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1.
The title complex, [Zn(C15H22BN6)(C2H3O2)] or (TpMe,Me)Zn(OAc), contains a tripodal tris(pyrazolyl)hydroborate ligand, a monodentate acetate ligand and a ZnII centre in a distorted tetrahedral coordination environment capped on one triangular face by a secondary Zn...O interaction with the second O atom of the acetate ligand. The four‐coordination of ZnII and the essentially monodentate character of the acetate ligand are due to the high steric demands of the ligand set, which prevent chelate formation and five‐coordination and lead to relatively long Zn—O and Zn—N bonds compared with related complexes of ZnII and other metals.  相似文献   

2.
A novel three‐dimensional ZnII complex, poly[aqua(μ4‐5‐carboxylato‐1‐carboxylatomethyl‐2‐oxidopyridinium)zinc(II)], [Zn(C8H5NO4)(H2O)]n, has been prepared by hydrothermal assembly of Zn(CH3COO)2·2H2O and 5‐carboxy‐1‐(carboxymethyl)pyridin‐1‐ium‐2‐olate (H2ccop). The ccop2− anions bridge the ZnII cations in a head‐to‐tail fashion via monodentate aromatic carboxylate and phenolate O atoms to form an extended zigzag chain which runs parallel to the [011] direction. One O atom of the aliphatic carboxylate group of the ccop2− ligand coordinates to the ZnII atom of a neighbouring chain thereby producing undulating layers which lie parallel to the (01) plane. A similar parallel undulating planar structure can be obtained if a path involving the other O atom of the aliphatic carboxylate group is considered. Thus, the aliphatic carboxylate group acts in a bridging bidentate mode to give extended –Zn–O–C–O–Zn– sequences running parallel to [001] which link the layers into an overall three‐dimensional framework. The three‐dimensional framework can be simplified as a 4‐connected sra topology with a Schläfli symbol of 42.63.8 if all the ZnII centres and ccop2− anions are regarded as tetrahedral 4‐connected nodes. The three‐dimensional luminescence spectrum was measured at room temperature with excitation and emission wavelengths of 344–354 and 360–630 nm, respectively, at intervals of 0.15 and 2 nm, respectively.  相似文献   

3.
The asymmetric unit of {[4,7‐bis(2‐amino­ethyl)‐1,4,7‐tri­aza­cyclo­nonan‐1‐yl]acetato}zinc(II) triaqua{μ‐[4,7‐bis(2‐amino­ethyl)‐1,4,7‐tri­aza­cyclo­nonan‐1‐yl]acetato}lithium(I)zinc(II) chloride diperchlorate, [Zn(C12H26N5O2)][LiZn(C12H26N5O2)(H2O)3]Cl(ClO4)2, obtained from the reaction between the lithium salt of 4,7‐bis(2‐amino­ethyl)‐1,4,7‐tri­aza­cyclo­nonane‐1‐acetate and Zn(ClO4)2, contains two ZnII complexes in which each ZnII ion is six‐coordinated by five N‐atom donors and one O‐­atom donor from the ligand. One carboxyl­ate O‐atom donor is not involved in coordination to a ZnII atom, but coordinates to an Li+ ion, the tetrahedral geometry of Li+ being completed by three water mol­ecules. The two complexes are linked via a hydrogen bond between a primary amine N—H group and the carboxyl­ate‐O atom not involved in coordination to a metal.  相似文献   

4.
In the mixed‐ligand metal–organic title polymeric compound, [Zn(C10H8O4)(C10H16N6)]n or [Zn(PBEA)(BTH)]n [H2PBEA is benzene‐1,4‐diacetic acid and BTH is 1,6‐bis(1,2,4‐triazol‐1‐yl)hexane], the asymmetric unit contains a ZnII atom, one half of a BTH ligand and one half of a doubly deprotonated H2PBEA ligand. Each ZnII centre lies on a crystallographic twofold rotation axis and is four‐coordinated by two O atoms from two distinct PBEA2− ligands and two N atoms from two different BTH ligands in a {ZnO2N2} coordination environment. The three‐dimensional topology of the title compound corresponds to that of a fivefold interpenetrating diamond‐like metal–organic framework.  相似文献   

