[Co(H_2O)(HPO_4)]·H_2O: The Layered Divalent Metal Monohydrogenphosphate Structure

ＩｎｔｒｏｄｕｃｔｉｏｎＳｉｎｃｅｔｈｅｐｉｏｎｅｅｒｗｏｒｋｓｏｆＣｌｅａｒｆｉｅｌｄａｎｄｃｏｗｏｒｋｅｒｓｉｎｔｈｅ 196 0ｓ ,1,2 ｌａｙｅｒｅｄｍｅｔａｌｐｈｏｓｐｈａｔｅｓｈａｖｅａｔｔｒａｃｔｅｄｍｕｃｈａｔｔｅｎｔｉｏｎｄｕｅｔｏｔｈｅｉｒａｐｐｌｉｃａｔｉｏｎｓｏｎｉｏｎｅｘ ｃｈａｎｇｅ ,ｉｎｔｅｒｃａｌａｔｉｏｎ ,ｈｅｔｅｒｏｇｅｎｅｏｕｓｃａｔａｌｙｓｉｓａｎｄｓｏｒｐ ｔｉｏｎ .3 7Ａｍｏｎｇｔｈｅｎｕｍｅｒｏｕｓｌａｍｅｌｌａｒｐｈａｓｅｓ ,ｔｈｅｐｒｏｔｏ ｔｙｐｉｃａｌ…     

Synthesis, Structure and Characterization of Two-dimensional Network Copper Complex [Cu_3(nta)_2(azpy)_2(H_2O)_2]·6H_2O

ＩｎｔｒｏｄｕｃｔｉｏｎＣｒｙｓｔａｌｅｎｇｉｎｅｅｒｉｎｇｏｆｓｕｐｒａｍｏｌｅｃｕｌａｒａｒｃｈｉｔｅｃｔｕｒｅｓｓｕｓｔａｉｎｅｄｂｙｃｏｏｒｄｉｎａｔｅｃｏｖａｌｅｎｔｂｏｎｄｓｏｒｈｙｄｒｏｇｅｎｂｏｎｄｓｒｅｐｒｅｓｅｎｔｓａｒａｐｉｄｌｙｅｘｐａｎｄｉｎｇｆｉｅｌｄｔｈａｔｏｆｆｅｒｓｐｏ ｔｅｎｔｉａｌｆｏｒｄｅｖｅｌｏｐｍｅｎｔｏｆｎｅｗｃｌａｓｓｅｓｏｆｆｕｎｃｔｉｏｎａｌｓｏｌｉｄｓ .1,2 Ｔｈｅａｒｃｈｉｔｅｃｔｕｒｅｓｏｆｃｏｏｒｄｉｎａｔｉｏｎｐｏｌｙｍｅｒｓｃａｎｂｅ…     

The Crystal and Molecular Structure of a New Macrocyclic Ligand, (H_6BDBPH)Br_6·4H_2O

1　ＩＮＴＲＯＤＵＣＴＩＯＮＯｎｅｏｆｏｕｒｃｕｒｒｅｎｔｉｎｔｅｒｅｓｔｓｆｏｃｕｓｅｓｏｎｔｈｅｄｅｓｉｇｎａｎｄｓｙｎｔｈｅｓｅｓｏｆｐｏｌｙａｚａｍａｃｒｏｃｙｃｌｉｃｌｉｇａｎｄｓ,ａｎｄｔｈｅｓｔａｂｉｌｉｔｉｅｓｏｆｃｏｒｒｅｓｐｏｎｄｉｎｇｍｅｔａｌｃｏｍｐｌｅｘｅｓ.Ｔｗｏｐｏｌｙａｚａｄｉｐｈｅｎｏｌｍａｃｒｏｃｙｃｌｅｓ,Ｒ(ｂａｂｐ) 2 (ｄｆｃ) 2 ａｎｄＲ (ｂａｃ) 2 (ｄｆｐ) 2 ;[1 ]ｏｎｅｏｃｔａａｚａ ｍａｃｒｏｃｙｃｌｅ,ＢＰＢＤ ;[2 ,3]ａｎｄｓｅｖｅｒａｌｈｅｘａａｚａｍａ…     

