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1.
In the title complex, poly[cadmium(II)‐μ2‐1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene‐di‐μ2‐thio­cyanato], [Cd(NCS)2(C12H12N6)]n, the CdII atom lies on an inversion centre in a distorted octa­hedral environment. Four N atoms from the thio­cyanate and 1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene (bbtz) ligands occupy the equatorial positions, and two S atoms from symmetry‐related thio­cyanate ligands occupy the axial positions. The benzene ring of the bbtz ligand lies about an inversion centre. Single thio­cyanate bridges link the CdII atoms into two‐dimensional sheets containing novel 16‐membered [Cd4(μ‐NCS‐N:S)4] rings. The bbtz ligands further link these two‐dimensional sheets into an unprecedented covalent three‐dimensional network for the cadmium–thio­cyanate system.  相似文献   

2.
In the crystal structure of the title complex, poly­[[di­azido­manganese(II)]‐di‐μ‐1,2‐bis­(imidazol‐1‐yl)­ethane‐κ4N3:N3′], [Mn(N3)2(C8H10N4)2]n or [Mn(N3)2(bim)2]n, where bim is 1,2‐­bis(imidazol‐1‐yl)­ethane, each MnII atom is six‐coordinated in a distorted octahedral coordination environment to four N atoms from four bim ligands and two N atoms from two azide ligands. The MnII atoms, which lie on inversion centres, are bridged by four bim ligands to form a two‐dimensional (4,4)‐network. The azide ligands are monodentate (terminal).  相似文献   

3.
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   

4.
In the crystal structure of the title complex, poly­[[di­azidocobalt(II)]‐di‐μ‐1,4‐bis(1,2,4‐triazol‐1‐yl­methyl)­benzene‐κ4N4:N4′], [Co(N3)2(bbtz)2]n, where bbtz is 1,4‐bis(1,2,4‐triazol‐1‐yl­methyl)­benzene (C12H12N6), the CoII atom, which lies on an inversion centre, is six‐coordinated by four N atoms from four bbtz ligands and by two N atoms from two azide ligands, in a distorted octahedral coordination environment. The CoII atoms are bridged by four bbtz ligands to form a two‐dimensional [4,4]‐network.  相似文献   

5.
In the search for potential ferroelectric materials, molecular‐based one‐, two‐ and three‐dimensional cadmium(II) organic–inorganic compounds have been of interest as they often display solid–solid phase transitions induced by a variation in temperature. A new cadmium dicyanamide complex, poly[4‐dimethylamino‐1‐ethylpyridin‐1‐ium [tri‐μ‐dicyanamido‐κ6N1:N5‐cadmium(II)]], {(C9H15N2)[Cd(C2N3)3]}n, was synthesized by the reaction of 4‐dimethylamino‐1‐ethylpyridin‐1‐ium bromide, cadmium nitrate tetrahydrate and sodium dicyanamide in aqueous solution. In the crystal structure, each CdII cation is octahedrally coordinated by six terminal N atoms from six anionic dicyanamide (dca) ligands. Neighbouring CdII cations are linked together by dicyanamide bridges to form a two‐dimensional coordination polymer. The organic cations are not involved in the formation of the supramolecular network.  相似文献   

6.
In the title complex, poly[copper(II)‐di‐μ2‐thio­cyanato‐μ2‐1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene], [Cu(NCS)2(C12H12N6)]n, the CuII atom lies on an inversion centre in a tetra­gonally distorted octa­hedral environment. Four N atoms from thio­cyanate and 1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene (bbtz) ligands fill the equatorial positions, and S atoms from symmetry‐related thio­cyanate ligands fill the axial positions. The benzene ring of the bbtz ligand lies about an inversion centre. Single thio­cyanate bridges link the CuII atoms into two‐dimensional sheets containing an unprecedented 16‐membered [Cu4(μ‐NCS‐N:S)4] ring. The bbtz ligands further link the two‐dimensional sheets into a three‐dimensional network.  相似文献   

