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1.
Coordination polymers constructed from metal ions and organic ligands have attracted considerable attention owing to their diverse structural topologies and potential applications. Ligands containing carboxylate groups are among the most extensively studied because of their versatile coordination modes. Reactions of benzene‐1,4‐dicarboxylic acid (H2BDC) and pyridine (py) with ZnII or CoII yielded two new coordination polymers, namely, poly[(μ4‐benzene‐1,4‐dicarboxylato‐κ4O:O′:O′′:O′′′)(pyridine‐κN)zinc(II)], [Zn(C8H4O2)(C5H5N)]n, (I), and catena‐poly[aqua(μ3‐benzene‐1,4‐dicarboxylato‐κ3O:O′:O′′)bis(pyridine‐κN)cobalt(II)], [Co(C8H4O2)(C5H5N)2(H2O)]n, (II). In compound (I), the ZnII cation is five‐coordinated by four carboxylate O atoms from four BDC2− ligands and one pyridine N atom in a distorted square‐pyramidal coordination geometry. Four carboxylate groups bridge two ZnII ions to form centrosymmetric paddle‐wheel‐like Zn22‐COO)4 units, which are linked by the benzene rings of the BDC2− ligands to generate a two‐dimensional layered structure. The two‐dimensional layer is extended into a three‐dimensional supramolecular structure with the help of π–π stacking interactions between the aromatic rings. Compound (II) has a one‐dimensional double‐chain structure based on Co22‐COO)2 units. The CoII cations are bridged by BDC2− ligands and are octahedrally coordinated by three carboxylate O atoms from three BDC2− ligands, one water O atom and two pyridine N atoms. Interchain O—H…O hydrogen‐bonding interactions link these chains to form a three‐dimensional supramolecular architecture.  相似文献   

2.
In the title compound, [Mn(C5H2N2O4)(H2O)2]n, the MnII ion has a distorted octahedral geometry and the 4‐oxido‐2‐oxo‐1,2‐dihydropyrimidine‐5‐carboxylate (Hiso2−) anion acts as a μ34‐bridging ligand. Two oxo O atoms from different Hiso2− ligands bridge two MnII ions, forming centrosymmetric dinuclear building blocks. Each dinuclear building block interacts with another four by the coordination of the oxide groups and carboxylate O atoms, producing a two‐dimensional framework in the ab plane. Hydrogen bonds further extend the two‐dimensional sheets into a three‐dimensional supramolecular framework.  相似文献   

3.
In catena‐poly­[[(di‐2‐pyridyl­amine‐κ2N,N′)silver(I)]‐μ‐nico­tinato‐κ2N:O], [Ag(C6H4NO2)(C10H9N3)]n, the AgI atom is tetracoordinated by two N atoms from the di‐2‐pyridyl­amine (BPA) ligand [Ag—N = 2.3785 (18) and 2.3298 (18) Å] and by one N atom and one carboxyl­ate O atom from nicotinate ligands [Ag—N = 2.2827 (15) Å and Ag—O = 2.3636 (14) Å]. Bridging by nicotinate N and O atoms generates a polymeric chain structure, which extends along [100]. The carboxyl O atom not bonded to the Ag atom takes part in an intrachain C—H⋯O hydrogen bond, further stabilizing the chain. Pairs of chains are linked by N—H⋯O hydrogen bonds to generate ribbons. There are no π–π interactions in this complex. In catena‐poly­[[(di‐2‐pyridyl­amine‐κ2N,N′)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato‐κ2O1:O2], [Ag(C7H5O4)(C10H9N3)]n, the AgI atom has a distorted tetrahedral coordination, with three strong bonds to two pyridine N atoms from the BPA ligand [Ag—N = 2.286 (5) and 2.320 (5) Å] and to one carboxyl­ate O atom from the 2,6‐di­hydroxy­benzoate ligand [Ag—O = 2.222 (4) Å]; the fourth, weaker, Ag‐atom coordination is to one of the phenol O atoms [Ag⋯O = 2.703 (4) Å] of an adjacent moiety, and this interaction generates a polymeric chain along [100]. Pairs of chains are linked about inversion centers by N—H⋯O hydrogen bonds to form ribbons, within which there are π–π interactions. The ribbons are linked about inversion centers by pairs of C—H⋯O hydrogen bonds and additional π–π interactions between inversion‐related pairs of 2,6‐di­hydroxy­benzoate ligands to generate a three‐dimensional network.  相似文献   

