NaSc3[HPO3]2[HPO2(OH)]6: Synthesis,Crystal Structure,and Thermal Decomposition

NaSc₃[HPO₃]₂[HPO₂(OH)]₆ was prepared by use of a phosphorus acid flux route. The crystal structure was determined from single‐crystal X‐ray diffraction data: triclinic, space group P$\bar{1}$ (No. 2), a = 7.4507(11) Å, b = 9.6253(17) Å, c = 9.6141(16) Å, α = 115.798(4)°, β = 101.395(4)°, γ = 101.136(3)°, V = 577.29(16) Å³ and Z = 1. The crystal structure of NaSc₃[HPO₃]₂[HPO₂(OH)]₆ contains two kinds of phosphate(III) groups: HPO₃^2– and HPO₂(OH)^–. Phosphate(III)‐tetrahedra, NaO₆ and ScO₆ octahedra together form a (3,6)‐connected net. During heating hydrogen and water are released and Sc[PO₃]₃ is formed as the main crystalline decomposition product.     

Crystal Structure of Iron(II) Acetate

In this paper the X‐ray structure and magnetic properties of iron(II) acetate – starting material for the synthesis of a wide range of iron complexes – are presented. The compound crystallises in the space group Pbcn and was identified as 2D coordination polymer consisting of iron atoms and acetate moieties with all the iron atoms hexacoordinate and different coordination modes for the acetate moieties. Additional hydrogen bond contacts lead to a porous coordination polymer with 1D channels in the size of mesopores. Temperature dependent magnetic measurements confirm that the complex is a high‐spin compound in the entire temperature range investigated with a room temperature magnetic moment of 5.4 μ_B. Field‐dependent magnetisation measurements reveal a slightly sigmoidal curve progression typical for metamagnetism.     

Dimorphic Modification of the Trinuclear Nickel(II) Complex [Ni3(NCS)6(pdz)6]: Synthesis,Crystal Structure,Thermal, Magnetic and Spectroscopic Properties

Reaction of nickel(II) thiocyanate and pyridazine (pdz) as organic spacer ligand leads to the formation of the ligand‐rich 1:2 (1:2 = metal to ligand ratio) trinuclear nickel(II) complex of composition [Ni₃(NCS)₆(pdz)₆]. Depending on the reaction solvent, different polymorphic modifications are obtained: Reaction in acetonitrile leads to the formation of the new modification 1I and reaction in ethanol leads to the formation of modification 1II reported recently. In their crystal structures discrete [Ni₃(NCS)₆(pdz)₆] units are found, in which each of the Ni²⁺ cations exhibits a NiN₆ distorted octahedral arrangement. The central Ni²⁺ cation is coordinated by four bridging pdz ligands and two thiocyanato anions in trans positions. Both thiocyanato anions exhibit the end‐on bridging mode. The peripheral Ni²⁺ cations are bridged by one thiocyanato anion and by two pdz ligands with the central Ni²⁺ cation. Further they are coordinated by two terminal N‐bonded thiocyanato anions and one terminal N‐bonded pdz ligand. The structure of 1I was determined by X‐ray single crystal structure investigation and emphasized by infrared spectroscopy. Magnetic measurements revealed a quasi Curie behavior with net ferromagnetic interactions for 1I and net antiferromagnetic interactions for 1II . Solvent‐mediated conversion experiments clearly show that modification 1I represents the thermodynamic most stable form at room temperature and that modification 1II is metastable. On thermal decomposition, both modification transform quantitatively in a new ligand‐deficient intermediate. Elemental analysis revealed a 3:4 compound of composition [Ni₃(NCS)₆(pdz)₄]. A structure model supported by IR spectroscopic investigations was assumed, in which three coordination modes of the thiocyanato anion exist, resulting in a 2D polymeric network.     

New Aquapentachlorochromate(III) Compounds: K2[CrCl5(H2O)] and (NH4)2[CrCl5(H2O)]

Synthesis and crystal structures of two new compounds, K₂[CrCl₅(H₂O)] ( I ) and (NH₄)₂[CrCl₅(H₂O)] ( II ) are reported. Both compounds were prepared from chromium(VI) salts by two different methods and reaction pathways of these syntheses are suggested. The crystal structures of these two aquapentachlorochromates(III) have been determined from three dimensional X‐ray data collected at low temperature, 173 K. The two structures are isomorphous and their unit cell dimensions are quite similar. They are orthorhombic, space groups Pnma, with Z = 4. Both structures are composed of [CrCl₅(H₂O)]^2? units held together by the counterion framework. The coordination around the chromium ion deviates from a regular octahedron due to the shorter equatorial chromium‐oxygen bond.     

