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1.
In the centrosymmetric dinuclear anions of the title bimetallic complex, {[Mg(H2O)6][Cu2(C8H2NO7)2]·2H2O}n, each CuII ion is strongly coordinated by four O atoms in a distorted square‐planar geometry. Two of these O atoms belong to phenolate groups and the other two to carboxylate groups from 5‐nitro‐2‐oxidoisophthalate (L1) trianions, derived from 5‐nitrobenzene‐1,2,3‐tricarboxylic acid (O2N–H3L). The phenolate O atoms bridge the two CuII ions in the anion. In addition, each CuII cation interacts weakly with a symmetry‐related carboxylate O atom of an adjacent L1 ligand, giving a square‐pyramidal coordination geometry. The copper residue forms a ladder‐like linear coordination polymer via L1 ligands. The [Mg(H2O)6]2+ cations sit on centres of inversion. The polymeric anions, cations and free water molecules are self‐assembled into a three‐dimensional supramolecular network via O—H...O hydrogen bonds.  相似文献   

2.
In the title compound, [Cu(C7H3N2O4)(C4H5N2)(H2O)], (I), pyridine‐2,6‐dicarboxylate (pydc2−), 2‐aminopyrimidine and aqua ligands coordinate the CuII centre through two N atoms, two carboxylate O atoms and one water O atom, respectively, to give a nominally distorted square‐pyramidal coordination geometry, a common arrangement for copper complexes containing the pydc2− ligand. Because of the presence of Cu...Xbridged contacts (X = N or O) between adjacent molecules in the crystal structures of (I) and three analogous previously reported compounds, and the corresponding uncertainty about the effective coordination number of the CuII centre, density functional theory (DFT) calculations were used to elucidate the degree of covalency in these contacts. The calculated Wiberg and Mayer bond‐order indices reveal that the Cu...O contact can be considered as a coordination bond, whereas the amine group forming a Cu...N contact is not an effective participant in the coordination environment.  相似文献   

3.
In the title coordination polymer, [Cd2(SO4)2(C13H8N4)(H2O)2]n, there are two crystallographically independent CdII centres with different coordination geometries. The first CdII centre is hexacoordinated by four O atoms of four sulfate ligands, one water O atom and one N atom of a 1H‐imidazo[4,5‐f][1,10]phenanthroline (IP) ligand, giving a distorted octahedral coordination environment. The second CdII centre is heptacoordinated by four O atoms of three sulfate ligands, one water O atom and two N atoms of one chelating IP ligand, resulting in a distorted monocapped anti‐trigonal prismatic geometry. The symmetry‐independent CdII ions are bridged in an alternating fashion by sulfate ligands, forming one‐dimensional ladder‐like chains which are connected through the IP ligands to form two‐dimensional layers. These two‐dimensional layers are linked by interlayer hydrogen bonds, leading to the formation of a three‐dimensional supramolecular network.  相似文献   

4.
The new asymmetric ligand 2‐{5‐[(pyridin‐4‐ylmethyl)sulfanyl]‐1,3,4‐oxadiazol‐3‐yl}phenol (HL) has been used to synthesize the novel discrete title binuclear metallocycle, [Cu2(C14H10N3O2S)2(C5H7O2)2] or Cu2L2(acac)2 (acac is acetylacetonate). Each CuII centre is five‐coordinate and adopts a square‐pyramidal geometry. Two ligands are connected by two CuII cations to form the dinuclear metallocycle, which lies across a crystallographic inversion centre. Discrete molecules are linked into a two‐dimensional structure through weak Cu...S, C—H...π and π–π interactions.  相似文献   