4.
The design and synthesis of new organic lgands is important to the rapid development of coordination polymers (CPs). However, CPs based on asymmetric ligands are still rare, mainly because such ligands are usually expensive and more difficult to synthesize. The new asymmetric ligand 4‐[4‐(1H‐imidazol‐1‐yl)phenyl]pyridine (IPP) has been used to construct the title one‐dimensional coordination polymer, catena‐poly[[[aqua{4‐[4‐(1H‐imidazol‐1‐yl‐κN3)phenyl]pyridine}cadmium(II)]‐μ‐5‐hydroxybenzene‐1,3‐dicarboxylato‐κ3O1,O1′:O3] monohydrate], {[Cd(C8H4O5)(C14H11N3)2(H2O)]·H2O}n, under hydrothermal reaction of IPP with CdII in the presence of 5‐hydroxyisophthalic acid (5‐OH‐H2bdc). The CdII cation is coordinated by two N atoms from two distinct IPP ligands, three carboxylate O atoms from two different 5‐OH‐bdc2− dianionic ligands and one water O atom in a distorted octahedral geometry. The cationic [Cd(IPP)2]2+ nodes are linked by 5‐OH‐bdc2− ligands to generate a one‐dimensional chain. These chains are extended into a two‐dimensional layer structure via O—H…O and O—H…N hydrogen bonds and π–π interactions.  相似文献   

5.
The title compound, [Cu2(C9H10NO3)2(NO3)2(C10H8N2)(H2O)2]n, contains CuII atoms and l ‐tyrosinate (l ‐tyr) and 4,4′‐bipyridine (4,4′‐bipy) ligands in a 2:2:1 ratio. Each Cu atom is coordinated by one amino N atom and two carboxylate O atoms from two l ‐tyr ligands, one N atom from a 4,4′‐bipy ligand, a monodentate nitrate ion and a water molecule in an elongated octahedral geometry. Adjacent Cu atoms are bridged by the bidentate carboxylate groups into a chain. These chains are further linked by the bridging 4,4′‐bipy ligands, forming an undulated chiral two‐dimensional sheet. O—H...O and N—H...O hydrogen bonds connect the sheets in the [100] direction. This study offers useful information for the engineering of chiral coordination polymers with amino acids and 4,4′‐bipy ligands by considering the ratios of the metal ion and organic components.  相似文献   

6.
The title complex, {[Ni(C15H11N4O2S)2(C10H8N2)(H2O)2]·H2O}n, was synthesized by the reaction of nickel chloride, 4‐{[(1‐phenyl‐1H‐tetrazol‐5‐yl)sulfanyl]methyl}benzoic acid (HL) and 4,4′‐bipyridine (bpy) under hydrothermal conditions. The asymmetric unit contains two half NiII ions, each located on an inversion centre, two L ligands, one bpy ligand, two coordinated water molecules and one unligated water molecule. Each NiII centre is six‐coordinated by two monodentate carboxylate O atoms from two different L ligands, two pyridine N atoms from two different bpy ligands and two terminal water molecules, displaying a nearly ideal octahedral geometry. The NiII ions are bridged by 4,4′‐bipyridine ligands to afford a linear array, with an Ni...Ni separation of 11.361 (1) Å, which is further decorated by two monodentate L ligands trans to each other, resulting in a one‐dimensional fishbone‐like chain structure. These one‐dimensional fishbone‐like chains are further linked by O—H...O, O—H...N and C—H...O hydrogen bonds and π–π stacking interactions to form a three‐dimensional supramolecular architecture. The thermal stability of the title complex was investigated via thermogravimetric analysis.  相似文献   