[H_2N(C_2H_4)_2NH_2]_4(H_3O)[PMo_2~VMo_6~(VI)V_4~(IV)O_(40)(V~(IV)O)_2]·H_2O: A New Highly Reduced, Bicapped Pseudo-Keggin Vanadylpolymolybdophosphate

Ｐｏｌｙｏｘｏｍｅｔａｌａｔｅｓ (ＰＯＭｓ)ｃｏｎｔａｉｎｉｎｇＫｅｇｇｉｎｍｏｉ ｅｔｉｅｓｈａｖｅｂｅｅｎｒｅｃｅｉｖｉｎｇｅｘｔｅｎｓｉｖｅａｔｔｅｎｔｉｏｎｉｎｒｅｃｅｎｔｙｅａｒｓｏｗｉｎｇｔｏｔｈｅｉｒｇｒｅａｔｆｕｎｄａｍｅｎｔａｌａｎｄｐｒａｃｔｉｃａｌｉｎｔｅｒ ｅｓｔ .1Ｅｓｐｅｃｉａｌｌｙｔｈｅｕｎｕｓｕａｌｅｌｅｃｔｒｏｎｉｃｐｒｏｐｅｒｔｙ (ｈｉｇｈｎｅｇａｔｉｖｅｃｈａｒｇｅｓ) ,ｏｎｅｏｆｔｈｅｍｏｓｔｉｍｐｏｒｔａｎｔｐｒｏｐｅｒｔｉｅｓｏｆＰＯＭｓ ,ｈａｓｐｏｔｅｎ…     

Synthesis and Crystal Structure of Two-dimensional Network Supramolecular Complex [Cu(dafo)_2(H_2O)_2](ClO_4)_2

ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｓｕｐｒａｍｏｌｅｃｕｌａｒｃｏｍｐｌｅｘｅｆｏｒｍｅｄｂｙｔｈｅｗｅａｋｉｎｔｅｒａｃｔｉｏｎｓ (ｅｌｅｃｔｒｏｓｔａｔｉｃｉｎｔｅｒａｃｔｉｏｎ ,ｈｙｄｒｏｇｅｎｂｏｎｄｓ ,ｖａｎｄｅｒＷａａｌｓｆｏｒｃｅ ,ｓｈｏｒｔ ｒａｎｇｅｅｘｃｌｕｓｉｏｎｆｏｒｃｅ ,ｅｔｃ .)ｏｆｍｏｒｅｔｈａｎｔｗｏｓｏｒｔｓｏｆｓｐｅｃｉｅｓｉｓａｎｏｒｇａｎｉｚｉｎｇｅｎｔｉｔｙｔｈａｔｕｓｕａｌｌｙｐｏｓｓｅｓｓｅｓｓｐｅｃｉａｌｓｔｒｕｃｔｕｒｅａｎｄｆｕｎｃｔｉｏｎ .1Ｓｕｐ…     

Synthesis and Crystal Structure of a Novel Hydrogen-Bonded Three-Dimensional Polymer [Zn(1,4-benzenedicarboxylate)-(pyridine)·H_2O]_n

