新型氰基桥联配位聚合物[Ni(en)2]2[Ni(CN)4]2·5H2O的合成、晶体结构和磁性质

分子组装在材料科学、催化和生物化学中具有潜在的应用前景,所以分子组装引起了化学、固体物理学和生物学等领域科学家们的普遍关注犤1犦。分子组装常用的方法是使用具有配位能力的金属配合物作为建筑块与过渡金属阳离子反应。氰基桥联多核配合物由于其结构的多样性和具有特别优异的磁性质,近10年来在配位化学领域倍受关注犤2～8犦。在系列配合物犤M(en)2犦犤Ni(CN)4犦(M=Ni,Cu,Zn,Cd等)中,犤Cu(en)2犦犤Ni(CN)4犦和犤Cd(en)2犦犤Ni(CN)4犦的晶体结构已经通过单晶衍射的方法测得犤9,10犦。在犤Cu(en)2犦犤Ni(CN)4犦中,Cu原子为六配…     

氰基桥联双核镝(Ⅲ)-铁(Ⅲ)配合物[DyFe(CN)6(DMF)4(H2O)3]·1.25H2O的合成与结构表征

A dinuclear complex [DyFe(CN)₆(DMF)₄(H₂O)₃]·1.25H₂O(DMF=N， N-dimethylformamide) 1 based on the cyanide as linkage was prepared and structurally characterized by X-ray single-crystal structure analysis. The Dy(Ⅲ) ion is eight coordinations in a square-antiprism arrangement and the Fe(Ⅲ) ion is six coordinations oriented octahedrally. The neutral units [DyFe(CN)₆(DMF)₄(H₂O)₃] are held together by hydrogen bonds formed by lattice water molecules， coordinated water molecules and nitrogen atoms of cyanide coming from other distinct complex units to afford a three-dimensional framework. CCDC： 192314.     

[Cu(Ⅱ)(DETA)]3[Cr(CN)6]2·5H2O(DETA=二乙烯三胺)氰桥配合物的结构和磁性研究

A new coordination complex [Cu(Ⅱ)(DETA)]₃[Cr(CN)₆]₂·5H₂O (DETA=diethylenetriamine) was synthesized, its crystal structure and magnetic properties were determined. The crystal crystallizes in monoclinic space group P2₁/c, with unit cell constants a=2.056 6(7) nm, b=1.440 7(5) nm, c=1.513 3(5) nm, β=95.996(6)°, and V=4.459(3) nm³, Z=4, D_c=1.499 g·cm^-3, F(000)=2 060，μ(Mo Kα)=1.936 mm^-1, R₁=0.052 3, wR₂=0.106 2. The structure consists of a one-dimensional chain of [Cu(DETA)]₂[Cr(CN)₆]⁺ and binuclear [Cu(DETA)][Cr(CN)₆]^-. The coordination geometries around Cu²⁺ atoms are distorted square-based pyramidal and distorted square, respectively. Magnetism studies show that there are ferromagnetic interactions between Cu²⁺ and Cr³⁺ ions. CCDC: 272213.     

[Cu(TOL)4]Cl2·2C2H5OH·2H2O的合成和晶体结构

三唑醇(Triadimenol,简写TOL)是一内吸性的广谱低毒杀菌剂,主要用于禾谷类作物,腥黑穗病、丝黑穗病、散黑穗病、白粉病、锈病等病害的防治[1～3].其化学名称为1-(4-氯苯氧基)-3,3-二甲基-1-(1H-1,2,4三唑-1基)丁基-2-醇,结构式如下:     

一维链状配位聚合物[M(H2bpb)(H2O)4](SO4)2·6H2O[M=Zn(Ⅱ)，Cu(Ⅱ)]的合成及晶体结构表征

设计并合成了一个含吡啶基团的柔性配体：N，N′-Bis(3-pyridylmethyl)-1，4-benzenedimethylamine(bpb)。通过bpb与硫酸锌及硫酸铜反应得到了两个新型具有一维链状结构的配位聚合物：[M(H₂bpb)(H₂O)₄](SO₄)₂·6H₂O[M=Zn(Ⅱ) 1，Cu(Ⅱ) 2]。X-射线晶体结构测定表明，这两个     

