Synthesis and Crystal Structure of a New Threedimensional Thiocyanate Supramolecular Compound [Cd（phen）（NCS）（SCN）]n

The compound [Cd（phen）（NCS）（SCN）]n（phen = 1,10-phenanthroline） was synthe- sized under hydrothermal conditions and characterized by IR and single-crystal X-ray diffraction. The complex is of monoclinic, space group C2/c with a = 14.607（3）, b = 10.505（2）, c = 10.631（2）A,β = 115.14（3）^o, V = 1476.8（5）A^3, C14H8CdN4S2, Mr = 408.76, Z = 4, F（000） = 800, μ = 1.757 mm^-1 and Dc = 1.839 g/cm^3. The final R = 0.0409 and wR = 0.0811 for 1367 observed reflections （I 〉 2σ（I））. In the title compound, each cadmium atom is six-coordinated and connected with two adjacent metal ions by two NCS bridges, creating a zigzag chain. The neighboring chains are linked to each other by the weak van der Waals＇ S…S interactions and π…π interactions to form a new three-dimensional supramolecular framework.     

Structure of 〔Na(DB18C6) (CH_3OH)〕_2W_6O_(19)·(DB18C6)·(CH_3OH)

1INrnODUCTIoNlnthepreviouspapers,wehavereportedthesynthesisandcrystalstructureofseveralcrownetherpolyoxometalates"-",nowwestudythestructureofthetitlecomplexandcompareitwithsomeothercrownetherpolyoxometalatecomplexes.2EXPERmENTALToal5OmLaqueoussolutioncontaining32g(1OOmol)Na,WO#.2H,Opre-justedtopH=3.5withchloricacid,14g(4Ommol)(n-Bu)'NBrwasadded,thenwhitepowderwasformed.ThewhiteprecipitateobtainedwithafiltrationwaskeptasthenewmaterialAinnextstep.AmixtureoflgAandO.3g(O.8mmol)DB18…     

Synthesis and Crystal Structure of ［Na（DB18C6）（CH_3OH）］_2Mo_6O_（19）·（DB18C6）·（CH_3OH）

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ［Ｎａ（ＤＢ１８Ｃ６）（ＣＨ_３ＯＨ）］_２Ｍｏ_６Ｏ_（１９）·（ＤＢ１８Ｃ６）·（ＣＨ_３ＯＨ）￥ＺｈｏｕＹｉｎ－Ｚｈｕａｎｇ；ＴｕＳｈｕ－Ｊｉｅ；ＪｉｎＸｉａｎｇ－Ｌｉｎ；ＬｉｕＳｈｕｎ－...     

二苯并18－冠－6铵与硫氰酸银配合物的晶体结构

标题化合物［（ＮＨ_４）（ＤＢ１８Ｃ６）］_２［Ａｇ（ＳＣＮ）_２］_２其晶体属三斜晶系，空间群为Ｐ１。晶胞参数：ａ＝１４．００３（２），ｂ＝１４．４６１（３），ｃ＝１４．８８７（２），ａ＝６６．５１（２），β＝６６．７０（１），γ＝７６．０９（２）°，Ｖ＝２５２７．１３　３，Ｍ_ｒ＝１２０５．０，Ｚ＝２，Ｄ_ｘ＝１．５８ｇ／ｃｍ~３，μ＝９．８８ｃｍ~（－１）。偏差因子Ｒ_ｗ＝０．０８１，独立可观测点数［Ｉ＞３σ（Ｉ）］为３３５１个，在配合物分子中，二苯并１８－冠－６与ＮＨ４~＋形成配阳离子，Ａｇ~＋与硫氰酸根形成配阴离子，二者以静电力形成配合物。银原子被两个ＳＣＮ~－的Ｓ原子桥联和硫氰酸根上的硫，氮杂配，使整个分子形成一条高分子长链。     

Synthesis and Crystal Structure of [Na（DB24C8）]2（WMo5O19）

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ［Ｎａ（ＤＢ２４Ｃ８）］_２（ＷＭｏ_５Ｏ_（１９））￥ＬｕＸｉａｏ－Ｍｉｎｇ；ＬｉｕＧｕｏ－Ｘｉａｎｇ；ＴｕＳｈｕ－Ｊｉｅ；Ｌｉｕｓｈｕｎ－Ｃｈｅｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔ?..     

