Inherently chiral biscalixarene cone–cone conformers consisting of calix[4]arene and calix[5]arene subunits

Inherently chiral biscalixarenes with hetero-cavities were synthesized by a covalent assembly of p-tert-butylcalix[5]arene with a 1,3-substituted calix[4]arene via 1,3-alkylation reaction and subsequent desymmetrization. The racemates were resolved by chiral HPLC method. ¹H NMR spectra, VT-NMR spectra, and theoretical calculations support that the calix[5]arene subunit of the inherently chiral calix[4][5]arene ester adopts a cone-in conformation, with the aromatic ring bearing the CH₂CO₂Et group tilting inward the calix[5]arene cavity. By contrast, such a cone-in structural feature of the calix[5]arene subunit disappears for the corresponding inherently chiral calix[4][5]arene carboxylic acid, due to the intramolecular hydrogen bonding between the carboxyl group and an ethereal oxygen of the glycolic chain.     

[Ni(cien)2]2[Mn(NCS)6]·H2O的合成、晶体结构

硫氰酸根的结构为N三C-S-,其两端的N原子和S原子分别有一对和三对孤对电子,因此,硫氰酸根可采用多种不同的配位模式与金属离子发生配位.硫氰酸根可作为单齿配体与一个金属离子配位,形成M-SCN或M-NCS的单核配合物,也可以作为桥联配体同时与两个、三个甚至四个金属离子配位形成多核配合物[1-3];另一方面,硫氰酸根是一个具有一定共轭性的偶极子,可传递磁相作用.因此,选择硫氰酸根作为桥联配体,将多个顺磁金属离子桥联形成一维、二维或三维结构的多核金属配合物分子,并研究它们的磁性已成为分子磁学的一个研究领域[4-6].本文仅报道标题配合物的合成与晶体结构.     

Synthesis and characterisation of [tris(1,3-dithiole-2-thione-4,5-dithiolato)-stannate]2−, [Q]2[Sn(dmit)3], [tris(1,3-dithiole-2-one-4,5-dithiolato)stannate]2−, [Q]2[Sn(dmio)3] and [tris(1,3-dithiole-2-thione-4,5-selenolato)stannate]2−, [Q]2[Sn(dsit)3], complexes: Analysis of the structural variations of the [Sn(dmit)3]2− and [Sn(dmio)3]2− dianions

[Tris(1,3-dithiole-2-thione-4,5-dithiolato)stannate]²⁻, [Q]₂[Sn(C₃S₅)₃], [tris(1,3-dithiole-2-one-4,5-dithiolato)stannate]²⁻, [Q]₂[Sn(C₃S₄O)₃], and [tris(1,3-dithiole-2-thione-4,5-diselenolato)stannate]²⁻ [Q]₂[Sn(C₃S₃Se₂)₃], complexes, have been synthesised and characterised. Crystal structure determinations of [Q]₂[Sn(C₃S₅)₃] (Q=1,4-dimethylpyridinium, monoclinic and orthorhombic forms; NMe₄, NEt₄, and PPh₄) and [NEt₄]₂[Sn(C₃S₄O)₃] revealed variations in the overall dianion structures. The geometry about tin in each case is essentially octahedral with the chelate bite angles in the range 80.7(5)–87.45(4)°: the range of Sn–S distances is 2.5207(18)–2.571(17) Å. A statistical analysis, carried out on the crystal structure data for the six complexes, indicated that the most critical factors in controlling the overall shape of the dianion were the distances of the Sn atom from the dithiolate ligand planes [Sn–OOP]. Interanionic S⋯S interactions, within the sum of the van der Waals’ radii for two S atoms, are affected by the size of the cation, Q; the secondary connectivity is 3-dimensional for the smallest cations, Q=1,4-dimethylpyridinium and NMe₄, in chains for the somewhat larger cation, NEt₄ and is absent for the still larger, PPh₄ cation.     

An Interesting Approach to Bis—calix [5] arene Analogue from Caxlix[6] arene

By 1,4-bridgine of p-tert-butylcalix [6] arene with 2,6-bis(bromomethyl)-4-methyl-anisole,a new type of bis-calix [5] arene analogue was obtained in high yield.     

Synthesis of calcium titanate from [Ca(H2O)3]2[Ti2(O2)2O(NC6H6O6)2]·2H2O as a cheap single-source precursor

Calcium titanate (CaTiO₃) was conveniently synthesized by thermal decomposition of a single-source precursor [Ca(H₂O)₃]₂[Ti₂(O₂)₂O(NC₆H₆O₆)₂]·2H₂O at low temperature. This single-source precursor was characterized by elemental analysis, IR spectrum, thermal gravimetric analysis and X-ray single crystal diffraction. The calcined products at different temperature were further characterized by powder X-ray diffractions and IR spectra. The morphology, microstructure, and crystallinity of the resulting CaTiO₃ materials have been characterized by SEM and TEM. The BET measurement revealed that the CaTiO₃ powders had a surface area of 14.0 m²/g. In addition, the microwave dielectric properties of the resulting CaTiO₃ material have been measured.     