7.
A new cadmium coordination polymer, [Cd(C5H2N2O4)(H2O)2]n, possesses a one‐dimensional zigzag chain structure built from CdII centers bridged sequentially by pairs of O and N atoms of the 5‐carboxyimidazole‐4‐carboxylate ligand. The CdII center is in a distorted octahedral geometry, being coordinated by two O atoms from two coordinated water mol­ecules [Cd—O = 2.322 (7) and 2.364 (7) Å], and by two N atoms [Cd—N = 2.222 (6) and 2.232 (6) Å] and two carboxyl O atoms [Cd—O = 2.383 (6) and 2.414 (6) Å] from two 5‐carboxyimidazole‐4‐carboxylate ligands.  相似文献   

8.
In the title cadmium(II) coordination polymer, poly[tri‐μ4‐adipato‐bis(2‐phenyl‐1H‐1,3,7,8‐tetraazacyclopenta[l]phenanthrene‐κ2N7,N8)tricadmium(II)], [Cd3(C6H8O4)3(C19H12N4)2]n, one of the Cd atoms is in a distorted pentagonal bipyramidal coordination environment, surrounded by five O atoms from three adipate (adip) ligands and two N atoms from one 2‐phenyl‐1H‐1,3,7,8‐tetraazacyclopenta[l]phenanthrene (L) ligand. A second Cd atom occupies an inversion center and is coordinated by six O atoms from six adip ligands in a distorted octahedral geometry. The carboxylate ends of the adip ligands link CdII atoms to form unique trinuclear CdII clusters, which are further bridged by the adip linkers to produce a two‐dimensional layer structure. Topologically, each trinuclear CdII cluster is connected to four others through six adip ligands, thus resulting in a unique two‐dimensional four‐connected framework of (4,4)‐topology. This work may help the development of the coordination chemistry of 1,10‐phenanthroline derivatives.  相似文献   

9.
The coordination geometry of the NiII atom in the title complex, poly[diazidobis[μ‐1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene‐κ2N4:N4′]nickel(II)], [Ni(N3)2(C12H12N6)2]n, is a distorted octahedron, in which the NiII atom lies on an inversion centre and is coordinated by four N atoms from the triazole rings of two symmetry‐related pairs of 1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene (bbtz) ligands and two N atoms from two symmetry‐related monodentate azide ligands. The NiII atoms are bridged by four bbtz ligands to form a two‐dimensional (4,4)‐network.  相似文献   

10.
In the coordination polymer catena‐poly[[[diaqua[5‐carboxy‐2‐(pyridin‐3‐yl)‐1H‐imidazole‐4‐carboxylato‐κ2N3,O4]lead(II)]‐μ‐5‐carboxy‐2‐(pyridin‐3‐yl)‐1H‐imidazole‐4‐carboxylato‐κ3N3,O4:N2] dihydrate], {[Pb(C10H6N3O4)(H2O)2]·2H2O}n, the two 5‐carboxy‐2‐(pyridin‐3‐yl)‐1H‐imidazole‐4‐carboxylate ligands have different coordination modes, one being terminal and the other bridging. The bridging ligand links PbII cations into one‐dimensional coordination polymer chains. The structure is also stabilized by intra‐ and interchain π–π stacking interactions between the pyridine rings, resulting in the formation of a two‐dimensional network. Extensive hydrogen‐bonding interactions lead to the formation of a three‐dimensional supramolecular network.  相似文献   

11.
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   

12.
In poly[[bis(μ‐4,4′‐bi‐1H‐pyrazole‐κ2N2:N2′)bis(3‐carboxyadamantane‐1‐carboxylato‐κO1)cobalt(II)] dihydrate], {[Co(C12H15O4)2(C6H6N4)2]·2H2O}n, (I), the Co2+ cation lies on an inversion centre and the 4,4′‐bipyrazole (4,4′‐bpz) ligands are also situated across centres of inversion. In its non‐isomorphous cadmium analogue, {[Cd(C12H15O4)2(C6H6N4)2]·2H2O}n, (II), the Cd2+ cation lies on a twofold axis. In both compounds, the metal cations adopt an octahedral coordination, with four pyrazole N atoms in the equatorial plane [Co—N = 2.156 (2) and 2.162 (2) Å; Cd—N = 2.298 (2) and 2.321 (2) Å] and two axial carboxylate O atoms [Co—O = 2.1547 (18) Å and Cd—O = 2.347 (2) Å]. In both structures, interligand hydrogen bonding [N...O = 2.682 (3)–2.819 (3) Å] is essential for stabilization of the MN4O2 environment with its unusually high (for bulky adamantanecarboxylates) number of coordinated N‐donor co‐ligands. The compounds adopt two‐dimensional coordination connectivities and exist as square‐grid [M(4,4′‐bpz)2]n networks accommodating monodentate carboxylate ligands. The interlayer linkage is provided by hydrogen bonds from the carboxylic acid groups via the solvent water molecules [O...O = 2.565 (3) and 2.616 (3) Å] to the carboxylate groups in the next layer [O...O = 2.717 (3)–2.841 (3) Å], thereby extending the structures in the third dimension.  相似文献   