7.
In the title mixed‐ligand metal–organic polymeric compound, [Cd(C10H8O4)(C8H12N6)]n or [Cd(PBEA)(BTB)]n [H2PBEA is benzene‐1,4‐diacetic acid and BTB is 1,4‐bis(1,2,4‐triazol‐1‐yl)butane], the asymmetric unit contains one CdII ion, one BTB molecule and one PBEA2− anion. The CdII ion is in a slightly distorted pentagonal–bipyramidal geometry, coordinated by five carboxylate O atoms from three distinct PBEA2− anions and by two BTB N atoms. There are two coordination patterns for the carboxylate groups of the PBEA2− ligand, one being a μ1‐η11 chelating mode and the other a μ2‐η21 bridging mode, while the BTB molecule shows a transtranstrans conformation. The crystal structure is constructed from the secondary building unit (SBU) [Cd2(CO2)4N2O2], in which the two metal centres are held together by two PBEA2− linkers. The SBU is connected by BTB and PBEA2− bridges to form a two‐dimensional grid‐like (4,4) layer with meshes of dimensions 14.69 × 11.28 Å.  相似文献   

8.
A new cadmium–thiocyanate complex, poly[4‐(dimethylamino)pyridin‐1‐ium [di‐μ‐thiocyanato‐κ2N:S2S:N‐thiocyanato‐κN‐cadmium(II)]], {(C7H11N2)[Cd(NCS)3]}n, was synthesized by the reaction of cadmium thiocyanate and 4‐(dimethylamino)pyridine hydrochloride in aqueous solution. In the crystal structure, each CdII ion is square‐pyramidally coordinated by three N and two S atoms from five different thiocyanate ligands, four of which are bridging. The thiocyanate ligands play different roles in the build up of the structure; one role results in the formation of [Cd2(NCS)2] building blocks, while the other links the building blocks and cations via N—H...S hydrogen bonds. The N—H...S hydrogen bonds and weak π–π stacking interactions are involved in the formation of both a two‐dimensional network structure and the supramolecular network.  相似文献   

9.
The crystal engineering of coordination polymers has aroused interest due to their structural versatility, unique properties and applications in different areas of science. The selection of appropriate ligands as building blocks is critical in order to afford a range of topologies. Alkali metal cations are known for their mainly ionic chemistry in aqueous media. Their coordination number varies depending on the size of the binding partners, and on the electrostatic interaction between the ligands and the metal ions. The two‐dimensional coordination polymer poly[tetra‐μ‐aqua‐[μ4‐4,4′‐(diazenediyl)bis(5‐oxo‐1H‐1,2,4‐triazolido)]disodium(I)], [Na2(C4H2N8O2)(H2O)4]n, (I), was synthesized from 4‐amino‐1H‐1,2,4‐triazol‐5(4H)‐one (ATO) and its single‐crystal structure determined. The mid‐point of the imino N=N bond of the 4,4′‐(diazenediyl)bis(5‐oxo‐1H‐1,2,4‐triazolide) (ZTO2−) ligand is located on an inversion centre. The asymmetric unit consists of one Na+ cation, half a bridging ZTO2− ligand and two bridging water ligands. Each Na+ cation is coordinated in a trigonal antiprismatic fashion by six O atoms, i.e. two from two ZTO2− ligands and the remaining four from bridging water ligands. The Na+ cation is located near a glide plane, thus the two bridging O atoms from the two coordinating ZTO2− ligands are on adjacent apices of the trigonal antiprism, rather than being in an anti configuration. All water and ZTO2− ligands act as bridging ligands between metal centres. Each Na+ metal centre is bridged to a neigbouring Na+ cation by two water molecules to give a one‐dimensional [Na(H2O)2]n chain. The organic ZTO2− ligand, an O atom of which also bridges the same pair of Na+ cations, then crosslinks these [Na(H2O)2]n chains to form two‐dimensional sheets. The two‐dimensional sheets are further connected by intermolecular hydrogen bonds, giving rise to a stabile hydrogen‐bonded network.  相似文献   

