination polyhedron of the K⁺ cation (CN = 8) is a bicapped trigonal prism somewhat distorted toward an antiprism. Complexes I and II contain H-bonded disordered cubes of the water molecules and the Cl^? or Br^? anions.     

Synthesis and structures of Cu<Superscript>I,II</Superscript> complexes with a 2,2´-bipyridine derivative bearing a (+)-3-carene moiety

The complex salt {[CuL₂][Cu₄I₆]?MeCN}_n (1) and the compound [Cu₄L₃I₄]?3 MeCN (2) (L is a chiral ligand bearing a natural monoterpene (+)-3-carene moiety) were synthesized. The crystal structures of compounds 1 and 2 were determined by X-ray diffraction. The structure of compound 1 consists of complex cations [CuL₂]²⁺ (N₃O₂ polyhedron is a trigonal bipyramid) and Cu^I coordination polymers (CuI₄ polyhedron is a tetrahedron) as anions. The experimental magnetic moment μ_eff at 300 K is 1.90 μ_B, which is consistent with the X-ray diffraction data and the assumption that compound 1 is mixed-valence. The structure of compound 2 comprises a tetranuclear Cu^I complex, in which three Cu atoms are coordinated by two N atoms of the ligand L and two I atoms, and the fourth Cu atom is coordinated by four I atoms (coordination polyhedra are distorted tetrahedra). Compounds L and 2 were found to influence the viability of human laryngeal carcinoma cells (Hep2). The IC₅₀ value for complex 2 (13.0±1.7 μM) is substantially smaller than IC₅₀ for compound L (30.5±0.5 μM).     

Synthesis and crystal structures of cobalt(III) and zinc(II) complexes derived from 4-chloro-2-[(2-morpholin-4-ylethylimino)methyl]phenol with urease inhibitory activity

A new mononuclear cobalt(III) complex, [CoL₂(N₃)]₂ · CH₃OH (I), and a new mononuclear zinc(II) complex, [ZnLCl(CH₃OH)] (II) (HL = 4-chloro-2-[(2-morpholin-4-ylethylimino)methyl]phenol), were prepared and structurally characterized by elemental analyses, infrared spectroscopy, and single- crystal X-ray diffraction. The crystal of I is monoclinic: space group P2₁/c, a = 18.742(2) Å, b = 15.197(2) Å, c = 25.646(2) Å, β = 125.996(3)°, V = 5909.8(11) ų, Z = 4. The crystal of II is monoclinic: space group P2₁/c, a = 7.257(1) Å, b = 24.707(2) Å, c = 9.637(1) Å, β = 101.557(2)°, V = 1692.9(3) ų, Z = 4. The Co atom in I is in an octahedral coordination, and the Zn atom in II is in a trigonal-bipyramidal coordination. The urease inhibitory test shows that complex I has strong urease inhibitory activity, while complex II has no activity.     

Double chains-copper(I)-based coordination polymer with strong blue fluorescent emission

A solvothermal reaction of Cu(CN) with triphenylphosphine yielded a double-chain coordination polymer of the formula C₂₀H₁₅Cu₂N₂P (I). X-ray diffraction study shows that complex I crystallizes in the monoclinic system, space group P2₁/n, with lattice parameters a = 9.3017(8), b = 12.4273(13), c = 16.0505(15) Å, β = 91.688(6)°, V = 1854.6(3) ų, Z = 4, and ρ_calcd = 1.581 mg m^?3. The Cu(I) atoms show difference in the coordination environment. Complex I emits strong blue fluorescence light (λ_em(max) = 516 nm), when it is excited by the UV light (λ_exc(max) = 250 nm) in the solid state at room temperature.     

Synthesis and structure of diethylenetriammonium tetrachloroaurates(III)

The (DienH₃)[AuCl₄]₃ · H₂O (I) and (DienH₃)₂[AuCl₄]Cl₅ (II) compounds were obtained by the reaction of HAuCl₄ with diethylenetriamine trihydrochloride (DienH₃Cl₃) in hydrochloric acid. The compounds were characterized by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. Crystals of I and II are monoclinic with space group P2₁/n. For I, a = 12.2314(3) Å, b = 14.6077(5) Å, c = 13.2680(5) Å, β = 106.7350(10)°, V = 2270.22(13) ų, Z = 8. For II, a = 6.62990(10) Å, b = 17.9026(5) Å, c = 10.3661(3) Å, β = 101.9230(10)°, V = 1203.83(5) ų, Z = 2. Both structures are ionic. The gold atoms in I and II have a 4 + 2 coordination environment. The Au-Cl bond lengths are within 2.276–2.294 Å, and the axial Au…Cl contacts are within 3.315–3.405 Å. The diethylenetriammonium cation in I and II has different conformations.     

