A coordination polymer with a (3,4)-connected (4·62)2(42 ·62 ·82) 2D network: synthesis,crystal structure and luminescent properties

The 2D Zn(II) coordination polymer with 2,3-dicarboxypyridine acid (2,3-H₂PDC) and dimethylamine (DMA) [Zn(2,3-PDC)(DMA)] _n (1) was synthesized under solvothermal conditions and characterized by FT-IR spectroscopy, TGA and luminescent analysis. X-ray crystallographic studies of 1 reveal that this metal-organic complex has an interesting (3,4)-connected 2D network with binary nodes. The Zn ions are four-connected nodes and the 2,3-PDC ligands are three-connected nodes. Luminescent study indicates 1 has an emissive maximum at 403?nm in the solid state at room temperature.     

SUBJECT INDEX TO VOLUME 42 (1999)

A CIDEP study of photolysis benzophenone radicals in the microheterogeneous phase systems ‘‘‘··‘·’······-··-·-·······················‘‘‘‘·。。‘‘‘‘。。‘。‘‘’‘‘‘‘‘‘‘‘‘。‘‘‘‘‘’’’”LU Tongxing.LI Ganzuo.SU Hongmei et a1.DSC study of phase transitions of cephalin pseudo-binary systems in excess water ’’’。。‘‘‘‘‘‘。‘‘’WANG Bangning.TAN FuCuring theory of ArAg type free radical polymerization(II) ——Charac…     

Supramolecular architectures based on As(lone pair)···π(aryl) interactions

As(lone pair)···π interactions provide stability to their crystal structures often leading to supramolecular chains and prevailing over As···X secondary contacts. The interaction (ca 8 kJ mol(-1)) arises from polarisation induced in the aryl ring by the As-lone pair plus the weak sharing of these electrons with the ring-C atoms.     

Synthesis and Structure of a Manganese(Ⅱ) Complex [Mn·(p-Methoxybenzoato)_2·(2,2'-bipy)·H_2O]·(p-methoxybenzoic Acid)

The title compound,{[MnL2·(2,2'-bipy)·H2O]·(HL)},has been synthesized (HL =p-methoxybenzoic acid,2,2'-bipy = 2,2'-bipyridine) by the reaction of MnCl2·6H2O with p-methoxybenzoic and 2,2'-bipyridine in an alcohol-water solution.It crystallizes in the triclinic system,space group P1 with a = 10.1138(5),b = 11.2811(5),c = 16.2210(8)(A),a = 77.5920(10),β= 72.1890(10),γ = 66.2320(10)°,Mr = 683.56,V= 1603.65(13) (A)3,Z= 2,Dc = 1.416 g/cm3,F(000)= 710,μ =0.473 mm-1,the final R = 0.0619 and wR = 0.1571 for 4724 observed reflections with I ＞ 2σ(I).The structure determined demonstrated that it is an isomeric modification of the structure reported before.The Mn atom is six-coordinated by two N and four O atoms,forming a distorted octahedral geometry.All Mn-O and Mn-N distances range from 2.113(3)～2.410(3) (A).There also.exists a dissociative p-methoxybenzoic acid beside the octahedron.     

碘·(N,N'-联吡啶)·(三苯基膦)合铜(Ⅰ)的合成和晶体结构

铜(I)配合物的研究在金属酶的化学模拟和配合物结构及反应性能等研究方面具有重要的理论和实际意义[1].但由于铜(I)配合物不稳定, 且在多数有机溶剂中的溶解度较小,铜(I)配合物的合成比较困难.我们在铜(I)配合物的合成方面积累了一些经验,合成了一系列含有三苯基膦和氮杂环配体的铜(I)配合物[CuX(PPh3)L]n[2～4] (n=1, X=I, L=1,10-phen; n=2, X=Br, I, L=C9H7N),并对它们的结构进行了研究.本文报道一个类似的新配合物[CuI(PPh3)(bpy)](I)的合成和晶体结构, 并把它与其它几个类似的配合物进行了对比.     