5.
The design and synthesis of polymeric coordination compounds of 3d transition metals are of great interest in the search for functional materials. The coordination chemistry of the copper(II) ion is of interest currently due to potential applications in the areas of molecular biology and magnetochemistry. A novel coordination polymer of CuII with bridging N,N′‐bis(2‐hydroxyphenyl)‐2,2‐dimethylpropane‐1,3‐diamine (H2L‐DM) and dicyanamide (dca) ligands, catena‐poly[[[μ2‐2,2‐dimethyl‐N,N′‐bis(2‐oxidobenzylidene)propane‐1,3‐diamine‐1:2κ6O,N,N′,O′:O,O′]dicopper(II)]‐di‐μ‐dicyanamido‐1:2′κ2N1:N5;2:1′κ2N1:N5], [Cu2(C19H20N2O2)(C2N3)2]n, has been synthesized and characterized by CHN elemental analysis, IR spectroscopy, thermal analysis and X‐ray single‐crystal diffraction analysis. Structural studies show that the CuII centres in the dimeric asymmetric unit adopt distorted square‐pyramidal geometries, as confirmed by the Addison parameter (τ) values. The chelating characteristics of the L‐DM2− ligand results in the formation of a CuII dimer with a double phenolate bridge in the asymmetric unit. In the crystal, the dimeric units are further linked to adjacent dimeric units through μ1,5‐dca bridges to produce one‐dimensional polymeric chains.  相似文献   

6.
The title compound, [CuBr(C6H7NO)2]Br·H2O, is an ionic mononuclear complex in which the [CuBr(C6H7NO)2]+ cation possesses distorted square‐pyramidal geometry. The CuII centre is coordinated by two neutral 2‐(pyridin‐2‐yl)methanol (2‐pyMeOH) ligands and a terminal bromide ligand. The 2‐pyMeOH ligands are coordinated in a bidentate chelating manner through the pyridine N and hydroxy O atoms, forming a five‐membered chelate ring with the CuII centre. The planes of the pyridine rings are twisted by 58.71 (14)° with respect to each other. The charge is balanced by a noncoordinating bromide anion which, together with a solvent water molecule, links the components through hydrogen bonds into infinite chains propagating along the a axis. The mononuclear cations appear to associate in pairs through weak interactions between the metal atom of one cation and the halogen atom of an adjacent cation.  相似文献   

7.
Coordination polymers are a thriving class of functional solid‐state materials and there have been noticeable efforts and progress toward designing periodic functional structures with desired geometrical attributes and chemical properties for targeted applications. Self‐assembly of metal ions and organic ligands is one of the most efficient and widely utilized methods for the construction of CPs under hydro(solvo)thermal conditions. 2‐(Pyridin‐3‐yl)‐1H‐imidazole‐4,5‐dicarboxylate (HPIDC2−) has been proven to be an excellent multidentate ligand due to its multiple deprotonation and coordination modes. Crystals of poly[aquabis[μ3‐5‐carboxy‐2‐(pyridin‐3‐yl)‐1H‐imidazole‐4‐carboxylato‐κ5N1,O5:N3,O4:N2]copper(II)dicopper(I)], [CuIICuI2(C10H5N3O4)2(H2O)]n, (I), were obtained from 2‐(pyridin‐3‐yl)‐1H‐imidazole‐4,5‐dicarboxylic acid (H3PIDC) and copper(II) chloride under hydrothermal conditions. The asymmetric unit consists of one independent CuII ion, two CuI ions, two HPIDC2− ligands and one coordinated water molecule. The CuII centre displays a square‐pyramidal geometry (CuN2O3), with two N,O‐chelating HPIDC2− ligands occupying the basal plane in a trans geometry and one O atom from a coordinated water molecule in the axial position. The CuI atoms adopt three‐coordinated Y‐shaped coordinations. In each [CuN2O] unit, deprotonated HPIDC2− acts as an N,O‐chelating ligand, and a symmetry‐equivalent HPIDC2− ligand acts as an N‐atom donor via the pyridine group. The HPIDC2− ligands in the polymer serve as T‐shaped 3‐connectors and adopt a μ3‐κ2N,O2N′,O′:κN′′‐coordination mode, linking one CuII and two CuI cations. The Cu cations are arranged in one‐dimensional –Cu1–Cu2–Cu3– chains along the [001] direction. Further crosslinking of these chains by HPIDC2− ligands along the b axis in a –Cu2–HPIDC2−–Cu3–HPIDC2−–Cu1– sequence results in a two‐dimensional polymer in the (100) plane. The resulting (2,3)‐connected net has a (123)2(12)3 topology. Powder X‐ray diffraction confirmed the phase purity for (I), and susceptibilty measurements indicated a very weak ferromagnetic behaviour. A thermogravimetric analysis shows the loss of the apical aqua ligand before decomposition of the title compound.  相似文献   