Synthesis and Characterization of p—[Perfluoro—1—（2—fluorosulfonylethoxy）]ethylated Polystyrene

A new fluorinated polystyrene bearing a p-sulbstiuted perfluoro[1-(2-fluorosulfonylethoxy)]ethyl group was synthesized via one-electron oxidation of polystyrene by perfluoro[2-(2-fluorosulfonylethoxy)]propionyl peroxide at different peroxide to polystyrene molar ratios.The yield of perfluoroalkylation decreases with the increase of the reactant molar ratio.The modified polymer has been characterized by various techniques:the ring pefluoro[1-(2-fluorosulfonylethoxy)]ethylation has been proved by FT-IR and ^19FNMR;the X-ray photoelectron spectra(XPS) show the maximum binding energy of F18,O18,C18(two kinds of carbon atoms,namely C-H and C-F)and S2p,respectively; desulfonylation of the fluorinated polystyrene appearing at 217℃ has been found by its thermogravimetric analysis (TGA).The determinations of contact angle,refractive index and glass transition temperature of the modified polymer have disclosed that when the contact angle increases with the increase of the molar ratio,the refractive index and glass transition temperature decrease.The polydispersity values indicate that the degradation of the polymer chains did not occur during the reaction.     

Synthesis,Crystal Structure and Selected Properties of Mono(dithiocarbamato)‐gold(I), AuS2CNH2

The title compound AuS₂CNH₂ was prepared from an aqueous solution by reaction of dicyanidoaurate [Au(CN)₂]^– with excess of ammoniumdithiocarbamate NH₄S₂CN H ₂ at pH ≈ 2. The compound crystallizes in the orthorhombic space group Cmma with a = 6.4597(2), b = 12.6556(3), and c = 5.3235(1) Å. The crystal structure comprises linear S–Au–S dumbbells forming unbranched zigzag chains in combination with the dithiocarbamate ligands. The three‐dimensional arrangement of the molecules is realized by aurophilic Au^I–Au^I and hydrogen bonding interactions, respectively. AuS₂CNH₂ presents orange luminescence due to a broad emission band between 12000 cm^–1 and 23000 cm^–1 (ν = 26316 cm^–1).     

Crystal Structure and Spectroscopic Properties of Bis[trans‐dichlorobis(2,2‐dimethylpropane‐1,3‐diamine)chromium(III)] Tetrachlorozincate

The structure of trans‐[Cr(Me₂tn)₂Cl₂]₂ZnCl₄ (Me₂tn = 2,2‐dimethylpropane‐1,3‐diamine) was determined by a single‐crystal X‐ray diffraction study at 173 K. The analysis reveals that there are three crystallographically independent chromium(III) complex cations in the title compound. The chromium(III) atoms are coordinated by four nitrogen atoms of Me₂tn and two chlorine atoms in a trans arrangement, displaying a distorted octahedral geometry. The two six‐membered chelate rings in three complex cations are oriented in an anti chair–chair conformation with respect to each other. The Cr–N and Cr–Cl bond lengths average 2.0862(2) and 2.3112(6) Å, respectively. The ZnCl₄^2– have slightly distorted tetrahedral arrangement with Zn–Cl lengths and the Cl–Zn–Cl angles are influenced by hydrogen bonding. The resolved absorption maxima in the electronic d–d spectrum were fitted with a secular determinant for a quartet energy state of the d³ configuration in a tetragonal field. It is confirmed that the nitrogen atoms of the Me₂tn ligand are strong σ donors, but the chloro ligands have weak σ‐ and π donor properties toward the chromium(III) ion.     

Synthesis,Spectral Properties,and Crystal Structure of {Methoxo[4-phenylbutane-2,4-dione(p-nitrobenzoyl) hydrazonato(2-)]oxovanadium(V)}

