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.     

Crystal structures of triphenylamylphosphonium iodide [Ph<Subscript>3</Subscript>AmP]I and triphenylamylphosphonium tetraiodide [Ph<Subscript>3</Subscript>AmP]I<Subscript>4</Subscript>

By reaction of triphenylamylphosphonium iodide [Ph₃AmP]I (I) with antimony iodide in acetone, triphenylamylphosphonium tetraiodide [Ph₃AmP]₂I₄ (II) was synthesized. Crystals of I consist of triphenylamylphosphonium cations and iodine anions. Compound II contains two types of tetrahedral triphenylamylphosphonium cations, iodine anions, and [I₃]^? anions. Atoms P have a distorted tetrahedral coordination in cations I and II (the CPC angles are 106.48(12)°–111.25(12)° in I and 107.05(9)°–112.62(10)° in II). The centrosymmetric trinuclear [I₃]^? anion in II is nearly linear (the I(2)I(1)I(3) angle is 178.65°, the I(1)–I(2) and I(1)–I(3) bond lengths are 2.8925(2) Å and 2.9281(2) Å, respectively).     

Kinetics and mechanism of the electrochemical reduction of [1,2-bis(tert-butylperoxy)ethyl]benzene under conditions of the in situ recovery of a platinum surface

The behavior of [1,2-bis(tert-butylperoxy)ethyl]benzene (I) on Pt electrode is studied by means of cyclic voltammetry (CVA). A comparison of the electrochemical properties of I and the properties of previously studied bridge-type 1,2,4,5-tetraoxane ((1,4)-1,4-dimethyl-7-(4-methylbenzyl)-2,3,5,6-tetraoxabicyclo[2.2.1]heptane) (II) shows that the biperoxide studied in this work is reduced on a Pt electrode at lower cathodic potentials and is resistant to electrooxidation.     

Synthesis and structural characterization of two new copper(II) complexes with 3-oxapentane-1,5-diamine using different molar ratio

The reactions of copper(II) nitrate with 3-oxapentane-1,5-diamine (Oda) were investigated under different molar ratio. In the case of a 1: 1 molar ratio of copper(II) nitrate and Oda, the mononuclear complex [Cu(Oda)(NO₃)₂] (I) was obtained. In contrast, the treatment of copper(II) nitrate with twice Oda afforded inorganic polymer {[Cu(μ-Oda)(Oda)] · (NO₃)₂} _n (II). The molecular structures of the two new complexes were determined from the elemental analyses, IR spectra and single-crystal X-ray diffraction (CIF files CCDC nos. 828193 (I) and 828018 (II)). Two Cu(II) complexes were both five-coordinated and forming a distorted square-base pyramidal geometry. Two complexes are stabilized by the intermolecular hydrogenbond.     

Exchange of halogens in the 3a,6a-diaza-1,4-diphosphapentalene derivatives: Crystal structures of iodides

1,4-Dichloro-3a,6a-diaza-1,4-diphosphapentalene (II) easily exchanges halogen with methyl iodide to form the corresponding 1,4-diiodo derivative (V) in a quantitative yield. The reaction of compound II with diiodine (1 equiv) affords compound III, the crystal structure of which contains 55% II and 45% V. Under the conditions of iodine excess (1 : 3), a ionic compound (IV) is formed, the crystal of which contains alternating layers consisting of planar networks [I₂I₃]? and heterocyclic cations [DDP–Cl]⁺. For the crystallographic information for compounds III–V, see CIF files CCDC no. 1560 410 (V), 1560 411 (III), and 1560 412 (IV).     

Crystal structures of the polymer copper(II) complexes with acylhydrazones of bromosalicylaldehyde derivatives

Polymer copper(II) complexes with 5-bromosalicylaldehyde heptanoylhydrazone (I) and 3,5-dibromosalicylaldehyde acetylhydrazone (II) are synthesized and structurally characterized. In complex I, the formation of the polymer is due to the coordination of the hydrazide nitrogen atom to the copper(II) ion of the adjacent fragment. In complex II, polymer formation is due to the binding of the monomer fragments by dipyridyl linkers (CIF files CCDC 947908 (I) and 947909 (II)).     

Molecular and crystal structure and stability of triiodides of quinolinium derivatives

1,2,4-Trimethylquinolinium triiodide (I) and 1-ethyl-2,4-dimethylquinolinium (II) triiodide are synthesized and studied by X-ray diffraction analysis. The layered structures of compounds I and II are formed by mixed stacks of cations and anions. Crystals of compound II consist of two types of anionic chains. The coordinating ability of the corresponding organic iodides toward molecular iodine in chloroform solutions is studied.     