Synthesis,Crystal Structure,Luminescence Sensing,and Photocatalytic Properties of a 2D Cobalt(II) Coordination Polymer Containing Bis(benzimidazole) Moieties

A new cobalt(II) coordination polymer, namely [Co(L)(Ndc)] _n (I), where L = 1,5-bis(5,6- dimethylbenzimidazole)pentane, H₂Ndc = 2,6-naphthalenedicarboxylic acid, was synthesized and characterized by elemental analysis, IR spectra, powder X-ray diffraction and single-crystal X-ray diffraction (CIF file CCDC no. 1548044). Complex I displays a 2D (4,4) layer which further extended into a 3D supramolecular framework via weak C–H···O hydrogen bondings. The luminescence explorations demonstrated that I exhibits highly selective and sensitive sensing for Cr₂O ₇ ^2? with high quenching efficiency K_sv value of 9.87 × 10³ L mol^?1 and low detection limit (0.24 μM (S/N = 3)). Meanwhile I also exhibits highly selective and sensitive sensing for Fe³⁺ with quenching efficiency K_sv = 3.6 × 10⁴ L mol^–1 and low detection limit (0.32 μM (S/N = 3)). Complex I exhibits higher photocatalytic activities for the degradation of methylene blue under UV irradiation. Additionally, the thermal behavior and electrochemical properties of the compound are also presented.     

Bis(citrato)germanates of bivalent 3<Emphasis Type="Italic">d</Emphasis> metals (Fe,Co, Ni,Cu, Zn): Crystal and molecular structure of [Fe(H<Subscript>2</Subscript>O)<Subscript>6</Subscript>][Ge(HCit)<Subscript>2</Subscript>] · 4H<Subscript>2</Subscript>O

In continuation of a systematic study of bis(citrate)germanates, we synthesized a number of heterometallic germanium(IV) and 3d metal complexes based in citric acid (H₄Cit) with the molecular formula [M(H₂O)₆][Ge(HCit)₂] · nH₂O, where M = Fe, n = 4 (I); Co, n = 2 (II); Ni, n = 2 (III); Cu, n = 1 (IV); Zn, n = 3 (V). The complexes were characterized by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. The X-ray diffraction analysis of compound I was performed. Crystals are monoclinic, a = 10.091(4) Å, b = 11.126(4) Å, c = 10.996(4) Å, β = 100.966(6)°, V = 1212.1(8) ų, Z = 4, space group P2₁/n, R1 = 0.0561 for 2266 reflections with I > 2σ(I). Compound I is composed of centrosymmetric octahedral complexes-[Ge(HCit)₂]^2? anions and [Fe(H₂O)₆]²⁺ cations—and crystallization water molecules. Structural units in compound I are combined by a hydrogen bond system.     

Preparation and physicochemical study of sodium hexamolybdometallates(III)

Sodium hexamolybdocobaltate(III) Na₃[CoMo₆O₁₈(OH)₆] · 8H₂O (I) and sodium hexamolybdochromate Na₃[CrMo₆O₁₈(OH)₆] · 8H₂O (II) were synthesized and studied by mass spectrometry, thermogravimetry, powder X-ray diffraction, and IR spectroscopy. The crystals are monoclinic. For compound a = 10.31 Å, b = 10.31 Å, c = 17.55 Å, β = 100.93°, V = 1834.77 ų, ρ_calcd = 3.04 g/cm³, Z = 3; for compound II: a = 10.33 Å, b = 10.33 Å, c = 17.59 Å, β = 100.98°, V = 1835.09 Å3, ρ_calcd = 3.01 g/cm³, Z = 3.     