ＩｎｔｒｏｄｕｃｔｉｏｎＤｅｓｉｇｎａｎｄｓｙｎｔｈｅｓｅｓｏｆｎｏｖｅｌｓｕｐｒａｍｏｌｅｃｕｌａｒｃｏｍ ｐｌｅｘｅｓｗｉｔｈｕｎｕｓｕａｌａｎｄｔａｉｌｏｒａｂｌｅｓｔｒｕｃｔｕｒｅｓａｒｅｆｕｎｄａ ｍｅｎｔａｌｓｔｅｐｓｉｎｄｉｓｃｏｖｅｒｙａｎｄｆａｂｒｉｃａｔｉｏｎｏｆｖａｒｉｏｕｓｔｅｃｈ ｎｏｌｏｇｉｃａｌｌｙｕｓｅｆｕｌｆｕｎｃｔｉｏｎａｌｓｕｐｒａｍｏｌｅｃｕｌａｒｄｅｖｉｃｅｓ .1 3Ｒｅｃｅｎｔｌｙ ,ｃｏｎｓｉｄｅｒａｂｌｅｅｆｆｏｒｔｓｈａｖｅｂｅｅｎｄｅｖｏｔｅｄｔｏｃｒ…     

Synthesis and Structure of Tungsten(Ⅵ)-citrate Complex K_6[W_2O_5(cit)_2]·5H_2O

ＩｎｔｒｏｄｕｃｔｉｏｎＲｅｓｓｓ［１，２］ｒｅｃｅｎｔｓｔｕｄｙｒｅｓｕｌｔｓｓｈｏｗｔｈａｔｔｈｅＦｅＭｏ－ｃｏｆａｃｔｏｒｃｏｎｓｉｓｔｓｏｆｔｗｏｃｕｂａｎｅｆｒａｇ－ｍｅｎｔｓ［Ｆｅ４Ｓ３］ａｎｄ［Ｆｅ３ＭｏＳ３］ｂｏｕｎｄｂｙｔｈｒｅｅ...     

Synthesis and Structure of Copper(Ⅱ) Complex [Cu(C_5H_5N)_2(H_2O)(C_6H_5COO)_2]

1　ＩＮＴＲＯＤＵＣＴＩＯＮＣｅｒｔａｉｎｃｏｐｐｅｒｃｏｍｐｌｅｘｅｓｈａｖｅｂｅｅｎｓｈｏｗｎｔｏｈａｖｅｕｎｕｓｕａｌｃｈｅｍｉｃａｌｐｒｏｐｅｒｔｉｅｓｓｕｃｈａｓｏｘｙｇｅｎｔｒａｎｓｆｅｒ,ｏｘｉｄａｔｉｖｅａｄｄｉｔｉｏｎａｎｄｈｏｍｏｇｅｎｏｕｓｃａｔａｌｙｔｉｃｈｙｄｒｏｇｅｎａｔｉｏｎ[1].Ｏｘｉｄａｔｉｖｅａｄｄｉｔｉｏｎｒｅａｃｔｉｏｎｓａｒｅｋｅｙｓｔｅｐｓｉｎｔｈｅａｃｔｉｖａｔｉｏｎｏｆσｂｏｎｄｓｉｎａｇｒｅａｔｎｕｍｂｅｒｏｆｃａｔａｌｙｔｉｃｐｒｏｃｅｓｓ.Ｃｏｐ…     

Synthesis and Thermodynamic Properties of MgO·B_2O_3·4H_2O

ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｒｅａｒｅｍａｎｙｋｉｎｄｓｏｆｍａｇｎｅｓｉｕｍｂｏｒａｔｅｓ ,ｂｏｔｈｎａｔｕｒａｌａｎｄｓｙｎｔｈｅｔｉｃ .Ａｂｏｒａｔｅｄｏｕｂｌｅｓａｌｔ (2ＭｇＯ·2Ｂ2 Ｏ3 ·ＭｇＣｌ2 · 14Ｈ2 Ｏ)ｎａｍｅｄｃｈｌｏｒｏｐｉｎｎｏｉｔｅｗａｓｏｂ ｔａｉｎｅｄｆｒｏｍｔｈｅｎａｔｕｒａｌｃｏｎｃｅｎｔｒａｔｅｄｓａｌｔｌａｋｅｂｒｉｎｅ .1Ｉｎｏｒｄｅｒｔｏｆｉｎｄｔｈｅｆｏｒｍｉｎｇｒｅｌａｔｉｏｎｂｅｔｗｅｅｎｔｈｅｄｏｕｂｌｅｓａｌｔａｎｄｍａｇｎｅｓｉｕｍ ｂｏｒａ…     