配合物[Co(phen)2(m-chlorobenzoic acid)2·(H2O)]·(H2O)2的水热合成、晶体结构电化学分析

The title complex has been synthesized with m-chlorobenzoic acid, 1,10-phenanthroline and cobalt perchlorate anhydrous in the solvent mixture of water and methanol. Crystal data for this complex: triclinic, space group P1, a=0.870 7(3) nm, b=1.284 4(4) nm, c=1.692 9(5) nm; α=75.430(5)°, β=77.562(5)°, γ=86.346(5)°, V=1.789 4(9) nm³, D_c=1.456 g·cm^-3, Z=2, F(000)=806. Final GooF=1.065, R₁=0.068 4, wR₂=0.127 5. The crystal stru-cture shows that the Cobaly ion is coordinated with four nitrogen atoms from two 1,10-phenanthroline molecules and two oxygen atoms from one m-chlorobenzoic acid molecule and one water molecule respectively, forming a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex is also reported. CCDC: 619087.     

一维链状镍配位聚合物{[Ni(4，4′-bipy)(2，4，6-TMBA)2(H2O)2]·(CH3OH)}n的合成、晶体结构及电化学性质

One dimensional chain nickel(Ⅱ) coordination polymer has been synthesized with 2，4，6-trimethylbenz-oic acid， 4，4′-bipyridine and nickel perchlorate anhydrous， and characterized in the solvent mixture of water and methyl-alcohol. Crystal data for this complex: monoclinic， space group C2/c， a=2.154 7(7) nm， b=1.131 9(2) nm， c=1.655 7(8) nm， β=129.66(3)°， V=3.108 7(19) nm³， D_c=1.370 g·cm^-3， Z=4， F(000)=1 360， final GooF=1.042， R₁=0.034 4， wR₂=0.078 7. The crystal structure shows that the nickel ion is coordinated with two nitrogen atoms of two 4，4′-bipyridine molecules and four oxygen atoms from two 2，4，6-trimethylbenzoic acid molecules and two water molecules， respectively， forming a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex is also reported. CCDC: 649415.     

配合物[Cd(m-nitrobenzoic acid)2(phen)2]·(H2O)2的合成、晶体结构及电化学性质

在乙醇和水的混合溶剂中以间硝基苯甲酸(m-nitrobenzoic acid)、邻菲咯啉(phen)为原料合成了一个新的配合物[Cd(m-nitrobenzoic acid)₂(phen)₂]·(H₂O)₂,该配合物晶体属三斜晶系,空间群P1。配合物中镉原子与2个phen的4个N原子和2个间硝基苯甲酸根的3个羧基氧原子配位形成七配位的五角双锥结构。电化学性质研究表明：标题配合物     

配位聚合物[Ni(cpna)(bpy)(H2O)]n的合成、晶体结构及磁性质

通过水热方法,采用H₂cpna(H₂cpna=5-(2′-carboxylphenyl))和bpy(bpy=2,2′-bipyridine)与Ni(OAc)₂·4H₂O反应,合成了一个具有二维结构的配位聚合物[Ni(cpna)(bpy)(H₂O)]_n (1),并对其结构和磁性质进行了研究。结构分析结果表明该聚合物的晶体属于单斜晶系,P2₁/c空间群。3个镍(Ⅱ)离子、3个cpna配体、3个2,2′-bpy配体和3个配位水分子形成了一个[Ni₃(cpna)₃(bpy)₃(H₂O)₃]环,这些环通过镍(Ⅱ)离子与cpna配体的配位作用形成了一个二维层状结构。层与层之间又通过π-π堆积作用形成了一个三维的配位框架。研究表明,该聚合物中相邻镍(Ⅱ)离子之间存在很弱的反铁磁相互作用。     

配合物[1-(4′-bromo-2′-fluorobenzyl)pyridinium]2[Ni(mnt)2]和[1-(4′-bromo-2′-fluorobenzyl)pyrazinium]2[Ni(mnt)2](mnt2-=maleonitriledithiolate dianion)的合成及晶体结构