Synthesis and crystal structure of 15α,20α-di(4-hydroxylphenyl)calix[4]pyrroles and 10α,20β-di(4-hydroxylphenyl)calix[4]pyrroles

In the presence of methanesulfonic acid as catalyst, the condensation reactions of 5,5′-dialkyldipyrromethanes with p-hydroxyacetophenone in methanol resulted in a mixture of the unexpected polysubstituted 15α,20α-di(4-hydroxylphenyl)calix[4]pyrroles and the expected 10α,20β-di(4-hydroxylphenyl)calix[4]pyrroles in comparable lower yields. The crystal structures of the new calix[4]pyrroles and their oxyacetate derivatives were successfully determined by X-ray diffraction and the intermolecular interactions in the solid state is briefly discussed.     

Synthesis and Crystal Structure of Two Decavanadates Cluster Metal Complexes: [Co(H2O)6]2[H2V10O28]·6H2O and (NH4)2[Ca(H2O)7]2[V10O28]

Two new decavanadate metal complexes, [Co(H₂O)₆]₂[H₂V₁₀O₂₈]·6H₂O (1) and (NH₄)₂[Ca(H₂O)₇]₂[V₁₀O₂₈] (2), have been synthesized under hydrothermal condition by using chlorhydric acid as the initiator at 120 °C. The aqueous NaVO₃ solution with an aqueous solution of CoCl₂·6H₂O were used for generating 1 and aqueous CaCl₂·2H₂O and NH₄VO₃ solution were employed for creating 2. Compound 1 consisted of discrete hexa-aqua-cobalt [Co(H₂O)₆]²⁺ cations, [H₂V₁₀O₂₈]⁴⁻ anions and non-coordination water molecules. Compound 2 were composed of hepta-aqua-calcium [Ca(H₂O)₇]²⁺ cations, ammonium NH₄ ⁺ and [V₁₀O₂₈]⁶⁻ anion. For compound 2, the distorted pentagonal bipyramid [Ca(H₂O)₇]²⁺ is uncommon. In the crystal lattice, hydrogen bonds played an important role on connecting cations, anions and non-coordinated water molecules to form the three-dimensional network.     

Synthesis, properties, and thermal decomposition of compounds [Co(En)3][Fe(CN)6] · 2H2O and [Co(En)3]4[Fe(CN)6]3 · 15H2O

Binary complex salts, [Co(En)₃][Fe(CN)6] · 2H₂O and [Co(En)₃]₄[Fe(CN)₆]₃ · 15H₂O, are synthesized. The properties of the salts and their thermolysis in air, dihydrogen, and argon are studied. Oxides of the central ions of the binary complex salts are found to be the thermolysis products in an oxidative atmosphere. Solid solutions (intermetallic compounds) CoFe are the thermolysis products in the reductive atmosphere, whereas intermetallides containing considerable amounts of C and N and an impurity of Co and Fe oxides are the thermolysis products in an inert atmosphere. Gaseous thermolysis products in dihydrogen and argon are NH₃, hydrocarbons, and ethylenediamine.     

Some reactions of [(η6-C6Me6)Ru(η6-[2.2]paracyclophane)]-[BF4]2 with nucleophiles

Single addition of the nucleophiles X⁻ (X = H, CN, OH) to the less sterically hindered ring in [(η⁶-C₆Me₆)Ru(η⁶-C₁₆H₁₆)][BF₄]₂ (1) proceeds smoothly to produce, as the sole product, [(exo-η⁵-C₆Me₆X)Ru(η⁶-C₁₆H₁₆)][BF₄]. Use of Na[BD₄] in place of Na[BH₄] gives the expected shift in ν(C-H_exo) in the infrared spectrum.     