8.
In the title compound, [Cu(C10H4O8)(C12H8N2)]n, the CuII cation has a four‐coordination environment completed by two N atoms from one 1,10‐phenanthroline (phen) ligand and two O atoms belonging to two di­hydrogen benzene‐1,2,4,5‐­tetra­carboxyl­ate anions (H2TCB2−). There is a twofold axis passing through the CuII cation and the centre of the phen ligand. The [Cu(phen)]2+ moieties are bridged by H2TCB2− anions to form an infinite one‐dimensional coordination polymer with a zigzag chain structure along the c axis. A double‐chain structure is formed by hydrogen bonds between adjacent zigzag chains. Furthermore, there are π–π stacking inter­actions between the phen ligands, with an average distance of 3.64 Å, resulting in a two‐dimensional network structure.  相似文献   

9.
The title compound, [(Z)‐4‐allyl‐2‐(2‐hydroxybenzylidene)thiosemicarbazide‐κS][(E)‐4‐allyl‐1‐(2‐oxidobenzylidene)thiosemicarbazidato‐κ3O,N1,S]copper(II) monohydrate, [Cu(C11H11N3OS)(C11H13N3OS)]·H2O, crystallized as a rotational twin in the monoclinic crystal system (space group Cc) with two formula unit (Z′ = 2) in the asymmetric unit, one of which contains an allyl substituent disordered over two positions. The CuII atom exhibits a distorted square‐planar geometry involving two differently coordinated thiosemicarbazone ligands. One ligand is bonded to the CuII atom in a tridentate manner via the phenolate O, azomethine N and thioamide S atoms, while the other coordinates in a monodentate manner via the S atom only. The complex is stabilized by an intramolecular hydrogen bond, which creates a six‐membered pseudo‐chelate metalla‐ring. The structure analysis indicates the presence of the E isomer for the tridentate ligand and the Z isomer for the monodentate ligand. The crystal structure contains a three‐dimensional network built from intermolecular O—H...O, N—H...O, O—H...N and N—H...S hydrogen bonds.  相似文献   

10.
In the title compound, [Cu(C6F5COO)2(C4H4N2)]n, (I), the asymmetric unit contains one CuII cation, two anionic pentafluorobenzoate ligands and one pyrazine ligand. Each CuII centre is five‐coordinated by three O atoms from three independent pentafluorobenzoate anions, as well as by two N atoms from two pyrazine ligands, giving rise to an approximately square‐pyramidal coordination geometry. Adjacent CuII cations are bridged by a pyrazine ligand and two pentafluorobenzoate anions to give a two‐dimensional layer. The layers are stacked to generate a three‐dimensional supramolecular architecture via strong intermolecular C—H...F—C interactions, as indicated by the F...H distance of 2.38 Å.  相似文献   

11.
The title compound, [Cu(C9H5N2O3)2(C2H6OS)2], consists of octahedrally coordinated CuII ions, with the 3‐oxo‐3,4‐dihydroquinoxaline‐2‐carboxylate ligands acting in a bidentate manner [Cu—O = 1.9116 (14) Å and Cu—N = 2.1191 (16) Å] and a dimethyl sulfoxide (DMSO) molecule coordinated axially via the O atom [Cu—O = 2.336 (5) and 2.418 (7) Å for the major and minor disorder components, respectively]. The whole DMSO molecule exhibits positional disorder [0.62 (1):0.38 (1)]. The octahedron around the CuII atom, which lies on an inversion centre, is elongated in the axial direction, exhibiting a Jahn–Teller effect. The ligand exhibits tautomerization by H‐atom transfer from the hydroxyl group at position 3 to the N atom at position 4 of the quinoxaline ring of the ligand. The complex molecules are linked through an intermolecular N—H...O hydrogen bond [N...O = 2.838 (2) Å] formed between the quinoxaline NH group and a carboxylate O atom, and by a weak intermolecular C—H...O hydrogen bond [3.392 (11) Å] formed between a carboxylate O atom and a methyl C atom of the DMSO ligand. There is a weak intramolecular C—H...O hydrogen bond [3.065 (3) Å] formed between a benzene CH group and a carboxylate O atom.  相似文献   