本文报道两个含双(马来二氰基二硫烯)镍(Ⅱ)配合物阴离子的离子对化合物。对阳离子为1-(4′-溴-2′-氟苄基)吡啶 盐时,生成配合物1。晶体数据:三斜晶系,空间P1群,a=0.7086(2)nm,b=1.0968(3)nm,c=1.1775(3)nm,α=69.914(5)°,β=89.495(5)°,γ=74.765(5)°,V=0.8259(4)nm³,Z=1。对阳离子为1-(4′-溴-2′-氟苄基)吡嗪鎓盐时,生成配合物2。晶体数据:单斜晶系,空间群P2₁/n,a=0.71554(17)nm,b=1.4262(3)nm,c=1.6725(4)nm,β=100.396(4)°,V=1.6788(7)nm³,Z=4。两个配合物中,阴离子为拟平面结构,镍原子均位于对称中心。变换对阳离子上的芳环种类对晶体的堆积结构产生影响。     

三维超分子[Ni(hmt)2(SCN)2(H2O)2][Ni(SCN)2(H2O)4](H2O)2的自组装,晶体结构及磁性质(hmt=六次甲基四胺)

Compound [Ni(hmt)₂(SCN)₂(H₂O)₂][Ni(SCN)₂(H₂O)₄](H₂O)₂ (hmt=hexamethylenetetramine) was pre-pared and structurally characterized by means of X-ray single crystal diffraction. The two neutral units [Ni(hmt)₂(SCN)₂(H₂O)₂] and [Ni(SCN)₂(H₂O)₄] are joined together through hydrogen bonds N…H-O, O…H-O and S…H-O. In the solid state, the compound has three-dimensional network structure. The determination of its variable-temperature magnetic susceptibilities (5～300K) shows that the magnetic behavior obeys the Curie-Weiss law over the whole temperature ranges.     

Crystal Structure of (H3O)4[(C2H5)4N]6 [Th2Cl4(H2O)12O]3[Re4Se4(CN)12]4

Crystals of the rhenium cluster complex (H₃O)₄[(C₂H₅)₄N]₆[Th₂Cl₄(H₂O)₁₂O]₃[Re₄Se₄(CN)₁₂]₄ are obtained in an acidic (HCl) aqueous solution by the reaction of cluster salt K₄[Re₄Se₄(CN)₁₂]·6H₂O with ThCl₄ and (C₂H₅)₄NCl. Single crystal X-ray analysis shows that the title compound is ionic and crystallizes in the cubic crystal system (a = 22.7322(3) ?, V = 11746.93(27) ?³, Z = 2, I4 3m space group, R = 0.0350). It contains [Th₂Cl₄(H₂O)₁₂O]²⁺ cations with two thorium atoms bonded to each other through the bridging oxygen atom forming an angle of 180° in the structure.     

[Gd2(Gly)6(H2O)4](ClO4)6(H2O)5的合成、晶体结构与热化学研究

利用微波技术合成了配合物[Gd₂(Gly)₆(H₂O)₄](ClO₄)₆(H₂O)₅, 进行了化学成分分析、红外表征和热重分析. 应用X衍射仪测定其晶体结构, 该晶体为一维链结构, 属三斜晶系, P 空间群, 晶胞参数: a＝1.1569(17) nm, b＝1.4138(2) nm, c＝1.5642(2) nm, α＝96.910(2)°, β＝102.735(2)°, γ＝105.512(2)°, V＝2.3606(6) nm³, Z＝2, D_c＝2.144 g•cm^－3. 采用精密溶解-反应量热计, 通过设计热化学循环, 计算出了该配合物的标准摩尔生成焓为 －(7960.73±3.23) kJ•mol^－1.     