5.
The asymmetric unit of the title compound, [Zn(C7H5O3)2(C10H8N2)], contains one monomeric zinc complex. The Zn atom is coordinated to one 2,2′‐bipyridyl ligand via both N atoms and to two salicyl­ate anions (Hsal) in a bidentate chelating manner involving carboxyl­ate O‐atom coordination. The complex exhibits a distorted octahedral geometry about the ZnII atom, with the `apical' positions occupied by one of the two N atoms of the bipyridyl ligand and an O atom from one Hsal ligand; the Zn atom is 0.168 (1) Å out of the `basal' plane. Two intramolecular six‐membered hydrogen‐bonded rings are present, generated from interactions between the carboxyl and hydroxyl groups of the salicyl­ate ligands. The crystal packing is governed by weak C—H⋯O and C—H⋯π interactions.  相似文献   

6.
The ZnII compounds, μ‐4,4′‐ethylenedibenzoato‐bis[acetatoaqua(dipyrido[3,2‐a:2′,3′‐c]phenazine)zinc(II)] dihydrate, [Zn2(C2H3O2)2(C16H10O4)(C18H10N4)2(H2O)2]·2H2O, (I), and catena‐poly[[[aqua(pyrazino[2,3‐f][1,10]phenanthroline)zinc(II)]‐μ‐4,4′‐ethylenedibenzoato] N,N‐dimethylformamide hemisolvate], {[Zn(C16H10O4)(C14H8N4)(H2O)]·0.5C3H7NO}n, (II), display very different structures because of the influence of the N‐donor chelating ligands. In (I), the coordination geometry of each ZnII centre is distorted octahedral, involving two N atoms from one dipyrido[3,2‐a:2′,3′‐c]phenazine (L1) ligand, and four O atoms from one bis‐chelating acetate anion, one bridging 4,4′‐ethylenedibenzoate (bpea) ligand and one water molecule. Adjacent ZnII atoms are bridged by one bpea ligand to form a dinuclear complex, and the dinuclear species is centrosymmetric. Two types of π–π interactions between neighbouring dinuclear species have been found: one is between the L1 ligands, and the second is between the L1 and bpea ligands. In this way, an interesting two‐dimensional supramolecular layer is formed. The layers are further linked by O—H...O and O—H...N hydrogen bonds, generating a three‐dimensional supramolecular network. In (II), each ZnII atom is square‐pyramidally coordinated by two N atoms from one pyrazino[2,3‐f][1,10]phenanthroline ligand, three O atoms from two different bpea ligands and one water molecule. The two bpea dianions are situated across inversion centres. The bpea dianions bridge neighbouring ZnII centres, giving a one‐dimensional chain structure in the ab plane. As in (I), two types of π–π interactions between neighbouring chains complete a three‐dimensional supramolecular structure. The results indicate that the structures of the N‐donor chelating ligands are the dominant factors determining the final supramolecular structures of the two compounds.  相似文献   

7.
The novel title ZnII coordination polymer, poly[bis(μ‐6‐thioxo‐1,6‐dihydropyridine‐3‐carboxylato‐κ2S:O)zinc(II)], [Zn(C6H4NO2S)2]n, consists of two crystallographically independent zinc centers and two 6‐mercaptonicotinate (Hmna) ligands. Each ZnII atom is four‐coordinated and lies at the center of a distorted tetrahedral ZnS2O2 coordination polyhedron, bridged by four Hmna ligands to form a two‐dimensional (4,4)‐network. Each Hmna ion acts as a bridging bidentate ligand, coordinating to two ZnII atoms through the S atom and a carboxyl O atom. The metal centers reside on twofold rotation axes. The coordination mode of the S atoms and N—H...O hydrogen‐bonding interactions between the protonated N atoms and the uncoordinated carboxyl O atoms give the extended structure a wavelike form.  相似文献   

8.
The crystal structure of the title compound, [CoCl(C18H37N4O2){ZnCl3}], has been determined by X‐ray diffraction.Cmeso‐5,5,7,12,12,14‐Hexa­methyl‐1,4,8,11‐tetra­aza­cyclotetradecane‐N‐acetate acts as a bridging ligand to coodinate with CoIII and ZnII ions. The CoIII ion is six‐coordinate in a nearly octahedral environment provided by one Cl atom, four N atoms of the bridging ligand, and one O atom. The ZnII ion is four‐coordinate in a distorted tetrahedral environment completed by three Cl atoms and an O atom of the bridging ligand.  相似文献   