The hydrazino complex {methoxo[4-phenylbutane-2,4-dione(p-nitrobenzoyl)hydrazonato(2-)]oxovanadium(V)}, VO(p-NO₂bhbzac)OCH₃, (1), has been prepared by the direct reaction of bis(benzoylacetonato) oxovanadium(IV), VO(bza)₂, with p-NO₂-C₆H₄C(O)NHNH₂, p-NO₂bh, in CH₃OH. The resulting compound contains benzoylacetone-(p-NO₂)benzoyl hydrazone as tridentate Schiff base-type ligand and OCH₃ group as Lewis base, both ligated to vanadium. The crystals are orthorhombic, with Z = 8, space group Pbca, a = 11.699(5) Å, b = 14.035(5) Å, c = 22.564(5) Å, R1 = 0.0756 and wR2 = 0.1302. The crystal structure demonstrated the square-pyramidal geometry of the VO_oxo(ONO)O coordination sphere with the oxo ligand at the apical position. The electronic absorption spectra revealed a ligand-to-metal charge-transfer (LMCT) band in the near UV region at _max = 23,700 cm^–1 (B = 5640 dm³ mol^–1 cm^–1) in CH₃CN, _max = 23,420 cm^–1 (B = 5550 dm³ mol^–1 cm^–1) in DMSO, and _max near 26,950 (sh) cm^–1 (B = 10,550 dm³ mol^–1 cm^–1) in CH₂Cl₂. The FT-IR spectra of (1) show the characteristic strong (V = O) stretching vibration at 993 cm^–1 and support the view that the oxovanadium complex is pentacoordinated and monomeric.     

Synthesis and Crystal Structure of Bis[a-chloro-(o-chloro-benzylidene)] Hydrazine

1 INTRODUCTION The azine derivatives are useful compounds because of their special properties. On the one hand, the azines and ,-dichloro-azines are very impor- tant intermediates[1, 2] for synthesizing s-tetrazines which have some peculiar properties, s…     

Oxamido‐bridged N4 Macrocyclic Complexes CuII/MII/CuII (M = Mn,Co): Synthesis,Crystal Structures and Magnetic Properties

Two new oxamido‐bridged N₄ macrocyclic complexes [(CuL)₂Mn(C₂H₅OH)₂](ClO₄)₂ · 2C₂H₅OH ( 1 ) and [(CuL)₂Co‐(C₂H₅OH)₂](ClO₄)₂ · 2C₂H₅OH ( 2 ) (H₂L = 2,3‐dioxo‐5,6:14,15‐di‐benzo‐7,13‐diphenyl‐1,4,8,12‐tetraazacyclo‐pentadeca‐7,13‐diene) have been synthesized and structurally characterized by X‐ray crystallographic investigations. In the two complexes, all copper(II) ions adopt a slightly distorted square‐planar configuration and the central manganese(II) and cobalt(II) ions are set in a distorted octahedral coordination sphere, connected to the other CuL fragments through exo‐cis oxamido bridges. The analyses of the magnetic properties were carried out by means of the theoretical expression of the magnetic susceptibility deduced from the spin Hamiltonian ? = –2J?₁?₂, leading to J = –14.58 cm^–1 for complex 1 and J = –26.95 cm^–1 for complex 2 , respectively.     

Synthesis and Characterization of Diorganotin(IV) Complexes Bearing Binary Schiff‐Bases and Crystal Structure of nBu2SnL1

Four novel diorganotin(IV) complexes with general formula R₂SnL (R = nBu, PhCH₂) were synthesized from diorganotin dichlorides and binary Schiff‐bases (H₂L) containing N₂O₂ donor atoms in the presence of sodium ethoxide. The Schiff bases were prepared by reactions of o‐phenylenediamine with 3‐tert‐butyl‐2‐hydroxy‐5‐methylbenzaldehyde (H₂L¹) and salicylaldehyde (H₂L²) respectively. The compounds were characterized by elemental analyses, IR, and NMR spectroscopy. The solid‐state crystal structure of the compound nBu₂SnL¹ was determined by single‐crystal structural analysis.     

Crystal Structure and Magnetic Properties of Copper(II) and Nickel(II) Binuclear Complexes with Bisacylhydrazones Based on 2,6‐Diformyl‐4‐methylphenol

The series of binuclear Cu(II) and Ni(II) complexes with an asymmetrical exchange fragment based on 2,6‐diformyl‐4‐methylphenol bishydrazone has been synthesized for the first time. The compositions and structures of both ligands and its complexes have been established with the data of IR, ¹H NMR, and extended X‐ray absorption fine structure (EXAFS) spectroscopical studies as well as magnetic measurements. The structure of [Ni₂L₃(μ‐Pz)] · 2CH₃OH (L = triply deprotonated form of bishydrazone, Pz = pyrazol) was confirmed by X‐ray crystallographic analysis. In this complex, the coordination environment of two nickel ions is quite different, one nickel atom is square‐planar and the other is distorted octahedral coordinated. The values of exchange parameter calculated in terms of HDVV theory have been compared with the features of an asymmetrical exchange fragment's electronic and geometrical structure.     