Hydrothermal Syntheses, Crystal Structure and Thermal Behavior of [(CH_3)_2NH_2]_2[B_5O_6(OH)_4]_2·[HCON(CH_3)_2] and [NH_3CH_2CH_2NH_3]_2·[B_(14)O_(20)(OH)_6]

Two novel organic base templated nonmetal borates [(CH₃)₂NH₂]₂[B₅O₆(OH)₄]₂·[HCON(CH₃)₂] ( ? ) and [NH₃CH₂CH₂NH₃]₂[B₁₄O₂₀(OH)₆] ( II ) have been synthesized under hydrothermal conditions, and characterized by elemental analyses, FT‐IR spectroscopy, X‐ray diffraction, and TG‐DTA. Their crystal structures were determined from single crystal X‐ray diffraction. The crystal structure of compound I is characterized by forming a 3D supramolecular structure with large channels along axes b and c through O? H···O hydrogen‐bonding among the [B₅O₆(OH)₄]^? anions. The crystal structure of compound II is characterized by forming a 3D supramolecular structure with large channels along axis a and direction [111] through O? H···O hydrogen‐bonding among the [B₁₄O₂₀(OH)₆]^4? anions. The templating organic amine cations in I and II are both obtained through in situ hydrothermal reactions, and are both located in the channels of the 3D supramolecular structure, respectively. Their thermal behavior has been also investigated.     

Synthesis and Crystal Structure of [H-amp]4[Mo8O26(DMF)2]·2H2O (amp = 2-Amino-6-methyl-pyridine)

The reaction of MoO2(acac)2 with 2-amino-6-methyl-pyridine (amp) in the mixed solvent of DMF (N,N-dimethylformamide) and water affords the title complex [H-amp]4- [Mo8O26(DMF)2]·2H2O which was characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction analysis with the following crystallographic data: C30H54Mo8N10O30, Mr = 1802.35, monoclinic, P21/n, a = 8.631(1), b = 24.260(3), c = 13.351(2)A,β= 104.688(3)°, V = 2704.2(7) A3, Z = 2, Dc = 2.213 g/cm3, μ =1.890 mm－1 and F(000) = 1760. The final R = 0.0281 and Wr = 0.0620 for 4935 observed reflections with I > 2σ(I). X-ray structure analysis has confirmed the existence of γ-[Mo8O26]4－ anion in the molecule. Eight MoO6 distorted octahedra share edges with short terminal Mo-O bonds from 1.691(3) to 1.749(2)A, medium bonds from 1.868(2) to 1.965(2) A And long bonds from 2.059(2) to 2.450(2) A. In the terminal site there exist two DMF ligands bound to the Mo atom through O atoms with the Mo-ODMF bond length of 2.166(3) A, affording a bond strength of 0.433. A three-dimensional network structure was formed through hydrogen bonds.     

[Ni(dien)_2]_2[Mn(NCS)_6]·H_2O的合成、晶体结构

硫氰酸根的结构为N≡C－S－，其两端的N原子和S原子分别有一对和三对孤对电子，因此，硫氰酸根可采用多种不同的配位模式与金属离子发生配位。硫氰酸根可作为单齿配体与一个金属离子配位，形成M－SCN或M－NCS的单核配合物，也可以作为桥联配体同时与两个、三个甚至四个金属离子配位形成多核配合物犤１～３犦；另一方面，硫氰酸根是一个具有一定共轭性的偶极子，可传递磁相作用。因此，选择硫氰酸根作为桥联配体，将多个顺磁金属离子桥联形成一维、二维或三维结构的多核金属配合物分子，并研究它们的磁性已成为分子磁学的一个研究领域…     

Crystal Structure of Binuclear Bridging Complex[(dppf)_2Pd_2 (Ⅱ) (μ-Cl)_2] [PF_6]_2

1INTRODUCTIoNFerrocenecontainingtransitionmeta1complexeshasarousedtheinterestofchemistsbecauseofitsnovelstructureandproperties"',Huangetal[2'3isynthesizedsomechainandbridgeformcomplexesandstudiedtheirIRandCV.Linetal[4isyn-thesizedthecrystalof[(dppf)PdCl,jO.5[(CH3),COj(dppf=1,11-(diphenylphosphine)-ferrocene)anddeterminedthestructurebyX-raydiffraction.Inthisarticlewereportthesynthesisandcrystalstructureof[(dppf),Pd,(ll)(p-Cl),j[PF,j2.2EXPERIMENTAL2.1PreparationAsolutionofO.86mm…     

Studies on Synthesis, Structure and Properties of Cobalt Complex [Co( Ⅰ ) (dppe)_2CO]_2[Co_2( Ⅱ ) (dppe)Cl_6O_2]

A cobalt complex with mixed valence state [Co( Ⅰ ) (dppe)2CO]2 [Co2 ( Ⅱ )(dppe) Cl]6O2] (dppe = 1,2 - bis(diphenylphosphino) ethane) has been prepared. The compound crystallizes in triclinic space group P1 with unit cell parameters: a=1. 1763(3) nm, b = 1. 2943(6) nm, c=2. 1507(9) nm, a=81. 44(4)°? ,β=82. 58(3)°, r = 79. 82(3)°, V = 3. 1691 nm3 and Z=1. The structure was solved by direct method according to ALPHA criterion and was refined by a block diagonal matrix least-squares procedure to final R= 0.084, Moreover, infared spectra, electronic reflection spectra and cyclic voltammetry curve were mearsured.     

