Syntheses, structures, and characterizations of four new lead(II) 5-sulfosalicylate complexes with both chelating and bridging neutral ligands

Four structurally diverse complexes, {[Pb(Hssal)(2,2'-bipy)](4,4'-bipy)0.5}n (1), [Pb2(Hssal)2(2,2'-bipy)2(4,4'-bipy)(H2O)2] (2), [Pb(Hssal)(phen)(4,4'-bipy)0.5]n (3), and [Pb(Hssal)(2,2'-bipy)(bpe)0.5]n (4), have been synthesized and characterized by elemental analyses, IR, thermogravimetric analyses, fluorescent spectra, and single-crystal X-ray analyses, where Hssal2- is doubly deprotonated 5-sulfosalicylate, 2,2'-bipy is 2,2'-bipyridine, phen is 1,10-phenanthroline, 4,4'-bipy is 4,4'-bipyridine, and bpe is trans-1,2-bis(4-pyridyl)ethylene. The structure of complex 1 possesses a one-dimensional ladderlike chain with guest 4,4'-bipy molecules, while the molecular structure of complex 2 is a dimeric species with a coordinating 4,4'-bipy ligand. Complex 3 consists of a one-dimensional ladderlike chain with monodentate 4,4'-bipyridine but somewhat different from that of complex 1. Complex 4 is a two-dimensional layer structure. In 1-4, all 5-sulfosalicylates are doubly deprotonated, and all carboxylate groups of Hssal2- chelate to PbII ions; however, the coordination modes of sulfonyl groups are different: syn-syn bridging in 1, noncoordinating in 2, syn-skew bridging in 3, and one-atom bridging in 4. The noncoordinating mode of sulfonate in PbII complexes containing 5-sulfosalicylate is first reported in this presentation. The 4,4'-bipy ligands act as guest molecules in 1, dimeric linkers in 2, and monodentates in 3. The pi-pi stacking interactions can be observed in complexes 1-3, whereas there is no such interaction in complex 4. The coordination spheres of PbII ions in 1-4 are controlled by three factors: the activity of a lone pair of electrons, weak Pb-O interactions, and pi-pi stacking interactions. The PbII lone pair in 4 is inactive, whereas in 1-3, they are stereochemically active. The thermal stability and fluorescent property of complexes 1-4 are different from those of PbII complexes only containing chelating ligands, [Pb(Hssal)(2,2'-bipy)(DMF)]n (5), and [Pb(Hssal)(2,2'-bipy)(H2O)]n (6), and [Pb(Hssal)(phen)(DMF)]n (7).     

Synthesis, characterization, and crystal structures of three new divalent metal carboxylate-sulfonates with a layered and one-dimensional structure

Hydrothermal reactions of 5-sulfoisophthalic acid (HO(3)SC(6)H(3)-1,3-(CO(2)H)(2), H(3)L) with M(II) carbonate (or oxide) and 4,4'-bipyridine (4,4'-bipy) (or 2,2'-bipyridine, 2,2'-bipy) resulted in three new metal carboxylate-sulfonate hybrids, namely, [CdL(H-4,4'-bipy)] (1) and [Cd(3)L(2)(2,2-bipy)(4)(H(2)O)(2)].2H(2)O (2) with layered structures and [ZnL(H-4,4'-bipy)(H(2)O)].2H(2)O (3), whose structure features a one-dimensional double chain. The cadmium(II) ion in complex 1 is seven-coordinated by five carboxylate oxygen atoms and one sulfonate oxygen atom from four ligands and a unidentate 4,4'-bipyridine. The interconnection of the cadmium(II) ions through bridging carboxylate-sulfonate ligands resulted in the formation of a <002> double layer with the bipyridyl rings orientated toward the interlayer space. Complex 2 has a different layered structure. Cd(1) is seven-coordinated by two bidentate chelating carboxylate groups from two ligands, a bidentate chelating 2,2'-bipy and an aqua ligand, and Cd(2) is octahedrally coordinated by two bidentate chelating 2,2'-bipy's, a sulfonate oxygen, and an aqua ligand. The coordination geometry around Cd(3) is similar to that of Cd(1) with the aqua ligand being replaced by an oxygen atom from the sulfonate group. The carboxylate-sulfonate ligand acts as pentadentate ligand, bridging with three cadmium(II) ions. The bridging of cadmium(II) ions through the carboxylate-sulfonate ligands resulted in the formation of <006> and <003> layers; the 2,2'-bipy molecules and [Cd(2)(2,2'-bipy)(2)(H(2)O)] cations are orientated to the interlayer space. Complex 3 features a 1D metal carboxylate-sulfonate double chain along the diagonal of the a- and b-axes. The zinc(II) ion is octahedrally coordinated by four carboxylate O atoms from three ligands, a unidentate 4,4'-bipy, and an aqua ligand. Each pair of zinc(II) ions is bridged by two carboxylate groups from two ligands to form a dimer, and such dimeric units are interconnected by bridging ligands to form a double chain. The sulfonate group of the carboxylate sulfonate ligand remains noncoordinated and forms a number of hydrogen bonds with aqua ligands as well as lattice water molecules.     