CRYSTAL AND MOLECULAR STRUCTURE OF { CNa(15-crown-5)]_n [Cd(SCN)_3]}_n

<正> The complex [Na(15-crown-5)] [Cd(SCN)3] (15-crown-5 = C10H20 O5) crysializes in monoclinic space group P21/c with a=10. 219(2) ,b= 10. 575(2) ,c= 20. 572(2) A ,β=98. 45(1)°,V= 2198. 7A3,Mr=529. 89,Z = 4,Dx=1. 600g/cm3,F (000) -1052,μ= 15. 708cm-1. The structure was solved by direct methods with the final R=0. 064. Results of structure analysis indicate that the Na ion is bonded by 15-crown-5 to form a complex cation and the Cd(Ⅱ) is bonded by six SCN ion to form an anion chain with a distorted octahedral coordination.     

Crystal structure and dynamic properties of a bimetallic cyano complex Cd(C4H8O2)Cu(CN)3 with an interpenetrating 3D framework containing a 1,4-dioxane bridging ligand as a rotor

The title complex Cd(C(4)H(8)O(2))Cu(CN)(3) has a 3D twofold interpenetrating framework structure. The structural base of the framework is a planar hexagonal network complex of [Cu(CN)(3)Cd](infinity) ,which is formed with cyanides connecting the coordination sites of Cu(i) ions with a triangle planar form and the equatorial coordination sites of Cd(ii) ions with a trigonal bipyramid form. The networks are stacked and a 1,4-dioxane molecule coordinates to two Cd(ii) ions in alternate networks as a bridging ligand. The 1,4-dioxane ligand penetrates a hexagonal window of the network sandwiched between the bridged networks. This 1,4-dioxane bridge completes the 3D twofold interpenetrating framework structure. (2)H-NMR powder patterns of the deuterated complex Cd(C(4)D(8)O(2))Cu(CN)(3) revealed the dynamics of the 1,4-dioxane bridge as a rotor. Above 253 K, the 1,4-dioxane ligand undergoes rotational motion combined with a ring inversion between two chair conformations. The free energy of activation DeltaG(double dagger) for the ring inversion was calculated to be 41.4(7) kJ mol(-1) at 298 K.     

Synthesis and X-ray structural analysis of a unique Co-crystallization complex of [NaSal]2DB24C8 and [KSal]2DB24C8

Sodium salicylate (NaSal where Sal=2-hydroxybenzoate), when mixed with dibenzo-24-crown-8 (DB24C8) yields a bimetallic complex [NaSal]₂DB24C8 in most polar organic media, while potassium salicylate (KSal) under similar conditions shows a tendency to yield 11 or 21 complexes depending upon medium or synthesis. However, the presence of both NaSal and KSal together results in a unique mixed cation complex of composition NaKSal₂DB24C8. This product melts sharply (190-92°C) without decomposition, displays IR spectral characteristics comparable to those of [Na(Sal)]₂DB24C8, and is stable in aqueous media as shown by the detectable cation effect on the UV absorption bands of Sal and DB24C8. Single crystal X-ray analysis of NaK(Sal)₂DB24C8 reveals that the system represents a co-crystallization complex of individual (KSal)₂DB24C8 and (NaSal)₂DB24C8 molecules. The crystals are monoclinic,P2₁/c,a=19.976(2) Å,b=9.031(1) Å,c=25.541(5) Å,=122.065(9)°, ų,T=298 K,Z=2+2, CuK =1.5418 Å, and 2 (2.5°–100°). FinalR factor for the 3012 observed reflections (F>3) is 0.092. Both the Na₂- and K₂-molecules possess crystallographic centers of symmetry with one metal and its associated anion on each side of the crown ring. However, the conformations of the crowns are very different in the two molecules, with the K₂-crown being nearly planar and the Na₂-crown being quite puckered. Four oxygen atoms from the DB24C8 (KO, 2.680–2.908 Å) and three carboxyl oxygen atoms (KO, 2.472–2.708 Å) from separate salicylate ions coordinate with each potassium. Three oxygens from the crown (NaO, 2.536–2.65 Å) and three carboxyl oxygens (NaO, 2.31–2.563 Å) coordinate with each sodium. The salicylate ions lie on opposite sides and nearly perpendicular (77.2°, Na₂-molecule; 82.7° K₂-molecule) to each crown but coordinate to both of the metal ions within a molecule. The K⁺K⁺ and Na⁺Na⁺ distances in the respective molecules are 3.95 and 3.34 Å. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82044 (18 pages).     