Crystallographic report: Crystal and molecular structure of tetramethylammoniumdiisothiocyanatotriphenyltin(IV), [NMe4SnPh3(NCS)2]

The structure of NMe₄SnPh₃(NCS)₂ is molecular, without any significant intermolecular contacts in the lattice. The trigonal plane around the tin atom is defined by three carbon atoms from the phenyl groups and the axial positions occupied by the NCS groups. Copyright © 2003 John Wiley & Sons, Ltd.     

(Ba6O)(ReN3)2: Synthesis,Crystal Structure and Physical Properties

The reaction of a mixture of barium and rhenium (3:1) at 850 °C under flowing nitrogen yielded the nitride‐oxide (Ba₆O)(ReN₃)₂ (R (No. 148); a = 8.1178(2) Å, c = 17.5651(4) Å; V = 1002.43(5) Å³; Z = 6). According to a structure refinement on X‐ray powder diffraction data, this compound is isostructural to a recently described nitride‐oxide of osmium of analogous composition. The structure consists of sheets of trigonal ReN₃ units and trigonal antiprismatic Ba₆O groups. The Ba–O distance of 2.73 Å is close to the sum of the respective ionic radii. The trigonal ReN₃^5– nitride anion displays a Re–N bond length of 1.94 Å, and is planar within the limits of experimental error. The constitution of the anion was confirmed by IR and Raman spectroscopy. The nitride‐oxide is stable up to 1000 °C, semiconducting (σ = 4.57 × 10^–3 Ω^–1 · cm^–1 at RT), and paramagnetic down to 25 K. A Curie–Weiss analysis resulted in a magnetic moment of μ = 0.68 μ_B per rhenium atom.     

配合物[Cu2(bpe)X2] n (bpe =1, 2–trans–(4–pyridyl)ethene, X=Cl, Br, I )的合成、晶体结构及热稳定性研究

以1,2-反式-二（4-吡啶基）乙烯桥连卤化铜分别得到配合物[Cu₂(bpe)Cl ₂] _n (1), [Cu₂(bpe)Br₂] _n (2) 和 [Cu₂(bpe)I₂] _n (3)。通过X-射线单晶衍射法对配合物1的结构进行了研究,晶体学数据：单斜晶系, P 2(1)/c空间群, a = 0.3788(8) nm, b = 1.5059(3) nm, c = 1.0875(2)nm, β = 96.262(4) °, V = 616.5(2)ų, Z = 2, S = 1.002,最终残差因子( I >2 σ ( I )) R ₁ = 0.0288, wR ₂ = 0.0579,对于全部数据 R ₁ = 0.0509, wR ₂ = 0.0615。元素分析及红外光谱分析表明,该类配合物为同晶化合物。另外,通过热重分析对配合物的热稳定性进行了研究。     

2,6‐Bis(pyrazol‐3‐yl)pyridine as Meridional Capping Ligand: Synthesis,Characterization, and Crystal Structure of the First Corresponding Hexanuclear Iron(III) Complex

Based on the 2,6‐bis(pyrazol‐3‐yl)pyridine ligand (H₂bpp) the hexanuclear iron(III) complex [Fe₆(bpp)₄(μ₃‐O)₂(μ‐OMe)₃(μ‐OH)Cl₂] ( 1 ) was synthesized. The reaction with iron(II) chloride and additional pyridine leads to the exclusive formation of the complex through self‐assembly process. Six octahedrally coordinated iron atoms are linked through the pyrazolido groups of four H₂bpp ligands. These are further linked through bridging hydroxido, methoxido, and oxido groups. The complex has been characterized by IR spectroscopy, ESI mass spectrometry, elemental analysis and X‐ray crystallography. Temperature‐dependent magnetic measurements indicate strong antiferromagnetic exchange interaction between the high‐spin iron(III) ions within the complex, which leads to an S = 0 spin ground state. As a result of the two Fe3(μ₃‐O) fragments two frustrated exchange pathways are present. In addition the properties of H₂bpp as a potential capping ligand for the synthesis of heteroleptic trinuclear complexes based on the triaminoguanidine core is investigated.     