Influence of the reaction conditions on the self-assembly of lead(II) 5-sulfosalicylate coordination polymers with chelating amine ligands

The synthesis and crystal structures of [Pb(Hssal)(2,2'-bipy)(DMF)]n (1), [Pb(Hssal)(2,2'-bipy)(H2O)]n (2), [Pb(Hssal)(phen)(DMF)]n (3), and [Pb3(ssal)2(phen)3]n (4) were reported, where Hssal2- and ssal3- are doubly and fully deprotonated 5-sulfosalicylates, 2,2'-bipy is 2,2'-bipyridine, and phen is 1,10-phenanthroline. Compounds 1-4 were synthesized by the various reaction conditions, such as reaction temperature, molar ratio, and pH, and these structures are formed by infinite chains or layers where Pb(II) ions are linked by Hssal2- or ssal3- bridges. Compound 1, which has a ladderlike chain, was formed in DMF/H2O. Compound 2 with a H2O molecule coordinated to Pb(II) was prepared by a hydrothermal reaction. Compounds 3 and 4 were synthesized in a higher pH compared to compounds 1 and 2, containing the 2,2'-bipy ligand. In 1-3, 5-sulfosalicylates are doubly deprotonated, whereas in 4, 5-sulfosalicylate is fully deprotonated. Coordination modes of Hssal2- and ssal3- ligands in 1-4 are novel and are first reported in this presentation. Although compounds 1 and 3 have the same structural topology, their aromatic-aromatic interactions are significantly different. The coordination spheres of Pb(II) ions in 1 and 3 are holodirected, whereas in 2 and 4, they feature somewhat hemidirected properties with small holes or gaps. Compound 4 exhibits some interesting features that (1) there is not any solvent in the structure, (2) there are extensively aromatic-aromatic stacking interactions among aromatic rings, and (3) there is also a weak interaction between Pb(II) atoms in the trinuclear motif.     

Synthesis and Fluorescent and Magnetic Properties of a New Europium Complex Eu(C_(20)H_(14)O_3N)_3(2,2'-bipy)(H_2O)·H_2O

A new europium(Ⅲ) complex Eu(C_(20)H_(14)O_3N)_3(2,2?-bipy)(H_2O)·H_2O has been synthesized with2-diphenylanine carbonyl benzoic acid and 2,2?-bipyridine as ligands.Crystal data for the complex are as follows:triclinic,space group ■,a=11.3334(5),b=16.0883(7),c=17.0116(8)?,α=70.411(4)o,β=82.435(4)o,γ=85.095(4)o,V=2894.0(2)?~3,D_c=1.484 g/cm~3,Z=2,μ=1.15 mm~(-1),F(000)=1320 and the final R=0.0447 and w R=0.0578.The Eu(Ⅲ) ion is coordinated by nine atoms to give a monocapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu~(3+):~5D_0→~7F_1 (592 nm) and ~5D_0→~7F_2 (616 nm),respectively.Also reported is the magnetic property of the complex.The complex exhibits antiferromagnetism in the temperature range of 300～2 K.     