N-对R苯基氮杂15冠5八钼多酸钠超分子配合物的合成与结构

为研究大环化合物对客体分子的选择性, 合成了通式为[NaL(Et2O)]2Na2Mo8O26的三种新型N-对R苯基氮杂15冠5八钼多酸钠超分子配合物(其中L分别为: N-苯基氮杂15冠5、N-对氯苯基氮杂15冠5和N-对甲苯基氮杂15冠5), 进行了元素分析, 红外光谱与核磁共振等结构参数的表征, 对R基为CH3的标题配合物作了X射线四圆衍射测定, 该晶体属单斜晶系, 空间群为P21/a,a=1.4590(4)nm, b=1.3817(3)nm, c=1.7639(5)nm, β=112.67(2)°, V=3.281(1)nm^3, Mr=2021.3, Dc=2.11g/cm^3,μ=2.37mm^-^1, F(000)=2048, R=0.045和Rw=0.057, 与[Na.(DB18C6)(CH3OH)M6O19和[Na(DB24C8)]2M6O19进行比较,结果表明: 大环化合物不仅对客体金属离子有分子识别性, 而且对与之抗衡的多酸阴离子也具有影响。     

Chemical and electrochemical formation of pseudorotaxanes composed of alkyl(ferrocenylmethyl)ammmonium and dibenzo[24]crown-8

Protonation of p-xylylaminomethylferrocene (1) and n-hexylaminomethylferrocene (2) by HCl and NH(4)PF(6) forms the ferrocenylmethyl(alkyl)ammonium salt. Inclusion of the compounds by dibenzo[24]crown-8 (DB24C8) produces [2]pseudorotaxanes, [(DB24C8)(1-H)](+)(PF(6)) and [(DB24C8)(2-H)](+)(PF(6)), respectively. X-ray diffraction of the former product indicates an interlocked structure composed of the axis and the macrocyclic molecule. Intermolecular N-H...O and C-H...O interactions and stacking of the aromatic planes are observed. [(DB24C8)(1-H)](+)(PF(6)), in the solid state, is characterized by IR spectroscopy and elemental analyses. A similar reaction of 1,1'-bis(p-xylylaminomethyl)ferrocene (3) forms a mixture of [2] and [3]pseudorotaxanes, [(DB24C8)(3-H(2))](2+)(PF(6))(2) and [(DB24C8)(2)(3-H(2))](2+)(PF(6))(2). The latter product having two DB24C8 molecules is isolated and characterized by X-ray crystallography. Formation of these pseudorotaxanes in a CD(3)CN solution is evidenced by (1)H NMR and mass spectrometry. Electrochemical oxidation of 1-3 at 0.4 V (vs Ag(+)/Ag) in the presence of TEMPOH (1-hydroxy-2,2,6,6-tetramethylpiperidine) and DB24C8 affords the corresponding pseudorotaxanes. The ESR spectrum of the reaction mixture indicates the formation of a TEMPO radical in high yield. Details of the conversion of the dialkylamino group of the ligand to the dialkylammonium group are investigated by using a flow electrolysis method linked to spectroscopic measurements. The proposed mechanism for the reaction involves the ferrocenium species, formed by initial oxidation, which undergoes electron transfer from nitrogen to the Fe(III) center, producing a cation radical at the nitrogen. Transfer of hydrogen from TEMPOH to the cation radical and inclusion of the resulting dialkylammonium species by DB24C8 yields the pseudorotaxanes.     