9.
Nine new coordination compounds have been synthesized by the reaction of salts of bivalent metal ions (a=ZnII, b=CuII, c=NiII, d=CoII) with the bis(benzoylhydrazone) derivative of 4,6‐diacetylresorcinol (H4L). Three kinds of complexes have been obtained: homodinuclear compounds [M2(H2L)2]?nH2O ( 1 a , 1 b , 1 c , and 1 d ), homotetranuclear compounds [M4(L)2]?n(solv) ( 2 a and 2 c ), and heterotetranuclear compounds [Zn2M2(L)2]?n(solv) ( 2 ab , 2 ac , and 2 ad ). The structures of the free ligand H4L?2 DMSO and its complexes [Zn2(H2L)2(DMSO)2] ( 1 a* ), [Zn4(L)2(DMSO)6] ( 2 a* ), and [Zn0.45Cu3.55(L)2(DMSO)6]?2 DMSO ( 2 ab* ) were elucidated by single‐crystal X‐ray diffraction. The ligand shows luminescence properties and its fluorimetric behavior towards MII metals (M=Zn, Cu, Ni and Co) has been studied. Furthermore, the solid‐state luminescence properties of the ligand and compounds have been determined at room temperature. 1H NMR spectroscopic monitoring of the reaction of H4L with ZnII showed the deprotonation sequence of the OH/NH groups upon metal coordination. Heteronuclear reactions have also been monitored by using ESI‐MS and spectrofluorimetric techniques.  相似文献   

10.
Two trinuclear CoII and ZnII complexes, [(CoL)2(OAc)2Co] and [(ZnL)2(OAc)2Zn], with an asymmetric Salen‐type bisoxime ligand [H2L = 4‐(N,N‐diethylamine)‐2,2′‐[ethylenediyldioxybis(nitrilomethylidyne)]diphenol] were synthesized and characterized by elemental analyses, IR, UV/Vis, and fluorescent spectroscopy. The crystal structures of the CoII and ZnII complexes were determined by single‐crystal X‐ray diffraction methods. The CoII atom is pentacoodinated by N2O2 donor atoms from the (L)2– unit and one oxygen atom from the coordinated acetate ion, resulting in a trigonal bipyramid arrangement. With the help of intermolecular hydrogen bonding C–H ··· O and C–H ··· π interactions, a self‐assembled continual zigzag chain‐like supramolecular structure is formed. The ZnII atom is pentacoodinated by N2O2 donor atoms from the (L)2– unit and one oxygen atom from the coordinated acetate ion, resulting in an almost regular trigonal bipyramid arrangement. A self‐assembled continual 1D supramolecular chain‐like structure is formed by intermolecular hydrogen bonding C–H ··· O and C–H ··· π interactions. Additionally, the photophysical properties of the CoII and ZnII complexes were discussed.  相似文献   

11.
The solvothermal reaction of Zn(OAc)2·2H2O with 3,3′‐(diazenediyl)dibenzoic acid (H2ADB) in H2O at 393 K afforded the title complex, [Zn(C14H8N2O4)(H2O)]n. The asymmetric unit contains half a ZnII cation, half an ADB ligand and half a water molecule. Each ZnII centre lies on a crystallographic twofold rotation axis and is five‐coordinated by four O atoms of bridging carboxylate groups from four ADB ligands and one O atom from a water molecule, forming a distorted trigonal–bipyramidal coordination geometry. The [Zn(H2O)] subunits are bridged by carboxylate groups to give one‐dimensional [Zn(μ‐COO)4(H2O)]n chains. The chains are linked by ADB ligands into two‐dimensional sheets, and these sheets are further connected to neighbouring sheets via hydrogen bonds (OW—HW...O), forming a three‐dimensional hydrogen‐bond‐stabilized structure with an unprecedented 374175262 topology.  相似文献   