Kinetics and mechanism of the anodic dissolution of gold in solutions of 1,5-diazabicyclo[3.1.0]hexane and its precursors

Studies of the electrochemical behavior of hexahydropyrimidine, 1,5-diazabicyclo[3.1.0]hexane, and 1,3-diaminopropane on a gold electrode via cyclic voltammetry allow us to conclude that gold anodes are subject to corrosion in presence these compounds, yielding complexes that migrate into the solutions and discharge on the counter electrode, producing gold metal deposit. 1,5-Diazabicyclo[3.1.0]hexane is found to form complexes with gold that are much more stable that those formed by hexahydropyrimidine and 1,3-diaminopropane.     

Tetraphenylantimony perrhenate and tetraphenylantimony chlorate: Syntheses and structures

The reaction of tetraphenylantimony chloride with sodium perrhenate or potassium chlorate yields tetraphenylantimony perrhenate (I) and tetraphenylantimony chlorate (II), respectively. Complex I was also synthesized from pentaphenylantimony and triphenylantimony diperrhenate in toluene. According to X-ray diffraction, crystals I and II consist of almost regular tetrahedral tetraphenylstibonium cations (CSbC, 109.4(2)°–109.5(7)° in I and 109.1(1)°–109.6(1)° in II) and [ReO₄]^? (OreO, 107.6(3)°–113.3(5)°) and [ClO₃]^? (OClO, 96.3(9)°, 116.4(5)°) anions, respectively. The average Sb-C bond lengths (2.094(3) Å in I, 2.097(2) Å in II) are close to the sum of the covalent radii of the Sb and C atoms. The average distances Re-O in complex I (1.672(4) Å) and Cl-O in complex II (1.315 Å) correspond to multiple bonds.     

Two 3D zinc-bpe frameworks constructed from 2-carboxyl/sulfo-terephthalate: Crystal structures and luminescent properties

Two new zinc(II) complexes with the formulas of [Zn(HTma)(Bpe)] (I) and [Zn_1.5(Stp) (Bpe)(H₂O)₂] (II), where H₃Tma = 1,2,4-trimellitic acid, Bpe = 1,2-bis(4-pyridyl)ethane, NaH₂Stp = monosodium 2-sulfoterephthalate, have been prepared under hydrothermal conditions. Structural syntheses show complex I is a five-fold interpenetrated three-dimensional structure based on the diamond-like networks, however, complex II is a Bpe-pillared three-dimensional framework (CIF files CCDC nos. 1404475 (I) and 140447 (II)). Thermоgravimetric analyses show that complex I possesses high thermal stability up to 325°C and the dehydrated product of complex II also begins to decompose from 357°C. The luminescent properties of the two complexes are investigated in solid state.     

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.     

Anion-assisted two group IIB metallic coordination architecture and luminescence performance

React of cadmium salts with 4,4'-bis((2-(pyridin-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)biphenyl (Bpbib) yields two one-dimensional (1D) coordination architectures of two new complexes—{[Cd₂(Bpbib)₂(NO₃)₄] ? CH₃OH} _n (I) and {[Cd(Bpbib)Cl₂] ? 2CH₃OH} _n (II). Complexes I and II were characterized by the elemental analyses, photoluminescence and emission spectra and single-crystal X-ray diffraction (CIF files CCDC nos. 1046021 (I), 1046022 (II)). Complex I is a helical array, whereas II features a zigzag pattern, depending upon the type of their associated anions. In addition to the primary organic linker, the counter anions also have a dominant influence on the overall structures, and even arouse the luminescence performance diversity.     

Synthesis,characterization, and biological activity of Cd(II) and Mn(II) coordination polymers based on pyridine-2,6-dicarboxylic acid

The coordination polymers (CPs) {[Cd(Pydc)(H₂O)₃] · PydcH₂} (I) and [Mn(Pydc)(H₂O)₃] · PydcH2} (II) were obtained by the reaction of CdSO₄ · 5H₂O or MnCl₂ · 4H₂O with pyridine-2,6-dicarboxylic acid (PydcH₂). The structures of the CPs I and II were characterized by IR, UV-Vis, TGA, and X-ray single crystal analysis (CIF files CCDC nos. 1417757 (I), 1417758 (II)). The network structures of I and II are constructed by an infinite number of discrete binuclear molecules and free PydcH2. The structures of the CPs I and II connected by the extensive H-bonds and π–π stacking, forming a 3D-network. The CPs I and II were screened to test their antimicrobial activities against different species of bacteria and fungi.     