一维链状配位聚合物[Cd(N-MeIM)_2(SCN)_2]_n的结构表征和电化学性能研究(英文)

0 IntroductionThe rapid development in the area of polymericmetalorganic frameworks (MOFs) continues to producevarious structures with interesting compositions andtopologies[1￣5] , along with potential applications asfunctional solid materials for molecular selection, ionexchange, and catalysis[6￣10]. By the careful selectionand design of organic ligands, such as linear isothio-cyanate-based building blocks, a wide variety of solid-state supramolecular architectures have been con-structed[1…     

Cation-π Interactions:Synthesis and Crystal Structure of Complex:[Na(DB18C6)]2[Pd(SCN)4]

The cation-π interactions have attracted much attention as an important noncovalent binding force. We have synthesized and characterized the first example[K(DB 18C6)]₂[Pd(SCN)₄] which exist K⁺-π interactions in crown ether compounds^[1]. However,the reported Na+ complexes structurally characterized by X-ray diffraction analysis have so far been limited to a few compounds. We now report the structure of complex:[Na(DB18C6)]₂[Pd(SCN)₄] which also exist Na⁺-n interactions.     

Synthesis and Crystal Structure of Complex:[K(DB24C8)(H2O)]2[Pd(SCN)4]0.5H2O

Crown ethers can form complexes with inorganic and organic cations. Much attention has been focused on characterizing the structure of crown ether complexes. However, the X-ray structures of dibenzo-24-crown-8 compelxes:[K(DB24C8)(H₂O)]₂[Pd(SCN)₄]0.5H₂O.     

Synthesis, Crystal Structure and Luminescent Property of a Novel 1-D Cadmium(Ⅱ) Complex: [Cd2(C8H3NO6)2(H2O)4]n·2nH2O

A novel one-dimensional chain-like coordination polymer constructed from 3-nitrobenzene-1,2-dicarboxylic acid, [Cd2(C8H3NO6)2(H2O)4]n·2nH2O, has been synthesized and its structure was determined by X-ray crystallography method. The crystal belongs to monoclinic, space group P21/c with a = 6.1252(8), b = 20.706(3), c = 8.8067(11) (A), β = 95.608(2)°, V= 1111.6(2)(A)3, Mr =751.12, Dc = 2.244 g/cm3, F(000) = 736, μ = 2.011 mm-1, Z = 2, the final R = 0.0262 and wR = 0.0692for 2338 observed reflections with I ＞ 2σ(I). The structure of the title compound presents a 1-D chain-like structure constructed by dimer units, [Cd2(CsH3NO6)2(H2O)4]n, through two carboxylate oxygen atoms. The fluorescence of the tifle compound has been also discussed in this paper.     

Synthesis and Crystal Structure of Poly{diaqua[N-(2-hydroxybenzyl)-D,L- aspartate]cadmium(II)}

1 INTRODUCTION Coordination-driven supramolecular assembly hasattracted great interest in constructing beautiful mo-tifs and developing new materials[1～5]. It is crucial toselect or synthesize suitable bridging organic li-gands[6～10]. The reduced Schiff base N-(2-hydro-xybenzyl)-D,L-amino acid is an excellent ligand forself-assembly with metal ions, not only due to itsprolific coordination sites but also its strong abilityto afford hydrogen bonding from secondary aminegroup and carbox…     