Pb(II) coordination and synergistic ion-exchange extraction by combinations of sulfonamide chelates and 2,2'-bipyridine

The disulfonamide ligands 1,2-C(6)H(4)(NH(2)SO(2)C(6)H(5))(2) (1) and 1,2-C(6)H(4)(NH(2)SO(2)C(6)H(4)-p-Bu(t))(2) (2), which are readily available in good yields from o-phenylenediamine and the corresponding sulfonyl chlorides, efficiently extract Pb(II) from water into 1,2-dichloroethane when used in synergistic combinations with 2,2'-bipyridine via an ion-exchange mechanism. The extraction was shown to proceed via the formation of a ternary Pb-sulfamido-2,2'-bipyridine complex. The X-ray crystal structure of the binary Pb-sulfamido complex 3 shows a coordination polymer with a stereochemically active lone pair on Pb formed by S=O-Pb axial coordination.     

Novel Pb(II), Zn(II), and Cd(II) coordination polymers constructed from ferrocenyl-substituted carboxylate and bipyridine-based ligands

Treatment of two kinds of ferrocenyl-substituted carboxylate ligands (3-ferrocenyl-2-crotonic acid, HOOC-CH=(CH(3))CFc (Fc=(eta(5)-C(5)H(5))Fe(eta(5)-C(5)H(4))) or O-ferrocecarbonyl benzoic acid, o-HOOCC(6)H(4)COFc with Pb(OAc)(2).3H(2)O, Zn(OAc)(2).2H(2)O, or Cd(OAc)(2).2H(2)O) resulted in four novel ferrocene-containing coordination polymers [[Pb(mu(2)-eta(2)-OOCCH=(CH(3))CFc)(2)].MeOH](n) (1), [[Zn(o-OOCC(6)H(4)COFc)(2)(4,4'-bipy)(H(2)O)(2)].2MeOH.2H(2)O](n) (4,4'-bipy = 4,4'-bipyridine) (2), [[Cd(o-OOCC(6)H(4)COFc)(2)(bpe)(MeOH)(2)].2H(2)O](n) (bpe = 1,2-bis(4-pyridyl)ethene) (3), and [Pb(o-OOCC(6)H(4)COFc)(eta(2)-o-OOCC(6)H(4)COFc)(bpe)](n)() (4). Their crystal structures have been characterized by single X-ray determinations. In polymer 1, Pb(II) ions are bridged by tridentate FcC(CH(3))=CHCOO(-) anions, forming an infinite chain [Pb(mu(2)-eta(2)-OOC=CH(CH(3))CFc)(2)](n). In polymers 2-4, there are three kinds of components, metal ions, o-FcCOC(6)H(4)COO(-) units, and organic bridging ligands. The bipyridine-based ligands connect metal ions leading to a one-dimensional chain with o-FcCOC(6)H(4)COO(-) units acting as monodentate or chelate ligands in the side chain. Such coordination polymers containing ferrocenyl-substituted carboxylate and bipyridine-based ligands are very rare. The solution-state differential pulse voltammetries of polymers 1-4 were determined. The results indicate that the half-wave potential of the ferrocenyl moieties is influenced by the Pb(II) ions in polymer 1 and strongly influenced by Zn(II), Cd(II), or Pb(II) ions in polymers 2-4. The thermal properties of the four polymers were also investigated.     

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a Zinc(Ⅱ)Complex with 2,2'-Diphenic Acid and 2,2'-Bipyridine Ligands

A new dinuclear complex[Zn(dpa)(bipy)(H2O)]2(dpa=2,2'-diphenic acid,bipy=2,2'-bipyridine)1 has been hydrothermally synthesized and structurally characterized by elemental analysis,IR,fluorescence spectrum and single-crystal X-ray diffraction.The complex crystallizes in monoclinic,space group P21/c with a=10.960(2),b=9.4841(18),c=20.599(4)(A),β=104.452(3)°,V=2073.4(7)(A)3,C48H36N4O10Zn2,Mr=959.55,Dc=1.537 g/cm3,μ(MoKa)=1.225 mm-1,F(000)=984,Z=2,the final R=0.0364 and wR=0.0843 for 2788 observed reflections(I>20(I)).In the crystal structure,the zinc atom is five-coordinated with two carboxylate oxygen atoms from different dpas,one coordinated water molecule and two nitrogen atoms from bipy ligands,showing a slightly distorted triangular bipyramidal geometry.Furthermore,it exhibits a zero-dimensional network structure with a sixteen-membered ring and shows yellow photoluminescent property at room temperature.     