13.
In the title coordination polymer, [Pb(C14H8N2O4)(CH3OH)2]n, the asymmetric unit contains half of a PbII cation, half of a 2,2′‐(diazene‐1,2‐diyl)dibenzoate dianionic ligand (denoted L2−) and one methanol ligand. Each PbII centre is eight‐coordinated by six O atoms of chelating/bridging carboxylate groups from four L2− ligands and two O atoms from two terminal methanol ligands, forming a distorted dodecahedron. The [PbL2(MeOH)2] subunits are interlinked via the sharing of two carboxylate O atoms to form a one‐dimensional [PbL2(MeOH)2]n chain. Adjacent chains are further connected by L2− ligands, giving rise to a two‐dimensional layer, and these layers are bridged by L2− linkers to afford a three‐dimensional framework with a 41263 topology.  相似文献   

14.
In the title coordination compound, [Zn(C12H6O4)(C14H14N4)]n, the two ZnII centers exhibit different coordination environments. One ZnII center is four‐coordinated in a distorted tetrahedral environment surrounded by two carboxylate O atoms from two different naphthalene‐1,4‐dicarboxylate (1,4‐ndc) anions and two N atoms from two distinct 1,4‐bis(imidazol‐1‐ylmethyl)benzene (1,4‐bix) ligands. The coordination of the second ZnII center comprises two N atoms from two different 1,4‐bix ligands and three carboxylate O atoms from two different 1,4‐ndc ligands in a highly distorted square‐pyramidal environment. The 1,4‐bix ligand and the 1,4‐ndc anion link adjacent ZnII centers into a two‐dimensional four‐connected (4,4) network. The two (4,4) networks are interpenetrated in a parallel mode.  相似文献   

15.
Bifunctional organic ligands are very popular for the design of coordination polymers because they allow the formation of a great diversity of structures. In the title coordination polymer, the new bifunctional inversion‐symmetric ligand 2,5‐bis(1H‐1,2,4‐triazol‐1‐yl)terephthalic acid (abbreviated as H2bttpa) links CdII cations, giving rise to the three‐dimensional CdII coordination polymer catena‐poly[diaqua[μ4‐2,5‐bis(1H‐1,2,4‐triazol‐1‐yl)terephthalato‐κ4O1:O4:N4:N4′]cadmium(II)], [Cd(C12H6N6O4)(H2O)2]n or [Cd(bttpa)(H2O)2]n. The asymmetric unit consists of half a CdII cation, half a bttpa2− ligand and one coordinated water molecule. The CdII cation is located on a twofold axis and is hexacoordinated in a distorted octahedral environment of four O and two N atoms. Four different bttpa2− ligands contribute to this coordination, with two carboxylate O atoms in trans positions and two triazole N atoms in cis positions. Two aqua ligands in cis positions complete the coordination sphere. The fully deprotonated bttpa2− ligand sits about a crystallographic centre of inversion and links two CdII cations to form a chain in a μ2‐terephthalato‐κ2O1:O4 bridge. This chain extends in the other two directions via the triazole heterocycles, producing a three‐dimensional framework. O—H…O hydrogen bonds and weak C—H…N interactions stabilize the three‐dimensional crystal structure. The FT–IR spectrum, X‐ray powder pattern, thermogravimetric behaviour and solid‐state photoluminescence of the title polymer have been investigated. The photoluminescence is enhanced and red‐shifted with respect to the uncoordinated ligand.  相似文献   