Quantum dynamics of dissociative adsorption of H_2 and D_2:The time-dependent wave packet method

Ｒｅｃｅｎｔｐｒｏｇｒｅｓｓｉｎｓｕｒｆａｃｅｓｐｅｃｔｒｏｓｃｏｐｙａｎｄｍｏｌｅｃｕｌａｒｂｅａｍｓｃａｔｔｅｒｉｎｇａｎｄｄｅｔｅｃｔｉｏｎｔｅｃｈｎｉｑｕｅｓｍａｋｅｓｉｔｎｏｗｐｏｓｓｉｂｌｅａｔｔｈｅｍｉｃｒｏｓｃｏｐｉｃｌｅｖｅｌｔｏａｃｃｕｒａｔｅｌｙｍｅａｓｕｒｅｓｕｃｈｔｈｉｎｇｓａｓｄｉｓｓｏｃｉａｔｉｏｎｒａｔｅｓ,ａｄｓｏｒｂａｔｅｂｉｎｄｉｎｇａｎｄｇｅｏｍｅｔｒｙ,ａｎｄｍｏｂｉｌｉｔｉｅｓｏｆａｄｓｏｒｂｅｄｓｐｅｃｉｅｓｏｎｓｕｒｆａｃｅｓ.Ｔｈｉｓｋｉｎｄｏｆｅ…     

A lvt‐type Framework [Cu2(tza)4]·ClO4·4H2O Derived from 1H‐tetrazole‐1‐acetic Acid

The reaction of 1H‐tetrazole‐1‐acetic acid (Htza) and perchloric acid with cuprous chloride with slow evaporation at room temperature gave a novel 3D porous Cu^II coordination polymer, [Cu₂(tza)₄] · ClO₄ · 4H₂O ( 1 ), (tza = tetrazole‐1‐acetate). The structure exhibits an unusual 3D microporous coordination framework built up by four coordinated Cu^II nodes and bidentate bridging tza ligands with lvt‐type topology. Furthermore, the magnetic properties of complex 1 were also investigated.     

An Efficient Synthesis of 2‐Substituted Benzoxazoles via RuCl3·3H2O Catalyzed Tandem Reactions in Ionic Liquid

An efficient synthesis of 2‐substituted benzoxazoles through RuCl₃·3H₂O catalyzed, air oxidized tandem reactions of 2‐aminophenols and aldehydes in [bmim]BF₄ was developed. This synthetic strategy has such advantages as mild reaction conditions, cost‐free oxidant, readily available starting materials, and recyclable catalyst and solvent. As an application, it was successfully used in the synthesis of the unreported 5‐(benzoxazol‐2‐yl)‐2′‐deoxyuridines with potential biological activities.     

Crystal structures of hydrates of simple inorganic salts. III. Water‐rich aluminium halide hydrates: AlCl3·15H2O,AlBr3·15H2O,AlI3·15H2O,AlI3·17H2O and AlBr3·9H2O

Water‐rich aluminium halide hydrate structures are not known in the literature. The highest known water content per Al atom is nine for the perchlorate and fluoride. The nonahydrate of aluminium bromide, stable pentadecahydrates of aluminium chloride, bromide and iodide, and a metastable heptadecahydrate of the iodide have now been crystallized from low‐temperature solutions. The structures of these hydrates were determined and are discussed in terms of the development of cation hydration spheres. The pentadecahydrate of the chloride and bromide are isostructural. In AlI₃·15H₂O, half of the Al³⁺ cations are surrounded by two complete hydration spheres, with six H₂O in the primary and 12 in the secondary. For the heptadecahydrate of aluminium iodide, this hydration was found for every Al³⁺.     