双过氧钒配合物与吡啶类配体相互作用的NMR研究

为探讨单齿/双齿吡啶类配体对反应平衡的影响,在模拟生理条件下(0.15mol·L-1NaCl溶液),应用多核(1H、13C和51V)多维(COSY,HSQC和HMBC)以及变温NMR技术研究双过氧钒配合物[OV(O2)2(D2O)]-/[OV(O2)2(HOD)]-(简写为bpV)与系列吡啶类配体的相互作用,研究结果表明bpV与有机配体的反应性从强到弱的顺序为:2,2′-联吡啶2,2′-联吡啶-4,4′-二甲酸根吡啶异烟酸根,这说明双齿吡啶类配体配位能力强于单齿配体,而不带羧基的吡啶类配体(单齿或双齿)配位能力强于所对应的带羧基的取代吡啶,竞争配位导致一系列新的6配位(配体为吡啶或异烟酸根)或7配位(配体为2,2′-联吡啶或2,2′-联吡啶-4,4′-二甲酸根)的过氧钒物种[OV(O2)2LL′]n-(LL′=吡啶类配体,n=1,2,3)生成。     

Two Metal-organic Frameworks（MOFs） Assembled from One Asymmetric Semirigid Multicarboxylate Ligand：Syntheses and Crystal Structural Characterizations

Hydrothermal reactions between a new flexible multicarboxylate ligand of 3-(2-carboxy-phenoxy)-benzoic acid(H2L) and transitional metal cations of M2+(M = Cu2+,Ni2+) in the presence of the secondary ligands of 1,10-phenanthroline(phen),2,2'-bipyridine(2,2?-bpy),and 4,4'-bipyridine(4,4'-bpy) afford two novel coordination polymers Ni2(H2O)2L2(phen)(μ-4,4'-bpy)(1) and CuIIL(2,2'-bpy)(2).Both compounds were characterized by X-ray crystallography.Crystal data of 1:C31H24N3NiO7,Mr = 609.24,monoclinic,space group P21/c,a = 17.560(8),b = 10.528(5),c = 30.613(15) ,V = 5659(5) 3,Z = 4,Dc = 1.430 g/cm3,F(000) = 502,μ = 0.739 mm-1,R = 0.0902,wR = 0.1346(I > 2σ(I)),S = 1.002.Crystal data of 2:C24H16CuN2O5,Mr = 475.93,monoclinic,space group P21/n,a = 9.8904(13),b = 11.0782(16),c = 18.321(3) ,β = 11.0782(16)°,V = 1993.8(5) 3,Z = 4,Dc = 1.585 g/cm3,F(000) = 972,μ = 1.137 mm-1,R = 0.0433,wR = 0.0723(I > 2σ(I)) and S = 1.004.Compound 1 displays a one-dimensional(1D) zigzag chain structure constructed from phen ligands and the deprotonated ligands of L2-,which further forms a ladder-shaped supramolecular architecture via the bridge of 4,4'-bpy ligand.Complex 2 also possesses a ladder-shaped architecture based on the dinuclear CuII units.     