One- or two-dimensional 2,3-naphtho crown ether complexes [Na(N15C5)]2[M(SCN)4] and [K(N18C6)]2[M(SCN)4] (M = Pd, Pt) constructed by pi-pi stacking interactions

Four novel 2,3-naphtho-15-crown-5 (N15C5) and 2,3-naphtho-18-crown-6 (N18C6) complexes [Na(N15C5)]2[Pd(SCN)4] (1), [Na(N15C5)]2[Pt(SCN)4] (2), [K(N18C6)]2[Pd(SCN)4] (3) and [K(N18C6)]2[Pt(SCN)4] (4) were synthesized and characterized by elemental analysis, FT-IR spectra and single-crystal X-ray diffraction. The structure analyses reveal that both 1 and 2 are assembled into zigzag chains by the strong intermolecular pi-pi stacking interactions between adjacent 2,3-naphthylene groups of N15C5. The molecules of complexes 3 and 4 are linked into 1D chains by the bridging K-O(ether) interactions between the adjacent [K(N18C6)]+ units and the resulting chains are constructed into a novel 2D network by inter-chain pi-pi stacking interactions between the neighboring 2,3-naphthylene moieties of N18C6. According to the supramolecular self-assemblies of complexes 1-4, two types of stacking model of naphthylene groups are given and discussed.     

One-dimensional Zigzag Chain Composed of HgI2 Unit and 2,5-Bis（4-pyridyl）- 1,3,4-thiadiazole： [HgI2（C12H8N4S）]

1 INTRODUCTION Much interest has been focused on the design and syntheses of supramolecular coordination polymers with novel topologies and structural motifs because of their encouraging potential applications in the fields of nonlinear optics, catalysis and separation, magnetism and molecular recognition[1, 2]. In princi- ple, control over the type and topology of the coor- dination polymers can be achieved by careful choice of ligand, metal coordination geometry preference, inorganic cou…     

三维金属有机骨架微孔晶体化合物Cd5(BTC)4(H2O)8·6H2O的合成与晶体结构

通过改变合成条件合成了最大宽度达到2.6 nm的特殊“Z”字形孔道的新型金属有机骨架微孔晶体化合物Cd5(BTC)4(H2O)8·6H2O, 并通过ICP、元素分析、热重(TGA)和X射线单晶衍射分析对其进行了表征.     

[Na(DB18-C-6)(H2O)2][Na(DB18-C-6)(SCN)2]：Two-Di-mensional Network Complex Assembled by π-π Stacking Interactios,Hydrogen Bonds and Electrostatic Interactions

A novel two‐dimensional network dibenzo‐18‐crown‐6 (DB18‐C6) complex: [Na (DB18‐C‐6) (H₂O)₂] [Na (DB18‐C‐6) (SCN)₂] has been isolated and characterized by elemental, IR and X‐ray diffraction analysis. The crystal structure belongs to monoclinic, space group P2₁/c with cell dimensions a = 1.06178(7), b = 1.40243(8), c = 3.03496(19) nm, β = 90.4220(10)°, V = 4.5292(5) nm³, Z=4, D_calcd =1.351 g/ cm³, F(000) = 1936, R₁ = 0.0369, wR₂ = 0.0821. The most interesting feature in this structure is that complex cation and complex anion form a two‐dimensional network via τ‐τ stacking interactions, hydrogen bonds and electrostatic interactions.     

三维无机-有机杂化骨架微孔材料Cd(HBTC)(EG)·8(H2O)的合成与结构

由于无机-有机杂化微孔晶体材料在选择性催化、分子识别和可逆性主客体分子(离子)交换等方面存在潜在的应用前景,已经越来越引起人们的广泛注意.传统的沸石和分子筛微孔晶体材料以硅酸盐、硅铝酸盐、磷铝酸盐和无机金属磷酸盐为骨架,新型的无机-有机杂化微孔晶体材料用刚性和热稳定性较好的有机分子和金属离子作为结构单元.均苯三甲酸(H3BTC)是常用的含氧有机配.