10.
The CdII three‐dimensional coordination poly[[[μ4‐1,4‐bis(1,2,4‐triazol‐1‐yl)but‐2‐ene]bis(μ3‐5‐carboxybenzene‐1,3‐dicarboxylato)dicadmium(II)] dihydrate], {[Cd2(C9H4O6)2(C8H10N6)]·2H2O}n , (I), has been synthesized by the hydrothermal reaction of Cd(NO3)2·4H2O, benzene‐1,3,5‐tricarboxylic acid (1,3,5‐H3BTC) and 1,4‐bis(1,2,4‐triazol‐1‐yl)but‐2‐ene (1,4‐btbe). The IR spectrum suggests the presence of protonated carboxylic acid, deprotonated carboxylate and triazolyl groups. The purity of the bulk sample was confirmed by elemental analysis and X‐ray powder diffraction. Single‐crystal X‐ray diffraction analysis reveals that the CdII ions adopt a five‐coordinated distorted trigonal–bipyramidal geometry, coordinated by three O atoms from three different 1,3,5‐HBTC2− ligands and two N atoms from two different 1,4‐btbe ligands; the latter are situated on centres of inversion. The CdII centres are bridged by 1,3,5‐HBTC2− and 1,4‐btbe ligands into an overall three‐dimensional framework. When the CdII centres and the tetradentate 1,4‐btbe ligands are regarded as nodes, the three‐dimensional topology can be simplified as a binodal 4,6‐connected network. Thermogravimetric analysis confirms the presence of lattice water in (I). Photoluminescence studies imply that the emission of (I) may be ascribed to intraligand fluorescence.  相似文献   

11.
As part of an exploration of new coordination polymers, a cadmium‐dicyanamide complex, namely poly[benzyltriethylammonium [tri‐μ‐dicyanamido‐κ6N 1:N5‐cadmium(II)]], {(C13H22N)[Cd(C2N3)3]}n , has been synthesized by the reaction of benzyltriethylammonium bromide, cadmium nitrate tetrahydrate and sodium dicyanamide in aqueous solution, and characterized by single‐crystal X‐ray diffraction at room temperature. In the crystal structure, each CdII cation is coordinated by six nitrile N atoms from six anionic dicyanamide (dca) ligands to furnish a slightly distorted octahedral geometry. Neighbouring CdII cations are linked by dicyanamide bridges to construct a two‐dimensional anionic layer coordination polymer. One amide N atom in the bridging dca ligand is disordered over two sites. The cations lie between the anionic frameworks and there are no hydrogen‐bond interactions between the cations and anions. The organic cations are not involved in the formation of the supramolecular network.  相似文献   

12.
In the title mixed‐ligand metal–organic polymeric complex, {[Co(NCS)2(C8H12N6)2]·2H2O}n, the asymmetric unit contains a divalent CoII cation, which sits on an inversion centre, two halves of two crystallographically distinct and centrosymmetric 1,4‐bis(1,2,4‐triazol‐1‐yl)butane (BTB) ligands, one N‐bound thiocyanate ligand and one solvent water molecule. The CoII atom possesses a distorted {CoN6} octahedral geometry, with the equatorial positions taken up by triazole N atoms from four different BTB ligands. The axial positions are filled by thiocyanate N atoms. In the crystal, each CoII atom is linked covalently to four others through the distal donors of the tethering BTB ligands, forming a neutral (4,4)‐topology two‐dimensional rhomboid grid layer motif, which is coincident with the (11) crystal planes. Magnetic investigations show that weak antiferromagnetic coupling exists between CoII atoms in the complex.  相似文献   

13.
Metal–organic frameworks (MOFs) based on multidentate N‐heterocyclic ligands involving imidazole, triazole, tetrazole, benzimidazole, benzotriazole or pyridine present intriguing molecular topologies and have potential applications in ion exchange, magnetism, gas sorption and storage, catalysis, optics and biomedicine. The 2‐[(1H‐1,2,4‐triazol‐1‐yl)methyl]‐1H‐benzimidazole (tmb) ligand has four potential N‐atom donors and can act in monodentate, chelating, bridging and tridentate coordination modes in the construction of complexes, and can also act as both a hydrogen‐bond donor and acceptor. In addition, the tmb ligand can adopt different coordination conformations, resulting in complexes with helical structures due to the presence of the flexible methylene spacer. A new three‐dimensional coordination polymer, poly[[bis(μ2‐benzene‐1,4‐dicarboxylato)‐κ4O1,O1′:O4,O4′2O1:O4‐bis{μ2‐2‐[(1H‐1,2,4‐triazol‐1‐yl)methyl‐κN4]‐1H‐benzimidazole‐κN3}dizinc(II)] trihydrate], {[Zn(C8H4O4)(C10H9N5)]·1.5H2O}n, has been synthesized by the reaction of ZnCl2 with tmb and benzene‐1,4‐dicarboxylic acid (H2bdic) under solvothermal conditions. There are two crystallographically distinct bdic2− ligands [bdic2−(A) and bdic2−(B)] in the structure which adopt different coordination modes. The ZnII ions are bridged by tmb ligands, leading to one‐dimensional helical chains with different handedness, and adjacent helices are linked by bdic2−(A) ligands, forming a two‐dimensional network structure. The two‐dimensional layers are further connected by bdic2−(B) ligands, resulting in a three‐dimensional framework with the topological notation 66. The IR spectra and thermogravimetric curves are consistent with the results of the X‐ray crystal structure analysis and the title polymer exhibits good fluorescence in the solid state at room temperature.  相似文献   