12.
Two new layered complexes with the formulas of {[Cu(H2O)(HL)2Cl](NO3)}n ( 1 ) and {[Cu(H2O)2(HL)2](NO3)2}n ( 2 ) were solvothermally synthesized by the reactions of the bulky conjugated 4′‐(4‐hydroxyphenyl)‐4,2′:6′,4′′‐terpyridine ligand (HL) with different CuII salts, which were further used as photocatalysts to achieve hydrogen production from water splitting. Single‐crystal structural analyses reveal that both complexes feature coplanar (4 4) layers with different connection manners between the HL extended Z‐shaped chains. More interestingly, 1 possessing more negative conduction band potential and higher structural stability exhibits a large hydrogen production rate of 2.43 mmol · g–1 · h–1, which is four times higher than that of 2 . Thus, the CuII‐based coordination polymers modified by the bulky conjugated organic ligand can become potentially promising non‐Pt photocatalysts for hydrogen production from water splitting.  相似文献   

13.
In the title compound, [Cu(C9H5N4O)Cl(C12H8N2)]n or [Cu(tcnoet)Cl(phen)]n, where phen is 1,10‐phenanthroline and tcnoet is 1,1,3,3‐tetracyano‐2‐ethoxypropenide, the axially elongated (4 + 2) coordination polyhedron around the CuII centre contains N atoms from three different tcnoet ligands. The resulting coordination polymer takes the form of sheets which are linked in pairs by a single C—H...N hydrogen bond to form bilayers. The bond lengths provide evidence for significant bond fixation in the phen ligand and extensive electronic delocalization in the tcnoet ligand, where the two –C(CN)2 units are rotated, in conrotatory fashion, out of the plane of the central C3O fragment.  相似文献   

14.
The title compund, [Cu2(OH)2(C22H25N3)2](ClO4)2, is a copper(II) dimer, with two [CuL]2+ units [L is bis(6‐methyl‐2‐pyridylmethyl)(2‐phenylethyl)amine] bridged by hydroxide groups to define the {[CuL](μ‐OH)2[CuL]}2+ cation. Charge balance is provided by perchlorate counter‐anions. The cation has a crystallographic inversion centre halfway between the CuII ions, which are separated by 3.0161 (8) Å. The central core of the cation is an almost regular Cu2O2 parallelogram of sides 1.931 (2) and 1.935 (2) Å, with a Cu—O—Cu angle of 102.55 (11)°. The coordination geometry around each CuII centre can be best described as a square‐based pyramid, with three N atoms from L ligands and two hydroxide O atoms completing the coordination environment. Each cationic unit is hydrogen bonded to two perchlorate anions by means of hydroxide–perchlorate O—H...O interactions.  相似文献   

15.
The CuII ion in the title complex, [Cu(C5H10NO3)2] or [Cu(He‐ala)2] [He‐ala = N‐(2‐hydroxy­ethyl)‐β‐alaninate], resides at the inversion centre of a square bipyramid comprised of two facially arranged tridentate He‐ala ligands. Each He‐ala ligand binds to a CuII ion by forming one six‐membered β‐alaninate chelate ring in a twist conformation and one five‐membered ethanol­amine ring in an envelope conformation, with Cu—N = 2.017 (2) Å, Cu—OCOO = 1.968 (1) Å and Cu—OOH = 2.473 (2) Å. The [Cu(He‐ala)2] mol­ecules are involved in a network of O—H⋯O and N—H⋯O hydrogen bonds, forming layers parallel to the (10) plane. The layers are connected into a three‐dimensional structure by van der Waals inter­actions, so that the mol­ecular centres form pseudo‐face‐centered close packing.  相似文献   

16.
The coordination mode of the dimethylmalonate ligand in the two title CuII complexes, {[Cu(C5H3O4)(H2O)]·H2O}n, (I), and [Cu(C5H3O4)(H2O)]n, (II), is the same, with chelated six‐membered, bis‐monodentate and bridging bonding modes. However, the coordination environment of the CuII atoms, the connectivity of their metal–organic frameworks and their hydrogen‐bonding interactions are different. Complex (I) has a perfect square‐pyramidal CuII environment with the aqua ligand in the apical position, and only one type of square grid consisting of CuII atoms linked via carboxylate bridges to three dimethylmalonate ligands, with weak hydrogen‐bond interactions within and between its two‐dimensional layers. Complex (II) has a coordination geometry that is closer to square pyramidal than trigonal bipyramidal for its CuII atoms with the aqua ligand now in the basal plane. Its two‐dimensional layer structure comprises two alternating grids, which involve two and four different dimethylmalonate anions, respectively. There are strong hydrogen bonds only within its layers.  相似文献   