Syntheses and crystal structures of copper(II) and nickel(II) complexes derived from 2-bromo-4-chloro-6-[(2-methylaminoethylimino)methyl]phenol

A new centrosymmetric mononuclear copper(II) complex [Cu(L)₂](ClO₄)₂ (I) and a new centrosymmetric mononuclear nickel(II) complex [Ni(L)₂(MeOH)₂](ClO₄)₂ (II), where L is the zwitterionic ligand 2-bromo-4-chloro-6-[(2-methylammonioethylimino)methyl]phenolate, have been prepared from the Schiff base 2-bromo-4-chloro-6-[(2-methylaminoethylimino)methyl]phenol with copper perchlorate and nickel perchlorate, respectively. The complexes were characterized by elemental analysis, infrared spectra, and single-cyrstal X-ray diffraction (CIF files CCDC nos. 1408054 (I) and 1407973 (II)). Complex I crystallizes in the monoclinic space group P2₁/c with unit cell dimensions a = 7.7736(4), b = 21.608(1), c = 8.5194(4) Å, β = 93.907(2)°, V = 1427.7(1) ų, Z = 2, R ₁ = 0.0546, and wR ₂ = 0.1531. Complex II crystallizes in the monoclinic space group P2₁/c with unit cell dimensions a = 21.324(3), b = 16.821(2), c = 9.425(1) Å, β = 90.114(2)°, V = 3380.5(7) ų, Z = 4, R ₁ = 0.0693, and wR ₂ = 0.1627. The Cu atom in I is in square planar coordination, and the Ni atom in II is in octahedral coordination.     

Structure and photoluminescence of Zn(II) and Сd(II) complexes with chiral bis-pyridine containing fragments of natural (–)-α-pinene

Complexes ZnLCl₂ (I) and [CdLCl₂] _n (IV), where L is chiral bis-pyridine containing fragments of natural monoterpenoide (–)-α-pinene are synthesized. Single crystals of [ZnLCl₂]·CH₂Cl₂ (II), [ZnLCl₂]·i-PrOH (III), and IV compounds are grown. The crystal structures of II and III are composed of mononuclear ZnLCl₂ complex molecules and solvate CH₂Cl₂ and i-PrOH molecules; the coordination polyhedron of the zinc atom Cl₂N₂ is a distorted tetrahedron. According to the single crystal XRD data, complex IV is a 1D coordination polymer; the coordination core CdN₂Cl₄ is a distorted octahedron and Cl atoms are bridging ligands. In the structures of II, III, and IV the L molecule functions as a bidentate chelate ligand. In the solid phase, complexes I and IV exhibit photoluminescence in the visible range (λ_max 505 nm and 460 nm respectively). The band intensity in the photoluminescence spectra of I and IV complexes considerably exceeds the band intensity in the spectrum of free L.     

Copper(II) and cobalt(II) complexes with a chiral 5-pyrazolone derivative obtained from the terpene (+)-3-carene: Synthesis and properties

The complexes [CuLCl₂] (I), [CoLCl₂] (II), and CuLBr₂ (III) (where L is the derivative of optically active 5-pyrazolone prepared from the terpene (+)-3-carene) were obtained and characterized. According to X-ray diffraction data, crystal structures I and II (orthorhombic crystal system) are built from mononuclear acentric molecules. In the resulting complexes, the Cu²⁺ or Co²⁺ ion coordinates two N atoms of the chelating bidentate ligand L and two Cl atoms, thus making a distorted tetrahedron. Intermolecular contacts and the hydrogen bonds Cl(1)…H-O(1) give rise to columns parallel to axis y. For complexes I and III, μ_eff = 1.83 and 1.81 μB, respectively; these values correspond to the electronic configuration d ⁹ . For complex II, μ_eff = 4.42 μB, which suggests the tetrahedral structure of the coordination entity CoCl₂N₂. Complexes I and III were studied by EPR spectroscopy.     

Crystal structure of adducts of copper(II) acetylacetonate and hexafluoroacetylacetonate with 4-aminopyridine