一种镧系-过渡金属二维氰桥配合物[Nd(DMSO)2(H2O)2][Ni(CN)4]Cl(DMSO=二甲亚砜)的合成和晶体结构(英)

The cyano-bridged bimetallic complex [Nd(DMSO)₂(H₂O)₂][Ni(CN)₄]Cl with two-dimensional gridding molecule structure was synthesized and characterized. In the complex all four cyano groups of unit Ni(CN)₄^2- are bound to Nd³⁺ ions. The crystal data for the title complex: monoclinic, space group P2₁/c, a=0.780 0(3) nm, b=1.509 7(6) nm, c=1.683 2(6) nm, β=115.231(14)°, Z=4, μ=4.311 mm^-1, final R₁=0.020 9, wR₂=0.045 4. CCDC: 272214.     

[Ni(phen)2(3,5-DMBA)](m-MBA)2(H2O)2配合物的合成、晶体结构及电化学分析

The title complex of nickel (II) with 3,5-dimethylbenzoic acid, m-methylbenzoic acid and 1,10- phenanthroline was synthesized and characterized. Crystal data for this complex: triclinic, space group P1, a=1.198 5(2) nm, b=1.315 3(2) nm, c=1.531 8(3) nm, α=92.602(3)°, β=103.292(3)°, γ=114.849(3)°, V=2.104 7(6) nm³, D_c=1.361 g·cm^-3, Z=2, F(000)=902, final GooF=1.071, R₁=0.067 2, wR₂=0.155 5. The crystal structure shows that the nickel ion is coordinated with four nitrogen atoms of two 1,10-phenanthroline molecules and two oxygen atoms of one 3,5-dimethyl benzoic acid molecule, forming a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex was also investigated. CCDC: 286966.     

以吡啶为配体的镍配合物[Ni(py)3(H2O)3] (1, 5-nds)的合成、晶体结构及性质研究

采用缓慢蒸发法, 在水溶剂中合成了含氮配体单核Ni(Ⅱ)配合物[Ni(py)₃(H₂O)₃] (1, 5-nds)(py=pyridine, 1, 5-nds=1, 5-萘二磺酸根离子)。采用X射线单晶衍射、红外光谱、热分析和紫外可见光谱等方法对配合物进行了表征。X射线单晶衍射表征结果表 明, 该配合物晶体属于单斜晶系, 空间群为C2/c。晶体学参数:a=1.569 46(17) nm, b=1.219 95(12) nm, c=1.454 71(16) nm, β=14.547 1(16)°, V=2.765 1(5) nm³, Z=4。考察了该配合物的磁性和荧光性质。     

[Co(HOC10H6COO)2(H2O)4]配合物的合成、晶体结构和性质研究

Complex [Co(HOC₁₀H₆COO)₂(H₂O)₄] was synthesized by reaction of hydroxy-2-naphthoic acid with CoCl₂·6H₂O. The compound was characterized by elemental analysis, IR and the structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P2₁/n with a=0.675 8(2) nm, b=0.518 15(14) nm, c=2.962 9(9) nm, β=94.925(8)°. V=1.033 6(5) nm³, Z=2, D=1.624 Mg·m^-3, F(000)=522. The Co atom has an octahedron coordination geometry and was six-coordinated with two oxygen atoms from two carboxylate ligands and four oxygen atoms from four water molecules. The complex molecules were linked by different hydrogen bonds to form a 2D network. The complex has thermal stability and shows a strong fluorescent emission at 421 nm (λ_ex=342 nm). CCDC: 250903.     

[NEt~4][Mn(salophen)(H~2O)~2]~2[Fe(CN)~6]·H~2O· CH~3OH超分子化合物的 合成和结构

室温下将[NEt~4]~3[Fe(CN)~6]和[Mn(salophen)(H~2O)(CH~3OH)]ClO~4反应,得到了超分子化合物[NEt~4][Mn(salophen)(H~2O)~2]~2[Fe(CN)~6]·H~2O·CH~3OH(salophenH~2=双水杨醛缩邻苯二胺),并对其进行了晶体结构测定。结果表明,该晶体属三斜晶系,空间群P1,晶胞参数a=1.2150(4)nm,b=1.4834(6)nm,c=1.6625(6)nm,α=81.896(7)°,β=76.980(8)°,γ=81.120(6)°,V=2.872(2)nm^3,Z=2,D~c=1.388g·cm^-^3。晶体的各部分间以氢键连接成网状超分子体系。