碘·(N,N'联吡啶)·(三苯基膦)合铜(I)的合成和晶体结构

铜（Ｉ）配合物的研究在金属酶的化学模拟和配合物结构及反应性能等研究方面具有重要的理论和实际意义［１］。但由于铜（Ｉ）配合物不稳定,且在多数有机溶剂中的溶解度较小,铜（Ｉ）配合物的合成比较困难。我们在铜（Ｉ）配合物的合成方面积累了一些经验,合成了一系列含有三苯基膦和氮杂环配体的铜（Ｉ）配合物［ＣｕＸ（ＰＰｈ３）Ｌ］ｎ［２～４］（ｎ＝１,Ｘ＝Ｉ,Ｌ＝１,１０ｐｈｅｎ;ｎ＝２,Ｘ＝Ｂｒ,Ｉ,Ｌ＝Ｃ９Ｈ７Ｎ）,并对它们的结构进行了研究。本文报道一个类似的新配合物［ＣｕＩ（ＰＰｈ３）（ｂｐｙ）］（Ｉ）的合成…     

[(C_(16)H_(32)N_4)~(-4)·2Mn~(2+)·4HCl·[(C_(16)H_(36)N_4)·2H_2O]多元包合物的晶体结构

[(4氮间杂六甲基十四烷环)~(-4)·2Mn~(2+)]·4HCl·[4氮间杂六甲基十四烷环)·2H_2O]的晶体结构已用单晶X线衍射技术测定完成。它属于三斜晶系,P_1空间群,晶胞参数a=9.028(2),b=11.055(2),c=12.202(4),α=71.70(2),B=88.41(2),γ=75.32(2)~°,Z=1。对于2597个可观察独立反射计算R=0.073。结构分析证实,该晶体存在有四类物种,由负4价的四氮间杂六甲基十四烷环(简称电负性大环Ⅱ),2个Mn~(2+)正离子,4个HCl分子和一个携带2个结晶水的4氮间杂六甲基十四烷环(简称电中性大环Ⅰ)组成。 4个HCl分子处于电负性大环Ⅱ的周围,大环Ⅱ和Mn~(2+)离子间按离子键特点取空间最稳定构型与电中性大环Ⅰ沿c方向周期性交替排布,构成四元包合物O~-、N~-、Cl~-等电负性强的离子之间形成很强的H键网。 六十年代以来,以四氨间杂六甲基十四烷环作配体,以Co~(2+)、Co~(3+)、Ni~(2+)等金属离子为络合中心的大环络合物,国外已有许多报导。这些结构的共同特点是大环配体的4个氮原子围绕金属离子以构成四配位或六配位结构,研究表明,络合以后金属的电子组态发生了变化。 近来,我们将Mn~(2+)与上述的配体反应,结果得到与上述结构绝然不同的化合物。NMR谱证实,该化合物中包含电中性和电负性两种大环。环伏安法测其锰离子是2价正离子(详见     

氯化二(羟胺根)·(羟胺—O)·水合氧钒(Ⅴ)[VO·(NH_2O)_2·(NH_3O)·H_2O]Cl的晶体结构

调节硫酸氧钒与盐酸羟胺溶液至pH～4制得的题目晶体属空间群P2_1/n,晶胞参数a=8.201,b=8.597,c=9.947A,β=93.00°,Z=4.结构解出精修后R因子为0.069.结果表明,不对称单位中二个羟胺根以侧接态与VO~(3+)配位,另一羟胺取端接态以O占据V的第五赤道配位位置,配位水处于氧钒基强键反位,Cl~-则在配阳离子界外以平衡电荷,晶体对的化学式确证为[(VO~(3+))(NH_2O~_)_2(NH_3O)(H_2O)][Cl~-]     

Formation of μ-dinitrogen (salen)osmium complexes via ligand-induced N···N coupling of (salen)osmium(VI) nitrides