Synthesis and Crystal Structure of Tetrakis(tetramethylammonium) Bis[decabromotetraselenate(II)]‐bis[dibromodiselenate(I)], [(CH3)4N]4[(Se4Br10)2(Se2Br2)2], the Salt of a Mixed‐Valence Bromoselenate(II/I) Anion

Brown crystals of [NMe₄]₄[(Se₄Br₁₀)₂(Se₂Br₂)₂] ( 1 ) were obtained from the reaction of selenium and bromine in acetonitrile in the presence of tetramethylammonium bromide. The crystal structure of 1 was determined by X‐ray diffraction and refined to R = 0.0297 for 8401 reflections. The crystals are monoclinic, space group P2₁/c with Z = 4 and a = 12.646(3) Å, b = 16.499(3) Å, c = 16.844(3) Å, β = 101.70(3)° (123 K). In the solid‐state structure, the anion of 1 is built up of two [Se₄Br₁₀]^2– ions. Each shows a triangular arrangement of three planar SeBr₄ units sharing a common edge through two μ₃‐bridging bromine atoms, and one SeBr₂ molecule, which is linked to the Se^II atoms of two SeBr₄ units; between the Se₄Br₁₀^2– ions a dimerized Se₂Br₂ molecule (Se₄Br₄) is situated and one Se^I atom of each Se₂Br₂ molecule has two weak contacts [3.3514(14) Å and 3.3952(11) Å] to two bromine atoms of one SeBr₄ unit. Four Se^I atoms of a dimerized Se₂Br₂ molecule are in a almost regular planar tetraangular arrangement. Contacts between the Se^II atom of the SeBr₂ molecule and the Se^II atoms of two SeBr₄ units are 3.035(1) Å and 3.115(1) Å, and can be interpreted as donor‐acceptor type bonds with the Se^II atoms of SeBr₄ units as donors and the SeBr₂ molecule as acceptor. The terminal Se^II–Br and μ₃‐Br–Se^II bond lengths are in the ranges 2.3376(10) to 2.4384(8) Å and 2.8036(9) to 3.3183(13) Å, respectively. The bond lengths in the dimerized Se₂Br₂ molecule are: Se^I–Se^I = 2.2945(8) Å and 3.1398(12), Se^I–Br = 2.3659(11) and 2.3689(10) Å.     

[Cs(NTO)(H_2O)]配合物的合成及表征

本文首次用碳酸铯与NTO直接合成新的Cs NTO配合物。采用元素分析和化学分析法确定了配合物的组成。用红外光谱法 ,热分析法和X ray粉末衍射法进行了物理化学表征     

Synthesis,Structure and Quantum Chemical Study on the Organotin Complex [Di（2,4,6-trichlorobenzyl）]tin Bis（quinoline-2-formate）

The title compound was prepared by the reaction of di（2,4,6-trichlorobenzyl） stannic chloride with quinoline-2-formate and characterized with elemental analysis, ^1H NMR, IR and X-ray diffraction methods. It crystallizes in monoclinic, space group P21/n with a = 1.3138（3）, b = 1.8756（4）, c = 1.4599（3） nm, β = 92.731（3）°, V = 3.5933（12） nm^3, Z = 4, Dc = 1.795 g/cm^3, μ（MoKa） = 1.425 mm^-1, F（000） = 1920, R = 0.0778, wR = 0.2286 （for Ⅰ〉 2σ（Ⅰ）） and R = 0.0932, wR = 0.2415 （for all data）. The independent reflections were 6359, among which 5030 were observed （Ⅰ〉 2σ（Ⅰ）） and used in the succeeding refinement. Structural analysis indicates that Sn is in a distorted octahedral coordination environment, and a three-dimensional network could be observed via intermolecular hydrogen bonds. Finally, the stability, frontier orbital composition and energy of the title compound were discussed with Lanl2dz basis set and G98W program.     

Synthesis,Crystal and Electronic Structure of the Nitridoaluminosilicate Ca5[Si2Al2N8]

Ca₅[Si₂Al₂N₈] was synthesized from elementary aluminum and silicon with phase‐pure tricalcium dinitride at 1280 K under dry argon in a sealed niobium ampoule. Ca₃N₂ was freshly prepared from distilled calcium metal in a dry nitrogen atmosphere. The compound crystallizes in form of transparent yellow distorted octahedra. In air and under moisture Ca₅[Si₂Al₂N₈] undergoes hydrolysis. The structure was determined from a single crystal to be orthorhombic (space group Pbcn – no. 60, a = 925.5, b = 614.0 and c = 1557.8 pm). The nitridoaluminate and ‐silicate substructures are separated into planes of edge and corner‐shared aluminate tetrahedra, which are linked by edge‐sharing double tetrahedral pillars of the silicate. The structure was confirmed by electrostatic and quantum mechanical analysis.