Synthesis and Crystal Structure of a 1-D Chain Zinc(Ⅱ) Coordinated Polymer with N-p-Tolysulfonyl-glutamine

A novel coordination polymer {[Zn(ts-gln)(bipy)]3H2O}n (ts-glnH2=N-p-toly-sulfonyl-glutamine,bipy=2,2-bipyridine) has been prepared and structurally characterized by X-ray diffraction method. It crystallizes in orthorhombic,space group P212121 with a=8.2622(5),b=16.6244(10),c=18.2807(10) ,V=2510.9(3) 3,C22H28N4O8SZn,Mr=573.91,Z=4,Dc= 1.518 g/cm3,μ(MoKa)=1.115 mm-1,F(000)=1192,the final R=0.0262 and wR=0.0662 for 5691 independent reflections with Rint=0.0240. The zinc(Ⅱ) atom is coordinated by N(3) and N(4) atoms of a bipy molecule,two carboxylate O(1) and O(2A) and amino N(1) atoms of ts-gln ligands,resulting in a square-pyramidal geometry. The title complex consists of an infinite zigzag chain of zinc(Ⅱ) ions linked by the carboxylate of N-p-tolysulfonyl-glutamine.     

The ligand, the metal and the 'Holey'-host: Synthesis, structural and magnetic characterisation of Co(II), Ni(II) and Mn(II) metal-organic frameworks incorporating 4,4'-dicarboxy-2,2'-bipyridine

We report herein the single crystal structures of four metal-organic framework complexes incorporating the 4,4'-dicarboxy-2,2'-bipyridine ligand, H(2)dcbp: alpha-[Co(dcbp)(H(2)O)(2)], 1; beta-[Co(dcbp)(H(2)O)(2)], 2, [Ni(dcbp)(H(2)O)(2)], and [[Mn(dcbp)].1/2DEF], 4 (DEF = diethylformamide). In each complex the ligand is deprotonated giving neutral species with 1:1 stoichiometry that form three-dimensional coordination polymers. Supramolecular isomerism (polymorphism) in 1 and 2 arises from the different ligand connectivity around the octahedral Co(II) centres. The two coordinated water molecules in 1 occupy cis positions, which are trans to the chelating bipyridine nitrogen atoms, leaving the carboxylate oxygen atoms in axial trans positions. In 2 all like donors occupy cis positions. Different modes of carboxylate coordination in 1 and 2 give dissimilar network topologies. A rare example of two interpenetrating 6(4)8(2)-b (quartz-like) chiral networks in 1 results from both dcbp carboxylate groups coordinating in a monodentate fashion to adjacent Co(II) centres, whereas in 2 only one carboxylate group bridges between adjacent Co(II) centres giving rise to a single chiral (10,3)-a net. In 1 and 2 the coordinated water molecules hydrogen bond to the non-coordinated carboxylate oxygen atoms. These interactions give rise to water-carboxylate double helices in , and support the coordination network in 2. Strikingly for a pair of dimorphs the crystal densities of 1 and 2 differ by ca. 0.3 g cm(-3)(1.654 vs. 1.940 g cm(-3), respectively). Compound 3 is isomorphous with 1 and likewise features two chiral interpenetrating nets of quartz topology. In 4, chelating bipyridine nitrogen atoms and four carboxylate oxygen atoms from a total of five adjacent dcbp ligands provide distorted octahedral geometry around Mn(II). The carboxylate groups bridge adjacent Mn(II) centres to produce bis-carboxylato chains which cross-link and generate a 3D network that is perforated with channels. The channels are occupied with disordered DEF molecules. The network topology in 4 is quite different to 1-3 and has a (4.6(2))(4(2).6)(4(3).6(6).8(6)) Schlafli notation. Magnetic susceptibility studies performed on 1, 2, [[Mn(dcbp)].1/2DMF] 5 (DMF = dimethylformamide) and [[Mn(dcbp)].2H(2)O] 6 reveal very weak antiferromagnetic coupling between the metal centres in each case.     