12.
The 2‐methylbiphenyl‐4,4′‐dicarboxylate (mbpdc2−) ligand has versatile coordination modes and can be used to construct multinuclear structures. Despite this, reports of the synthesis of coordination complexes involving this ligand are scarce. The title compound, poly[[triaquadi‐μ3‐hydroxido‐hexakis(μ4‐2‐methylbiphenyl‐4,4′‐dicarboxylato)calcium(II)hexazinc(II)] monohydrate], {[CaZn6(C15H10O4)6(OH)2(H2O)3]·H2O}n , has been prepared by the hydrothermal assembly of Zn(NO3)2·6H2O, CaCl2 and 2‐methylbiphenyl‐4,4′‐dicarboxylic acid. Two ZnII atoms adopt a four‐coordinated distorted tetrahedral geometry by bonding to three O atoms from three different 2‐methylbiphenyl‐4,4′‐dicarboxylate (mbpdc2−) dianionic ligands and one bridging hydroxide O atom. For the remaining ZnII atom, a five‐coordinate environment is completed half the time by one carboxylate O atom, and then the same carboxylate O atom and an aqua O atom are present the other half of the time, giving a six‐coordinate environment. The CaII atom is coordinated by six O atoms to give an octahedral coordination geometry. The supramolecular secondary building unit (SBU) is a hamburger‐like heptanuclear unit (Zn6CaO30) and these units are interconnected through mbpdc2− carboxylate groups to generate a three‐dimensional framework with the pcu topology. The single net leaves voids that are filled by mutual interpenetration of an independent equivalent framework in a twofold interpenetrating architecture. The title compound shows thermal stability up to 673 K. The excitation and luminescence data showed the emission of a bright‐blue fluorescence.  相似文献   

13.
In the title compound, {[Zn(C8H4O5)(C12H10N2)]·0.5C12H10N2}n or {[Zn(HO‐BDC)(bpe)]·0.5bpe}n [HO‐H2BDC is 5‐hydroxyisophthalic acid and bpe is 1,2‐bis(pyridin‐4‐yl)ethene], the asymmetric unit contains a ZnII atom, one HO‐BDC ligand, one coordinated bpe ligand and half a noncoordinating bpe molecule with crystallographic inversion symmetry. Each ZnII centre is four‐coordinated by two O atoms from two distinct HO‐BDC ligands and two N atoms from two different bpe ligands in a ZnO2N2 coordination environment. The three‐dimensional topology of the title compound corresponds to a fourfold interpenetrating diamondoid coordination polymer network, with the uncoordinated bpe ligands located in the cavities, hydrogen bonded to the main network via the hydroxy group of the HO‐H2BDC ligand.  相似文献   

14.
In the C2‐symmetric dinuclear title complex, [Zn2(C18H13N4O2)2(C2H3O2)2]·4H2O, each ZnII ion is five‐coordinated in a distorted trigonal bipyramidal fashion by one carboxylate O atom from one benzoate ligand, one imine N atom and two pyridyl N atoms from a second benzoate ligand, and one O atom from an acetate anion. The two Zn atoms are bridged by the two benzoate ligands, forming a dinuclear structure with a 14‐membered macrocycle. Adjacent dinuclear units are further connected by extensive hydrogen bonds involving the solvent water molecules, giving a three‐dimensional hydrogen‐bonded framework. The framework can be regarded as an example of the four‐connected node network of the PtS topology.  相似文献   

15.
The complexes [2‐(1H‐imidazol‐4‐yl‐κN3)ethylamine‐κN]bis(tri‐tert‐butoxysilanethiolato‐κS)cobalt(II), [Co(C12H27O3SSi)2(C5H9N3)], and [2‐(1H‐imidazol‐4‐yl‐κN3)ethylamine‐κN]bis(tri‐tert‐butoxysilanethiolato‐κS)zinc(II), [Zn(C12H27O3SSi)2(C5H9N3)], are isomorphous. The central ZnII/CoII ions are surrounded by two S atoms from the tri‐tert‐butoxysilanethiolate ligand and by two N atoms from the chelating histamine ligand in a distorted tetrahedral geometry, with two intramolecular N—H...O hydrogen‐bonding interactions between the histamine NH2 groups and tert‐butoxy O atoms. Molecules of the complexes are joined into dimers via two intermolecular bifurcated N—H...(S,O) hydrogen bonds. The ZnII atom in [(1H‐imidazol‐4‐yl‐κN3)methanol]bis(tri‐tert‐butoxysilanethiolato‐κ2O,S)zinc(II), [Zn(C12H27O3SSi)2(C4H6N2O)], is five‐coordinated by two O and two S atoms from the O,S‐chelating silanethiolate ligand and by one N atom from (1H‐imidazol‐4‐yl)methanol; the hydroxy group forms an intramolecular hydrogen bond with sulfur. Molecules of this complex pack as zigzag chains linked by N—H...O hydrogen bonds. These structures provide reference details for cysteine‐ and histidine‐ligated metal centers in proteins.  相似文献   