16.
The title compound, {[Cd2(C9HNO8)(H2O)4]·H2O}n, consists of two crystallographically independent CdII cations, one tetrabasic pyridine‐2,3,5,6‐tetracarboxylate (pdtc) anion, four coordinated water molecules and one solvent water molecule. The CdII cations have distorted square‐antiprismatic (one pyridine N, six carboxylate O and one water O atom) and octahedral (three carboxylate O and three water O atoms) coordination environments. Each pdtc ligand employs its pyridine and carboxylate groups to chelate and bridge seven CdII cations. The square‐antiprismatic coordinated CdII cations are linked by pdtc ligands into a lamellar framework structure, while the octahedral coordinated CdII cations are bridged by the μ2‐carboxylate O atoms and the pdtc ligands into a chain network that further joins neighbouring lamellae into a three‐dimensional porous network. The cavities are filled with solvent water molecules that are linked to the host through complex hydrogen bonding.  相似文献   

17.
The title coordination polymer, poly[bis(μ4‐biphenyl‐2,2′‐dicarboxylato)(dipyrido[3,2‐a:2′,3′‐c]phenazine)manganese(II)], [Mn2(C14H8O4)2(C18H10N4)]n, was obtained through the reaction of MnCl2·4H2O, biphenyl‐2,2′‐dicarboxylic acid (H2dpdc) and dipyrido[3,2‐a:2′,3′‐c]phenazine (L) under hydrothermal conditions. The asymmetric unit contains two crystallographically unique MnII ions, one unique L ligand and two unique dpdc ligands. One Mn ion is six‐coordinated by four O atoms from three different dpdc ligands and two N atoms from one L ligand, adopting a distorted octahedral coordination geometry. The distortions from ideal octahedral geometry are largely due to the presence of chelating ligands and the resulting acute N—Mn—N and O—Mn—O angles. The second Mn ion is coordinated in a distorted trigonal bipyramidal fashion by five O atoms from four distinct dpdc ligands. Four MnII ions are bridged by the carboxylate groups of the dpdc ligands to form an unusual tetranuclear MnII cluster. Clusters are further connected by the aromatic backbone of the dicarboxylate ligands, forming a one‐dimensional chain structure along the b axis. The title compound is the first example of a chain structure based on a tetranuclear MnII cluster.  相似文献   

18.
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   

19.
The title compound, {[U(C12H14O4)O2(H2O)]·H2O}n, is the first actinide complex featuring adamantanecarboxylate ligands. The metal ion possesses a pentagonal–bipyramidal UO7 coordination involving two axial oxide ligands [U—O = 1.732 (5) and 1.764 (5) Å] and five equatorial O atoms [U—O = 2.259 (5)–2.494 (4) Å] of aqua and carboxylate ligands. The latter display pseudo‐chelating and bridging coordination modes of the carboxylate groups that are responsible for the generation of the centrosymmetric discrete uranium–carboxylate [UO2(μ‐RCOO)2UO2] dimers [U...U = 5.5130 (5) Å] and their connection into one‐dimensional chains. Hydrogen bonding involving two coordinated and two solvent water molecules [O...O = 2.719 (7)–2.872 (7) Å] yields centrosymmetric (H2O)4 ensembles and provides noncovalent linkage between the coordination chains to generate a three‐dimensional network structure.  相似文献   

20.
A two‐dimensional MnII coordination polymer (CP), poly[bis[μ2‐2,6‐bis(imidazol‐1‐yl)pyridine‐κ2N3:N3′]bis(thiocyanato‐κN)manganese] [Mn(NCS)2(C11H9N5)2]n, (I), has been obtained by the self‐assembly reaction of Mn(ClO4)2·6H2O, NH4SCN and bent 2,6‐bis(imidazol‐1‐yl)pyridine (2,6‐bip). CP (I) was characterized by FT–IR spectroscopy, elemental analysis and single‐crystal X‐ray diffraction. The crystal structure features a unique two‐dimensional (4,4) network with one‐dimensional channels. The luminescence and nitrobenzene‐sensing properties were explored in a DMF suspension, revealing that CP (I) shows a strong luminescence emission and is highly sensitive for nitrobenzene detection.  相似文献   

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