Single crystal X-ray diffraction is used to investigate two synthesized β-diketonate complexes of copper(II) with aminopyridine: Cu(4-NH₂Py)(aa)₂ (I) and Cu(4-NH₂Py)(hfa)₂ (II). The crystals of I and II have a monoclinic system; the unit cell parameters of I are: P2₁/n space group, a = 8.2921(3) Å, b = 14.7243(5) Å, c = 13.4970(4) Å, β = 102.426(1)°, V = 1609.32(9) ų, Z = 4; for II: C2/c space group, a = 23.5704(5) Å, b = 11.4977(2) Å, c = 16.0285(3) Å, β = 109.265(1)°, V = 4100.6(1) ų, Z = 8. The structures of I and II are molecular; they are composed of isolated molecules. The coordination polyhedron of the copper atom is formed by the O atoms of two acetylacetonate ligands (Cu-O 1.940(2)–2.171(2) I and the O atoms of two hexafluoroacetylacetonate ligands (Cu-O 1.940(2)–2.215(3) Å) in II. The molecules of 4-NH₂Py are bonded to the copper atom via the nitrogen atom of the aromatic ring (Cu-N 2.008(2) Å in I and Cu-N 1.978(3) Å in II). Noncoordinated amino groups join the molecules of the complexes together by means of N-H…O hydrogen bonds.     

Self assembly of three new copper coordination polymers based on N-[(3-pyridine)-sulfonyl]aspartate: Synthesis and structure

Three new copper coordination polymers [Cu(L) · 6H₂O] _n (I), [Cu₂(L)₂] _n (II), and [Cu(HL)₂] _n (III), where H₂L is N-[(3-pyridine)-sulfonyl]aspartate, have been synthesized and characterized by singlecrystal X-ray diffraction (CIF files CCDC nos. 1435871 (I), 1435872 (II), 1435873 III), elemental analysis and IR spectra. Moreover, the variable-temperature magnetic susceptibility had been studied for complex I. A structural comparison of these polymers suggests that different reaction temperatures play important role in the construction of resulting architectures for I–III.     

Synthesis and crystal structure of a 1D coordination polymer Cu<Subscript>3</Subscript>(Mip)<Subscript>4</Subscript>(2,2′-Bipy)<Subscript>2</Subscript> (H<Subscript>2</Subscript>Mip = 5-methylisophthalic acid, 2,2′-Bipy = 2,2′-bipyridine)

A new metal-organic coordination polymer Cu₃(Mip)₄(2,2′-Bipy)₂ (I), where H₂Mip = 5-methylisophthalic acid, 2,2′-Bipy = 2,2′-bipyridine has been hydrothermally synthesized and characterized by IR, elemental analysis, single-crystal X-ray diffraction analysis, and powder X-ray diffraction. The X-ray diffraction analysis reveals that I crystallizes in the triclinic crystal system, space group P \(\bar 1\) and exhibits a one-dimensional chain structure, which contains a trinuclear [Cu₃(Mip)₂(HMip)₂(2,2′-Bipy)₂] subunit, and the adjacent subunits are bridged by Mip anions into a 1D chain. Unit cell parameters for I: a = 10.239(2), b = 11.249(2), c = 11.971(2) Å, α = 82.01(1)°, β = 65.03(2)°, γ = 84.32(2)°, V = 1236.5(4) ų, Z = 2.     

Synthesis,crystal structure,and antibacterial activity of oxovanadium(V) complexes derived from <Emphasis Type="Italic">N</Emphasis>'-[1-(5-fluoro-2-hydroxyphenyl)methylidene]nicotinohydrazide and <Emphasis Type="Italic">N</Emphasis>'-(5-fluoro-2-hydroxybenzylidene)-2-hydroxynaphthylhydrazide

Two new oxovanadium(V) complexes, [VOL¹(OCH₃)(CH₃OH)] (I) and [VOL²(OCH₃)] (II), where L¹ and L² are the di-anionic form of N'-[1-(5-fluoro-2-hydroxyphenyl)methylidene]nicotinohydrazide and N'-(5-fluoro-2-hydroxybenzylidene)-2-hydroxynaphthylhydrazide, respectively, have been synthesized and characterized by elemental analysis, FT-IR spectra, and single crystal X-ray determination (CIF files CCDC nos. 891852 (I), 891853 (II)). The crystal of I is monoclinic: space group P2₁/c, a = 8.061(1), b = 15.293(2), c = 13.471(2) Å, ß = 92.595(2)°, V = 1658.8(4) ų, Z = 4. The crystal of II is monoclinic: space group P2₁/n, a = 7.4454(9), b = 8.0833(9), c = 28.906(2) Å, ß = 92.644(2)°, V = 1737.8(3) ų, Z = 4. The V atom in I is in an octahedral coordination, and that in II is in a square-pyramidal coordination. The antibacterial activity of the compounds against various bacteria was assayed.