17.
The title compound, [CuNa(C4H3O7S)(C10H8N2)(H2O)3]n, consists of one CuII cation, one NaI cation, one 2‐sulfonatobutanedioate trianion (SSC3−), one 2,2′‐bipyridyl (bpy) ligand and three coordinated water molecules as the building unit. The coordination of the CuII cation is composed of two pyridyl N atoms, one water O atom and two carboxylate O atoms in a distorted square‐pyramidal coordination geometry with an axial elongation. The NaI cation is six‐coordinated by three water molecules and three carboxylate O atoms from three SSC3− ligands in a distorted octahedral geometry. Two SSC3− ligands link two CuII cations to form a Cu2(SSC)2(bpy)2 macrocyclic unit lying across an inversion centre, which is further linked by NaI cations via Na—O bonds to give a one‐dimensional chain. Interchain hydrogen bonds link these chains to form a two‐dimensional layer, which is further extended into a three‐dimensional supramolecular framework through π–π stacking interactions. The thermal stability of the title compound has also been investigated.  相似文献   

18.
The structure of the title compound, [Cu2(C19H18N3O)2](ClO4)2, was reported with insufficient accuracy because of a twinning problem by Adams, Bailey, Campbell, Fenton & He [J. Chem. Soc. DaltonTrans. (1996), pp. 2233–2237]. The dinuclear phenolate‐bridged CuII complex has an inversion centre.  相似文献   

19.
Coordination polymers (CPs) built by coordination bonds between metal ions/clusters and multidentate organic ligands exhibit fascinating structural topologies and potential applications as functional solid materials. The title coordination polymer, poly[diaquabis(μ4‐biphenyl‐3,4′,5‐tricarboxylato‐κ4O3:O3′:O4′:O5)tris[μ2‐1,4‐bis(1H‐imidazol‐1‐yl)benzene‐κ2N3:N3′]dicopper(II)dicopper(I)], [CuII2CuI2(C15H7O6)2(C12H10N4)3(H2O)2]n, was crystallized from a mixture of biphenyl‐3,4′,5‐tricarboxylic acid (H3bpt), 1,4‐bis(1H‐imidazol‐1‐yl)benzene (1,4‐bib) and copper(II) chloride in a water–CH3CN mixture under solvothermal reaction conditions. The asymmetric unit consists of two crystallographically independent Cu atoms, one of which is CuII, while the other has been reduced to the CuI ion. The CuII centre is pentacoordinated by three O atoms from three bpt3− ligands, one N atom from a 1,4‐bib ligand and one O atom from a coordinated water molecule, and the coordination geometry can be described as distorted trigonal bipyramidal. The CuI atom exhibits a T‐shaped geometry (CuN2O) coordinated by one O atom from a bpt3− ligand and two N atoms from two 1,4‐bib ligands. The CuII atoms are extended by bpt3− and 1,4‐bib linkers to generate a two‐dimensional network, while the CuI atoms are linked by 1,4‐bib ligands, forming one‐dimensional chains along the [20] direction. In addition, the completely deprotonated μ4‐η1111 bpt3− ligands bridge one CuI and three CuII cations along the a (or [100]) direction to form a three‐dimensional framework with a (103)2(10)2(42.6.102.12)2(42.6.82.10)2(8) topology via a 2,2,3,4,4‐connected net. An investigation of the magnetic properties indicated a very weak ferromagnetic behaviour.  相似文献   

20.
The preparation and X‐ray and spectroscopic studies of the title copper(II) complex, [Cu(C12H8N3O2)(CN)(H2O)], are reported. The CuII cation is five‐coordinated, forming a distorted square‐planar pyramid with an Addison τ parameter of 0.14. The UV–vis spectrum shows a dd transition of the CuII centre at 638 nm, and the electron paramagnetic resonance (EPR) spectrum confirms that the CuII cation has an axial symmetry coordination and that the unpaired electrons occupy the dx2y2 orbital. Cyclic voltammetric studies show two irreversible oxidation and reduction peaks.  相似文献   

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