16.
The title novel two‐dimensional coordination polymer, {[Zn2(C10H8N3O2)4]·H2O}n, features a {Zn2L2} bimetallic ring repeat unit {L is the 3‐[(1H‐1,2,4‐triazol‐1‐yl)methyl]benzoate ligand}. Each ZnII cation of the bimetallic ring is further bonded to two other L ligands, resulting in a novel infinite two‐dimensional network structure with two channels of different sizes. The crystallographically unique ZnII atom is thus six‐coordinated in a distorted octahedral environment of four carboxylate O atoms and two triazole N atoms. Two of these networks interpenetrate in an orthogonal arrangement to form the full three‐dimensional framework, with disordered water molecules located in the channels.  相似文献   

17.
The protonation and ZnII/CuII complexation constants of tripodal polyamine ligand N1‐(2‐aminoethyl)‐N1‐(1H‐imidazol‐4‐ylmethyl)‐ethane‐1,2‐diamine (HL) were determined by potentiometric titration. Three new compounds, i.e. [H3(HL)](ClO4)3 ( 5 ), [Zn(HL)Cl](ClO4) ( 6 ) and {[Zn(L)](ClO4)}n ( 7 ) were obtained by reactions of HL · 4HCl with Zn(ClO4)2 · 6H2O under different reaction pH, and they were compared with the corresponding CuII complexes reported previously. The results indicate that the reaction pH and metal ions have remarkable influence on the formation and structure of the complexes.  相似文献   

18.
The asymmetric unit of the title compound, [Zn(C10H6NO2)2(C12H8N2)]·1.5C3H7NO, contains one monomeric zinc com­plex and 1.5 disordered di­methyl­form­amide solvate mol­ecules. The Zn atom is coordinated to one 1,10‐phenanthroline ligand and to two iso­quinoline­carboxyl­ate anions (IQC?) via their N and O atoms. The complex exhibits a distorted octahedral geometry around the ZnII atom, with the apical positions occupied by the O atoms of the IQC? ligands. The Zn atom lies 0.049 (1) Å out of the basal plane. The crystal packing is characterized by several hydrogen bonds.  相似文献   

19.
In the title coordination polymer, catena‐poly[[bis[{1‐[(1H‐benzimidazol‐2‐yl‐κN3)methyl]‐1H‐tetrazole}zinc(II)]‐bis(μ4‐pentane‐1,5‐dioato‐1:2:1′:2′κ4O1:O1′:O5:O5′)] methanol disolvate], {[Zn(C5H6O4)(C9H8N6)]·CH3OH}n, each ZnII ion is five‐coordinated by four O atoms from four glutarate ligands and by one N atom from a 1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐tetrazole (bimt) ligand, leading to a slightly distorted square‐pyramidal coordination environment. Two ZnII ions are linked by four bridging glutarate carboxylate groups to generate a dinuclear [Zn2(CO2)4] paddle‐wheel unit. The dinuclear units are further connected into a one‐dimensional chain via the glutarate ligands. The bimt ligands coordinate to the ZnII ions in a monodentate mode and are pendant on both sides of the main chain. In the crystal, the chains are linked by O—H...O and N—H...O hydrogen bonds into a two‐dimensional layered structure. Adjacent layers are further packed into a three‐dimensional network through van der Waals forces. A thermogravimetric analysis was carried out and the photoluminescent behaviour of the polymer was investigated.  相似文献   

20.
In catena‐poly[[aqua[1,3‐bis(pyridine‐3‐ylmethoxy)benzene‐κN]zinc(II)]‐μ2‐benzene‐1,4‐dicarboxylato‐κ2O1:O4], [Zn(C8H4O4)(C18H16N2O2)(H2O)]n, each ZnII centre is tetrahedrally coordinated by two O atoms of bridging carboxylate groups from two benzene‐1,4‐dicarboxylate anions (denoted L2−), one O atom from a water molecule and one N atom from a 1,3‐bis[(pyridin‐3‐yl)methoxy]benzene ligand (denoted bpmb). (Aqua)O—H...N hydrogen‐bonding interactions induce the formation of one‐dimensional helical [Zn(L)(bpmb)(H2O)]n chains which are interlinked through (aqua)O—H...O hydrogen‐bonding interactions, producing two‐dimensional corrugated sheets.  相似文献   

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