含氟二羧酸和含氮配体与过渡金属(Ⅱ)配合物的合成、表征及晶体结构

水热法合成了5个新的配位聚合物:[Cd(TFSA)(2,2’-bpy)2]n(1),[Mn(HFGA)(phen)2]n(2),[Co(TFSA)(bpp)2(H2O)2]n(3),[Zn(TFSA)(bpp)2(H2O)2]n(4)和[Cu(HFGA)(phen)]n(5)(TFSA=四氟丁二酸,HFGA=六氟戊二酸,2,2’-bpy=2,2’-联吡啶,phen=1,10-邻菲啰啉,bpp=1,3-二吡啶基丙烷),通过X射线单晶衍射确定了配合物的晶体结构.配合物1和2具有相似的1D链结构,四氟丁二酸和六氟戊二酸以两个单齿羧基氧原子分别配位于Cd2+和Mn2+离子,2,2’-联吡啶和1,10-邻菲啰啉分别螯合配位于Cd2+和Mn2+离子.配合物3和4具有相似的1D链结构,1,3-二吡啶基丙烷以两个端基氮原子桥联金属离子,四氟丁二酸和六氟戊二酸分别以单齿方式配位.配合物5是具有{4.82}拓扑的2D网结构,六氟丁二酸配体通过单齿/双齿-桥联模式连接Cu2+离子.5个配合物均通过分子间弱作用进一步构筑成3D超分子结构.     

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a Zinc（II） Complex with 2,2′-Diphenic Acid and 2,2′-Bipyridine Ligands

A new dinuclear complex [Zn(dpa)(bipy)(H2O)]2 (dpa = 2,2'-diphenic acid, bipy = 2,2'-bipyridine) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P21/c with a = 10.960(2), b = 9.4841(18), c = 20.599(4), β = 104.452(3)o, V = 2073.4(7)3, C48H36N4O10Zn2, Mr = 959.55, Dc = 1.537 g/cm3, μ(MoKα) = 1.225 mm-1, F(000) = 984, Z = 2, the final R = 0.0364 and wR = 0.0843 for 2788 observed reflections (I > 2σ(I)). In the crystal structure, the zinc atom is five-coordinated with two carboxylate oxygen atoms from different dpas, one coordinated water molecule and two nitrogen atoms from bipy ligands, showing a slightly distorted triangular bipyramidal geometry. Furthermore, it exhibits a zero-dimensional network structure with a sixteen-membered ring and shows yellow photoluminescent property at room temperature.     

Metal complexes as templates: syntheses, structures, and luminescent properties of two zinc phosphonocarboxylates with ABW-zeolite topology

Two novel zinc phosphonocarboxylates, Zn(3)(pbc)(2)(bpy)(H(2)O)·H(2)O (1) and Zn(2)(pbc)(2)·Zn(bpy)(H(2)O)(4)·2H(2)O (2) (pbc = 4-phosphono-benzoic acid, bpy = 2,2'-bipyridine), were hydrothermally synthesized and structurally characterized. Both of them exhibit zeolitic ABW topology in which double-zigzag inorganic chains are cross-linked by the organic parts. It is notable that the metal complex Zn(bpy)(H(2)O)(x) plays different roles in the two compounds. In 1, the Zn(bpy)(H(2)O) units coordinate with the phosphonate and carboxylate oxygen atoms and participate in the construction of the three-dimensional framework. In 2, the in situ generated [Zn(bpy)(H(2)O)(4)](2+) cation acts as a template, which directs the ABW-type open-framework by strong hydrogen bonds. It is the first example where a metal complex is used as a template in the synthesis of metal phosphonates. The luminescent properties of 1 and 2 are also investigated.     

Synthesis, structures, and magnetic properties of transition metal compounds with 2,2'-dinitrobiphenyl-4,4'-dicarboxylate and N,N'-chelating ligands

Solvothermal reactions of Co(II), Ni(II), Zn(II) salts with 2,2'-dinitrobiphenyl-4,4'-dicarboxylate (dnpdc) and 2,2'-bipyridyl-like chelating ligands yielded five compounds formulated as [Co(dnpdc)(bipy)](n)·nH(2)O (1), [M(dnpdc)(phen)](n) (2, M = Co; 3, M = Ni; 4, M = Zn) and [Co(dnpdc)(biql)](n)·2nH(2)O (5) (bipy = 2,2'-bipyridine, phen = 1,10-phenanthroline and biql = 2,2'-biquinoline). With bipy or phen as coligands, compounds 1-4 exhibit isomorphous 3D M(dnpdc) metal-organic frameworks in which double carboxylate bridged chains are interlinked by the backbones of the dicarboxylate ligands. The bipy or phen ligands are involved in interchain hydrogen bonding or π-π interactions to form 1D zipper-like arrays in the rhombic channels of the frameworks, playing a templating role and determining the channel dimensions. The biql coligand is too bulky for the 1D double carboxylate bridged chain and the rhombic channel. Instead, in compound 5, the dnpdc ligands link metal ions into 1D zigzag metal-organic chains and the biql ligands are arranged into 2D (6,3) arrays through extensive π-π stacking interactions. In compounds 1-3, the double carboxylate bridges in the nonplanar syn-skew conformation mediate ferromagnetic interactions along the chains, while the chelating ligands provide supramolecular pathways for interchain antiferromagnetic interactions. The π-π interactions in 5 also evoke weak antiferromagnetic interactions.     