A one‐dimensional coordination polymer formed from the reaction of 1,1‐diphenyl‐3,3′‐[(1R,2R)‐cyclohexane‐1,2‐diylbis(azanediyl)]dibut‐2‐en‐1‐one with MnCl2·4H2O

In the title coordination polymer, catena‐poly[[dichloridomanganese(II)]‐μ‐1,1‐diphenyl‐3,3′‐[(1R,2R)‐cyclohexane‐1,2‐diylbis(azaniumylylidene)]dibut‐1‐en‐1‐olate‐κ²O:O′], [MnCl₂(C₂₆H₃₀N₂)]_n, synthesized by the reaction of the chiral Schiff base ligand 1,1‐diphenyl‐3,3′‐[(1R,2R)‐cyclohexane‐1,2‐diylbis(azanediyl)]dibut‐2‐en‐1‐one (L) with MnCl₂·4H₂O, the asymmetric unit contains one crystallographically unique Mn^II ion, one unique spacer ligand, L, and two chloride ions. Each Mn^II ion is four‐coordinated in a distorted tetrahedral coordination environment by two O atoms from two L ligands and by two chloride ligands. The Mn^II ions are bridged by L ligands to form a one‐dimensional chain structure along the a axis. The chloride ligands are monodentate (terminal). The ligand is in the zwitterionic enol form and displays intramolecular ionic N⁺—H...O⁻ hydrogen bonding and π–π interactions between pairs of phenyl rings which strengthen the chains.     

Lithium carnallite,LiCl·MgCl2·7H2O

The title compound, lithium magnesium chloride heptahydrate, LiCl·MgCl₂·7H₂O, was analyzed in 1988 by powder X‐ray diffraction [Emons, Brand, Pohl & Köhnke (1988). Z. Anorg. Allg. Chem. 563 , 180–184] and a monoclinic crystal lattice was determined. In the present work, the structure was solved from single‐crystal diffraction data. A trigonal structure was found, exhibiting a network structure of Mg(H₂O)₆ octahedra and Li(H₂O)Cl₃ tetrahedra connected by H...Cl hydrogen bonds. The [Li(H₂O)]⁺ unit is coordinated by distorted edge‐connected Cl⁻ octahedra.     

复合物HNO···H2O2内N-H···O蓝移氢键的理论研究

A theoretical study on the blue-shifted H-bond N-H…O and red-shifted H-bond O-H…O in the complexHNO…H_2O_2 was conducted by employment of both standard and counterpoise-corrected methods to calculate thegeometric structures and vibrational frequencies at the MP2/6-31G(d),MP2/6-31 G(d,p),MP2/6-311 q G(d,p),B3LYP/6-31G(d),B3LYP/6-31 G(d,p) and B3LYP/6-311 G(d,p) levels.In the H-bond N-H…O,the calcu-lated blue shift of N-H stretching frequency is in the vicinity of 120 cm~(-1) and this is indeed the largest theoreticalestimate of a blue shift in the X-H…Y H-bond ever reported in the literature.From the natural bond orbital analy-sis,the red-shifted H-bond O-H…O can be explained on the basis of the dominant role of the hyperconjugation.For the blue-shifted H-bond N-H…O,the hyperconjugation was inhibited due to the existence of significant elec-tron density redistribution effect,and the large blue shift of the N-H stretching frequency was prominently due tothe rehybridization of sp~n N-H hybrid orbital.     