Synthesis and characterization of the organoimidopolyoxomolybdates [ n -Bu4N]2[Mo6O17(≡NAr)2] (Ar = 2-ethyl-6-methylphenyl and 2-isopropyl-6-methylphenyl)

Two new bifunctionalized arylimido derivatives of hexamolybdate, [n-Bu₄N]₂[Mo₆O₁₇(C₆H₃N-2-C₂H₅-6-CH₃)₂] (1) and [n-Bu₄N]₂[Mo₆O₁₇(C₆H₃N-2-CH(CH₃)₂-6-CH₃)₂]?·?H₂O (2), in which the two organoimido groups are covalently bonded to hexamolybdate at the cis positions, were synthesized by self-assembled metathesis of α-octamolybdate and organoimido ligands with N,N′-dicyclohexylcarbodiimide as dehydration agent, and characterized by elemental analysis, ¹H NMR, IR and electronic spectroscopy, and X-ray diffraction analysis. Both derivatives have short Mo–N bond distances [Mo(1)–N(1), 1.740(3)?Å; Mo(2)–N(2), 1.739(3)?Å for 1 and Mo(1)–N(1), 1.734(3)?Å; Mo(2)–N(2), 1.741(3)?Å for 2] and form dimers via π–π stacking in the crystalline state.     

Synthesis of novel calix[4]crown telomers and selective extraction of cesium ions

p-tert-Butylcalix[4]diazacrown-4 telomer, which contains hard and soft ion binding sites, was synthesized. It exhibited high selectivity toward cesium ions. The binding sites may complex alkali metal ions selectively.     

Synthesis and ‘click’ cycloaddition reactions of tetramethoxy- and tetrapropoxy-2-(ω-azidoalkyl)calix[4]arenes

2-(ω-Chloroalkyl)tetramethoxycalix[4]arenes are converted to 2-(ω-azidoalkyl)tetramethoxy- and cone-2-(ω-azidoalkyl)tetrapropoxycalix[4]arenes, the former by substitution and the latter by demethylation to 2-(ω-chloroalkyl)tetrahydroxycalix[4]arenes, which are O-propylated before substitution of azide for chloride. The azide-terminated calixarenes undergo Cu(I)-catalyzed 1,3-cycloaddition to terminal alkynes to give 1,4-disubstituted 1,2,3-triazoles, demonstrating the potential to couple calixarenes from a tether at the 2-position (methylene bridge) to substrates that bear a terminal alkyne group. The cone conformation of cone-2-(4-chlorobutyl)tetrapropoxycalix[4]arene has been confirmed by X-ray diffraction.     

Synthesis and mesomorphic properties of calix[4]resorcinarene–triphenylene oligomers

By controlling the mol ratios of reactants, novel calix[4]resorcinarene–triphenylene monomer, dimer and tetramer were designed and synthesised in yields of 50–60% via Click chemistry. Their structures were characterised by NMR and MS. Their liquid crystalline behaviours were studied by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction analysis. The more triphenylene units on calix[4]resorcinarene resulted in the wider temperature scopes of mesophase and higher phase transition temperatures. The monomer 6 and dimer 7 showed the mixed columnar mesophase with hexagonal columnar structure and disordered lamellar columnar structure, and compound 8 possessed only disordered lamellar columnar mesophase. These research results suggest that calix[4]resorcinarene was a good platform to construct columnar liquid crystal and the mesomorphic properties were greatly influenced by the substituted numbers of mesogen units on calix skeleton.     

The unusual stability of [NpO2Cl4]2−: Synthesis and characterisation of [NpO2(DPPMO2)2Cl]2[NpO2Cl4] and [Ph3PNH2]2[NpO2Cl4]

The [NpO₂(DPPMO₂)₂Cl][NpO₂Cl₄] complex (where DPPMO₂ = bis(diphenylphosphino)methanedioxide) contains the linear neptunyl group, {NpO₂}²⁺, with two bidentate P=O donor ligands. Coordinating anion Cl^? fills the fifth equatorial coordination site yielding a complex of general formula [NpO₂(DPPMO₂)₂X]₂[Y] (1) (where X = Cl^? and Y = [NpO₂Cl₄]^2?. Reaction between our newly prepared neptunium starting material [NpO₂Cl₂(thf)]_n and phosphinimine ligand produced crystals of [Ph₃PNH₂]₂[NpO₂Cl₄] (2). Compounds 1 and 2 have been structurally characterised.