Combined effects of diamines and carboxylate bridges on structural and magnetic properties of a series of polynuclear copper(II) complexes with 1,1-cyclobutanedicarboxylic acid

Six new copper(II) complexes of formula [Cu(mu-cbdca)(H2O)]n (1) (cbdca = cyclobutanedicarboxylate), [Cu2(mu-cbdca)2(mu-bipy)2]n (2) (bipy = 4,4'-bipyridine), [Cu(mu-cbdca)(mu-bpe)]n (3) (bpe = 1,2-bis(4-pyridyl)ethane), [Cu(mu-cbdca)(bpy)]2 (4) (bpy = 2,2'-bipyridine), [Cu(terpy)(ClO4)]2(mu-cbdca).H2O (5) (terpy = 2,2':6',2' '-terpyridine), and [Cu(cbdca)(phen) (H2O)].2H2O (6) (phen = 1,10-phenanthroline) were obtained and structurally characterized by X-ray crystallography. Complex 1 is a two-dimensional network with a carboxylate bridging ligand in syn-anti (equatorial-equatorial) coordination mode. Complexes 2 and 3 are formed by chains through syn-anti (equatorial-apical) carboxylate bridges, linked to one another by the corresponding amine giving two-dimensional nets. Complexes 4 and 5 are dinuclear, with the copper ions linked by two oxo (from two different carboxylate) bridging ligands in 4 and with only one carboxylate showing the unusual bis-unidentate mode in complex 5. Complex 6 is mononuclear, with the carboxylate linked to copper(II) in a chelated form. Intermolecular hydrogen bonds and pi-pi stacking interactions build an extended two-dimensional network. Magnetic susceptibility measurements of complexes 1-5 in the temperature range 2-300 K show the occurrence of weak ferromagnetic coupling for 1 and 4 (J = 4.76 and 4.44 cm(-1), respectively) and very weak antiferromagnetic coupling for 2, 3, and 5 (J = -0.94, -0.67, and -1.61 cm(-1), respectively). Structural features and magnetic values are compared with those reported for the similar copper(II) malonate and phenylmalonate complexes.     

Structural insights into the coordination and extraction of Pb(II) by disulfonamide ligands derived from o-phenylenediamine

The o-phenylenediamine-derived disulfonamide ligands 1 and 2 complex and efficiently extract Pb(II) from water into 1,2-dichloroethane via ion-exchange, in combination with 2,2'-bipyridine (97.5% and 95.0%, respectively, for 1:1 ligand-to-Pb ratios). The corresponding Pb(II)-sulfonamido binary complexes of ligands 1 and 2 (3 and 4, respectively), and ternary complexes with 2,2'-bipyridine (5 and 6, respectively), were isolated and characterized. (1)H NMR spectra of the organic phases after extraction show the formation of ternary Pb-sulfonamido-bipy complexes. X-ray characterization of 3, 4, and the ternary complex 5 consistently demonstrates four primary coordination sites and a stereochemically active lone pair on Pb. The X-ray structure of 3 shows a pseudo trigonal bipyramidal configuration on Pb, with the lone pair occupying one of the equatorial sites, and the formation of an unusual "hemidirected" coordination polymer via axial S=O-Pb coordination. The same axial S=O-Pb coordination pattern with two DMSO molecules is observed in the structure of 4.[2(CH(3))(2)SO)], thus rationalizing the high solubility of the binary complexes in strongly coordinating solvents. In contrast, the X-ray structure of the ternary complex 5 reveals a distorted four-coordinate configuration with only weak S=O-Pb coordination leading to dimer formation, thus explaining its higher solubility in weakly coordinating solvents. FT-IR spectroscopy confirms the X-ray data, since the ligand nu(S)(=)(O) stretching frequencies shift to lower values in the binary Pb(II)-sulfonamido complexes and are again altered upon formation of the ternary Pb(II)-sulfonamido-bipy complexes, as would be expected for 2,2'-bipy complexation and hindered S=O-Pb coordination.     