Treatment of [N(n)Bu(4)][Os(VI)(N)Cl(4)] with a stoichiometric amount of H(2)L (L = N,N'-bis(salicylidene)-o-cyclohexylenediamine dianion) in the presence of PF(6)(-) or ClO(4)(-) in MeOH affords [Os(VI)(N)(L)(OH(2))](PF(6)) 1a and [Os(VI)(N)(L)(CH(3)OH)](ClO(4)) 1b, respectively. The structure of 1b has been determined by X-ray crystallography and the Os≡N bond distance is 1.627(3) ?. In the presence of a N-donor heterocyclic ligand in CH(3)CN, 1a reacts at room temperature to afford the mixed-valence μ-N(2) (salen)osmium species [(X)(L)Os(III)-N≡N-Os(II)(L)(X)](PF(6)), 2-14 (X = py 2; 4-Mepy 3; 4-(t)Bupy 4; pz 5; 3-Mepz 6; 3,5-Me(2)pz 7; Im 8; 1-MeIm 9; 2-MeIm 10; 4-MeIm 11; 1,2-Me(2)Im 12; 2-Meozl 13; 4-MeTz 14). These complexes are formed by ligand-induced N···N coupling of two [Os(VI)≡N](+) to give initially [Os(III)-N(2)-Os(III)](2+), which is then reduced to give the more stable mixed-valence species [Os(III)-N(2)-Os(II)](+). Cyclic voltammograms (CVs) of 2-14 show two reversible couples, attributed to Os(III,III)/Os(III,II) and Os(III,II)/Os(II,II). The large comproportionation constants (K(com)) of (5.36-82.3) × 10(13) indicate charge delocalization in these complexes. The structures of 3 and 14 have been determined by X-ray crystallography, the salen ligands are in uncommon cis-β configuration. Oxidations of 4 and 14 by [Cp(2)Fe](PF(6)) afford the symmetrical species [(X)(L)Os(III)-N≡N-Os(III)(L)(X)](PF(6))(2) (X = 4-(t)Bupy 15; 4-MeTz 16). These are the first stable μ-N(2) diosmium(III,III) complexes that have been characterized by X-ray crystallography.     

Emerging supramolecular synthons: C-H···π(chelate) interactions in metal bis(1,1-dithiolates)

Crystal structures of transition and main group element 1,1-dithiolates are shown to be partially sustained by C-H···π(chelate) interactions. For the planar binary bisdithiocarbamates, C-H···π(MS(2)C) interactions lead to aggregation patterns ranging from a 0-D four molecule aggregate to a 3-D architecture but with the majority of structures featuring 1-D or 2-D supramolecular assemblies.     

K_(10)[H_2W_(12)O_(42)]·11H_2O的合成及晶体结构分析

在水溶液中反应制得无色透明的标题化合物单晶 ,单晶X -射线结构分析表明 ,属单斜晶系 ,空间群P2 1,晶胞参数 :a=1.15 47(2 )nm ,b =1.430 9(3)nm ,c =1.5 495 (3)nm ,β =10 5 .41(3)° ,V =2 .46 81(9)nm3,Z =2 ,Dc=4.6 39Mg/m3,对 5 45 4个独立衍射点 (I>2δ(I) )进行全矩阵最小二乘法修正后 ,可靠性因子R =0 .0 487     

A Pseudo-Keggin Compound: Hydrothermal Synthesis and Crystal Structure of (DETAH)(DETAH_3)_3[V_(18)O_(42)(PO_4)]·(PO_4)·2H_2O

The novel vanadophosphate (DETAH)(DETAH3)3[V18O42(PO4)]·(PO4)·2H2O has been synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic, space group C2/c with a = 23.857(3), b = 12.9619(18), c = 20.204(3) , β = 105.692(2)°, V = 6015.0(14) 3, Z = 4, Dc = 2.473 g/cm3, Mr = 2239.68, F(000) = 4432, R = 0.0725, wR = 0.1524 and GOOF = 1.095. The metaloxo cluster contains a novel six-capped pesudo-Keggin structure unit which encloses a disorder PO43- guest.     

Concerted halogen and hydrogen bonding in [RuI2(H2dcbpy)(CO)2]···I2···(CH3OH)···I2···[RuI2(H2dcbpy)(CO)2

A new type of concerted halogen bond-hydrogen bond interaction was found in the solid state structure of [RuI(2)(H(2)dcbpy)(CO)(2)]···I(2)···(MeOH)···I(2)···[RuI(2)(H(2)dcbpy)(CO)(2)]. The iodine atoms of the two I(2) molecules interact simultaneously with each other and with the OH group of methanol of crystallization. The interaction was characterized by single crystal X-ray measurements and by computational charge density analysis based on DFT calculations.     