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 and structural properties of thiapyridinophane and its complex with Ni(II) and Ag(I)

The 2,11-dithia[3.3](3,5)pyrdinophane (L¹) has been synthesized by a new method and characterized by ¹H NMR, which is used to form coordination complexes C₁₄H₁₄N₄O₆S₂Ni (I) by addition of Ni²⁺ cation and C₁₄H₁₄N₃O₃S₂Ag (II) by addition of Ag⁺ cation. 2,11,20-Trithia[3.3.3](3,5)pyridinophane (L²) and 2,11,20,29-tetrathia[3.3.3.3](3,5)pyridinophane (L³) have also been synthesized as by-products. Single-crystal X-ray analysis reveals that the conformation of the L¹ is syn(boat-chair), complexes I and II also adopt syn(boat-chair) (CIF files CCDC nos. 1400332 (I) and 700724 (II)). While in I, Ni(II) is coordinated with L¹ with two nitrogen and four oxygen atoms, in II, Ag(^I) is coordinated with L¹ by two nitrogen and two sulfur atoms came from four ligands. In complexes I and II, the formation of three-dimensional structure depends on π???π stacking and 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.     

Crystal structure,fluorescence spectroscopy,and electrochemical property of two neodymium coordination polymers with phenoxy acids

Two nine-coordination coordination polymers of neodymium, [Nd₂(p-C₈H₄O₄)(o-C₈H₄O₄)₂ ? 4H₂O] _n (I), [Nd₂(C₁₀H₄O₈)(C₁₀H₂O₈) ? 2H₂O] _n (II), have been prepared by hydrothermal reaction of Nd(NO₃)₃ ? 6H₂O with terephthalic acid and phthalic acid, or benzenetetracarboxylic anhydride and determined by means of IR, UV, fluorescence, TG-DTA, cyclic voltammetry (CV) and X-ray single-crystal diffraction methods (CIF files CCDC nos. 1006206 (I), 979309 (II)). Yellow-green luminescence could been observed at 391 nm (λ_ex = 305 nm) for complex I and 370 nm (λ_ex = 331 nm) for the complex II. The emission of complexes I and II may be due to the π* → n transition, which may be assigned to the ligand-to-metal charge-transfer bands. Compared with complex II, the complex I exhibits a stronger fluorescence intensity for the different coordinated environment. Cyclic voltammetric measurement of the two compounds reveal that the compounds both have a couple of irreversible redox peak, indicating that the two polymers were both corresponded to the unusual Nd(III)/Nd(V).     

Synthesis,Crystal Structure,and Luminescent Properties of Two Zn<Superscript>II</Superscript>/Cd<Superscript>II</Superscript> Coordination Polymers Based on 1,4-Bis(pyridine-3-Ylmethoxy)benzene

Two polymeric frameworks, [Zn(Dpb)(Oba)] _n (Ι) and [Cd(Dpb)(2,6-Pda)H₂O] _n · nH₂O (II) (Dpb = 1,4-bis(pyridin-3-ylmethoxy)benzene, H₂Oba = 4,4'-oxybis(benzoic acid), 2,6-H₂Pda = 2,6-pyridyl-dicarboxylate), have been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction method (CIF files CCDC 1488269 (Ι), 1488270 (II)). Complex Ι is a 2D layer structure, which is constructed from 1D double chain. Complex II is a 1D chain. The luminescent properties of Ι, II have been investigated with fluorescent spectra in the solid state, I and II displayed a strong fluorescent emission at room temperature.     

Copper(II) complexes of mono-condensed N,O-donor Schiff base ligands: Synthesis,crystal structures,and antibacterial activity

Two new copper(II) complexes, [Cu(L¹)₂] (I) and [Cu(L²)₂] (II), where L¹ = 2-bromo-4-chloro- 6-(isopropyliminomethyl)phenolate and L² = 2-bromo-4-chloro-6-[(2-hydroxyethylimino)methyl]phenolate, have been prepared and structurally characterized by X-ray crystallography (CIF files CCDC nos. 1445936 (I) and 1445935 (II)). In both complexes, the Cu atoms are coordinated by two phenolate oxygen and two imino nitrogen, giving square planar geometry. The complexes have been tested on various strains of bacteria to study their antibacterial effects.     

Volatile dimethylgold(III) β-iminovinylthionates: Synthesis,structure, and properties

Volatile dimethylgold(III) β-iminovinylthionates, (CH₃)₂Au(CH₃CSCHC(NH)CH₃) (I) and (CH₃)₂Au(CF₃CSCHC(NH)CH₃) (II), were studied. For complexes I and II, the synthesis is described and data from elemental analysis, IR and UV/Vis spectra, DTA, and X-ray diffraction are given. The structures of I and II are composed of monomeric complexes combined into polymeric stack-type associates. The distorted square environment of gold is formed by sulfur and nitrogen atoms of the chelating ligand and two carbon atoms of the methyl groups. For complex I, the average Au-S bond length is 2.260 Å, the Au-N bond length is 2.137 Å, and the chelate angle SAuN is 94.1°; for II, these values are 2.355 Å, 2.088 Å, and 93.7°, respectively.