Synthesis, Crystal Structure and Water-induced Reversible Crystal-to-amorphous Transformation Property of [{Ni(IBG)(4,4'-bipy)(a2O)2}·3a2O]n

A novel NiⅡ complex[{Ni(IBG)(4,4'-bipy)(H2O)2}·3H2O]n1(H2IBG=isophthaloylbisglycine and 4,4'-bipy=4,4'-bipyridine)has been synthesized and characterized by singlecrystal X-ray diffraction,elemental analysis,IR spectra and thermogravimetric analysis.It crystallizes in monoclinic,space group P2/c with a=15.5420(7),b=22.4344(1),c=8.3455(5)(A),β=101.538(3)°,V=2670.1(7)(A)3,Z=4,C22H32N4NiO13,Mr=619.23,Dc=1.443 g/cm3,F(000)=1296.0,μ(MoKa)=0.750 mm-1,the final R=0.0570 and wR=0.1445 for 2296 observed reflections with I>2σ(I).In the structure,the NiⅡ metal center is coordinated in an octahedral environment arranged by two water molecules,two carboxylate oxygen atoms and two nitrogen atoms from two4,4'-bipy ligands.Thermal decomposition and powder X-ray diffraction results indicate that the transformation from the crystal form,[{Ni(IBG)(4,4'-bipy)(H2O)2}·3H2O]n,to the amorphous powder,Ni(IBG)(4,4'-bipy)(H2O)2,is reversible,so the latter form may be utilized as an absorbing agent for water and water vapor.     

刚性配体2,2-联吡啶诱导的双咪唑金属超分子配合物的合成与晶体结构

合成了3种新的超分子配合物[Cd(H2biim)(2,2'-bipy)(NO3)2] (1), [Cu(H2biim)(2,2'-bipy)(H2O)](NO3)2 (2)和[Zn(H2biim)(2,2'-bipy)(H2O)](NO3)2 (3) (H2biim＝双咪唑; 2,2'-bipy＝2,2'-联吡啶), 并通过X射线单晶衍射测定了其结构. 配合物1～3均为单斜晶系, 属于P2(1)/c空间群, 在1中, Cd(II)为六配位, 它与双咪唑的2个氮原子, 联吡啶的2个氮原子和2个硝酸根的2个氧原子配位. 在2和3中, Cu(II)和Zn(II)均为五配位的, 它们与双咪唑的2个氮原子、2,2'-联吡啶的两个氮原子和一个水分子配位. 1～3的对称单元均通过双咪唑、硝酸根和水之间形成的氢键R21(7), R21(4) 和R44(18)构筑了1D链状超分子.     

基于2,2＇,6,6＇-联苯四酸的两个新配位聚合物的水热合成与晶体结构

通过2,2＇,6,6’-联苯四酸与相应金属硝酸盐和第二配体的水热反应合成了2个具有不同结构的配位聚合物[Co(bta)0.5(2,2’-bipy)(H2O)]n(1)和{[Cd2,(bta)(H2biim)2(H2O)]·H2O}n(2)(H4bta=2,2’,6,6’-联苯四酸,2,2'-bipy=2,2’-联吡啶,H2biim=1H,1’H-2,2’-联咪唑),并测定了其晶体结构.1和2都是一维链结构,并且1和2都属于单斜晶系,P21/c空间群.bta配体在1和2中分别采取η6,μ4六齿和η5,μ4-五齿配位模式,同时bta配体中2个苯环的夹角在化合物1和2中分别是64.80°和64.86°.1与2分别在170℃和120℃以下保持热稳定性.