Synthesis and Structural Characterization of Adduct Cu_2(phen)_2·3(FCA)·(ClO_4)·2H_2O

Differentkindsofcopper(II)carboxylateadductshavebeensynthesizedandalsodinuclearcopper(Il)complexeshavebeenearlystUdiedasusefulmodelstoestablishmagneto-structUra1correlationsforspinexchangebetWeenmetalions.CostaIshowedthestructureof[Cu,(ll-OOCFc),(bpy),(ClO')(CH,Oand[Cu,(n-OOCFc),(bpy)(CH,OH),]' .Asfarasweknow,thecopper(II)compoundscontainingFCAandphenhavenotbeenreported.TheligandofFCAwassynthesizedaccordingtothefoIlowingscheme2.3:Asolutioncontainingl98mg(lmmol)ofphenandl5mLofmet…     

(enH_2)_4Na_4H_3[(VO)_(12)O_6B_(18)O_(42)]·8H_2O的水热合成和晶体结构

在水热的条件下合成了多钒硼酸盐(enH2)4Na4H3[(VO)12O6B18O42]8H2O, 化学式为C8H59B18N8Na4O68V12 (Mr=2253.45), 用单晶X射线衍射方法测定了它的结构, 该晶体属单斜晶系, P21/n空间群, 晶胞参数为a = 13.8989(4), b = 16.1954(5), c = 14.4520(4) ?β = 94.7490(5), V= 3241.95(16) ?, Z = 2, Dc = 2.308 g/cm3, ?= 1.819mm-1, F(000) = 2234, 4798个可观察衍射点(I > 2s(I)), 最终结构精修到偏离因子R = 0.0449, wR = 0.1163, S = 0.996。在该化合物的结构中, V12B18簇是由环状的B18O42通过18个B(μ3-O)V键被2个V6O18环夹在中间组成的, V12B18簇通过4个Na+与相邻的簇相连, 形成二维网状结构, 孔道尺寸为6.109×10.562 拧?     

A Pseudo-Keggin Compound:Hydrothermal Synthesis and Crystal Structure of (DETAH)(DETAH3)3[V18O42(PO4)]·(PO4)·2H2O

The novel vanadophosphate (DETAH)(DETAH3)3[V18O42(PO4)]·(PO4)·2H2O has been synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic, space group C2/c with a=23.857(3), b=12.9619(18), c=20.204(3) (A), β=105.692(2)°, V=6015.0(14) (A)3, Z=4, Dc=2.473 g/cm3, Mr=2239.68, F(000)=4432, R=0.0725, wR=0.1524 and GOOF=1.095. The metaloxo cluster contains a novel six-capped pesudo-Keggin structure unit which encloses a disorder PO43- guest.     

The gold(i)···lead(ii) interaction: a relativistic connection

The crystal structure of complex [Pb{HB(pz)₃}Au(C₆Cl₅)₂] 1 displays an unsupported Au(i)···Pb(ii) interaction. This complex emits at 480 nm in the solid state due to an aurate(i) to lead(ii) charge transfer, in which the existence of a metallophilic interaction is a pre-requisite. Ab initio calculations show a very strong Au(i)···Pb(ii) closed-shell interaction of –390 kJ mol^–1, which has an ionic plus a dispersive (van der Waals) nature strengthened by large relativistic effects (>17%).     

新钽酸盐K_6FeTa_(15)O_(42)的合成与表征

在K2O -Fe2O3-Ta2O5 三元系统中 ,新发现存在钽酸盐K6FeTa15O42,使用X射线衍射(XRD)、电子探针微区分析(EPMA)、扫描电镜(SEM)、差热分析(DTA)等方法对该化合物的晶体结构、成分、形态、光学性质、溶解性、熔点及密度进行了研究。新化合物K6FeTa15O42 晶体属于六方晶系,空间群P63/mcm,晶胞参数a=0.91221(1)nm,c=1.21084(4)nm,Z=1,V=0.87258nm3。     

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of Complex [Cd(phen)3]·(ClO4)2·(p-MBA)2·(H2O)2

One new cadmium complex [Cd(phen)3]·(ClO4)2·(p-MBA)2·(H2O)2 has been hydro- thermally synthesized by reacting p-methylbenzoic acid (p-MBA), 1,10-phenanthroline (phen) and cadmium perchlorate. It crystallizes in the triclinic system, space group P, with a = 1.2809(3), b = 1.3431(3), c = 1.3734(3) nm, α = 84.259(4), β = 71.603(3), γ = 74.424(3)o, V = 2.1594(8) nm3, Dc = 1.532 g/cm3, Z = 2, F(000) = 1008, μ = 0.697 mm-1, R = 0.0646 and wR = 0.1648. The crystal structure shows that the cadmium ion is coordinated with six nitrogen atoms from three 1,10-phenanthroline molecules, forming a distorted octahedral coordination geometry. The result of electrochemical property analysis shows that the electron transfer in the electrode reaction is irreversible.