Synthesis and Characterization of the first Copper(II) Complex of 6‐Azathymine. The Crystal Structure of [[CuCl2(H2O)2(AT)}2] · 2H2O; (AT = 6‐Azathymine)

The reaction of 3, 4‐dihydro‐6‐methyl‐3‐thioxo‐1, 2, 4‐triazin‐5(2H)‐one (6‐aza‐2‐thiothymine, AAT, 1 ) with copper(I) chloride in presence of hydrochloric acid in methanol gives the complex [{CuCl₂(H₂O)₂(AT)}₂] · 2H₂O, 2 , AT = 6‐azathymine) in excellent yield. 2 was characterized by IR spectroscopy and elemental analyses as well as mass spectrometry. Also single‐crystal X‐ray diffraction studies on compound 2 revealed that AT acts as a monodentate ligand in the centrosymmetric binuclear complex via its oxygen atom. Crystal data for 2 at —80 °C: space group P2₁/c with a = 550.1(1), b = 2712.5(1), c = 729.7(1) pm, β = 95.99(1)°, Z = 2, R₁ = 0.0213.     

Synthese und Kristallstruktur der Rhenium(VII)‐Nitridchloride ReNCl4 und ReNCl4·H2O

Syntheses and Crystal Structures of the Rhenium(VII) Nitride Chlorides ReNCl₄ and ReNCl₄·H₂O Rhenium(VII) nitride chloride, ReNCl₄ ( 1 ) is obtained in form of brown needles with metallic luster by the reaction of ReCl₅ with Cl₃VNCl at 140 °C under vacuum in a sealed glass ampoule. It crystallizes in the tetragonal space group I4 with the lattice parameters a = 826.7(4), c = 405.1(2) pm, and Z = 2. The square pyramidal molecules are connected by asymmetric nitrido bridges to form chains along the crystallographic c axis. The shorter Re‐N distance of 163.0(5) pm corresponds to a triple bond, while the pronounced longer distance of 242.0(5) pm can be interpreted with a weak donor bond. The reaction of ReCl₅ with VN at 170 °C under vacuum in a sealed glass ampoule yields red needles of ReNCl₄·H₂O ( 2 ). It crystallizes in the orthorhombic space group Pnma with a = 1075.4(2), b = 1108.5(2), c = 547.7(5) pm and Z = 4. The Re atoms exhibit a distorted octahedral coordination with the aqua ligand in trans position to the nitrido ligand. The Re‐N triple bond has a bond distance of 166.1(11) pm. The complexes are connected by hydrogen bridges O‐H···N to form chains.     

Preparation of 1,6‐naphthyridine‐2,5(1H,6H)‐diones

Novel method for the synthesis of 3‐acyl‐1,6‐dialkyl‐7‐methyl‐1,6‐naphthyridine‐2,5(1H,6H)‐diones (2) was developed. The reaction of 2‐acyl‐1‐alkylamino‐1‐ethoxyethylenes (1) with acetyl chloride or β‐keto amide 3 with acetyl chloride in the presence of p‐toluenesulfonic acid gave 2 in moderate yield (14‐59% yield).     

3Mg(OH)2·MgSO4·8H2O: A Metastable Phase in the System Mg(OH)2‐MgSO4‐H2O

In the course of investigations relating to magnesia oxysulfate cement the basic magnesium salt hydrate 3Mg(OH)₂ · MgSO₄ · 8H₂O (3–1–8 phase) was found as a metastable phase in the system Mg(OH)₂‐MgSO₄‐H₂O at room temperature (the 5–1–2 phase is the stable phase) and was characterized by thermal analysis, Raman spectroscopy, and X‐ray powder diffraction. The complex crystal structure of the 3–1–8 phase was determined from high resolution laboratory X‐ray powder diffraction data [space group C2/c, Z = 4, a = 7.8956(1) Å, b = 9.8302(2) Å, c = 20.1769(2) Å, β = 96.2147(16)°, and V = 1556.84(4) ų]. In the crystal structure of the 3–1–8 phase, parallel double chains of edge‐linked distorted Mg(OH₂)₂(OH)₄ octahedra run along [–110] and [110] direction forming a pattern of crossed rods. Isolated SO₄ tetrahedra and interstitial water molecules separate the stacks of parallel double chains.