14.
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   

15.
The title CdII compound, {[Cd2(C13H7NO4)2(H2O)4]·5H2O}n, was synthesized by the hydrothermal reaction of Cd(NO3)2·4H2O and 5‐(pyridin‐4‐yl)isophthalic acid (H2L). The asymmetric unit contains two crystallographically independent CdII cations, two deprotonated L2− ligands, four coordinated water molecules and five isolated water molecules. One of the CdII cations adopts a six‐coordinate octahedral coordination geometry involving three O atoms from one bidentate chelating and one monodentate carboxylate group of two different L2− ligands, one N atom of another L2− ligand and two coordinated water molecules. The second CdII cation adopts a seven‐coordinate pentagonal–bipyramidal coordination geometry involving four O atoms from two bidentate chelating carboxylate groups of two different L2− ligands, one N atom of another L2− ligand and two coordinated water molecules. Each L2− ligand bridges three CdII cations and, likewise, each CdII cation connects to three L2− ligands, giving rise to a two‐dimensional graphite‐like 63 layer structure. These two‐dimensional layers are further linked by O—H...O hydrogen‐bonding interactions to form a three‐dimensional supramolecular architecture. The photoluminescence properties of the title compound were also investigated.  相似文献   

16.
The coordination geometry of the ZnII atom in the title complex, [Zn2(NCS)4(C6H8N6)2], is that of a distorted tetra­hedron, in which the ZnII atom is coordinated by four N atoms from the triazole rings of two symmetry‐related 1,2‐bis­(1,2,4‐triazol‐1‐yl)ethane ligands and two thio­cyanate ligands. Two ZnII atoms are bridged by two organic ligands to form a dimer. The dimer lies about an inversion center.  相似文献   

17.
A series of 2‐(1H‐1,2,4‐triazol‐1‐yl)‐2H‐1,4‐benzothiazines were designed and synthesized by condensation of 1,2,4‐triazole‐substituted ω‐bromoacetophenones and o‐aminothiophenols with the aid of K2CO3 under mild conditions with moderate to high yields. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:332–336, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20434  相似文献   

18.
Assemblies of pyrazine‐2,3‐dicarboxylic acid and CdII in the presence of bis(1,2,4‐triazol‐1‐yl)butane or bis(1,2,4‐triazol‐1‐yl)ethane under ambient conditions yielded two new coordination polymers, namely poly[[tetraaqua[μ2‐1,4‐bis(1,2,4‐triazol‐1‐yl)butane‐κ2N4:N4′]bis(μ2‐pyrazine‐2,3‐dicarboxylato‐κ3N1,O2:O3)dicadmium(II)] dihydrate], {[Cd2(C6H2N2O4)2(C8H12N6)(H2O)4]·2H2O}n, (I), and poly[[diaqua[μ2‐1,2‐bis(1,2,4‐triazol‐1‐yl)ethane‐κ2N4:N4′]bis(μ3‐pyrazine‐2,3‐dicarboxylato‐κ4N1,O2:O3:O3′)dicadmium(II)] dihydrate], {[Cd2(C6H2N2O4)2(C6H8N6)(H2O)2]·2H2O}n, (II). Complex (I) displays an interesting two‐dimensional wave‐like structure and forms a distinct extended three‐dimensional supramolecular structure with the help of O—H...N and O—H...O hydrogen bonds. Complex (II) has a three‐dimensional framework structure in which hydrogen bonds of the O—H...N and O—H...O types are found.  相似文献   

19.
The title CdII coordination framework, [Cd(C15H8O5)(H2O)]n or [Cd(bpdc)(H2O)]n [H2bpdc is 2‐(4‐carboxybenzoyl)benzoic acid], has been prepared and characterized using IR spectroscopy, elemental analysis, thermal analysis and single‐crystal X‐ray diffraction. Each CdII centre is six‐coordinated by two O atoms from one 2‐(4‐carboxylatobenzoyl)benzoate (bpdc2−) ligand in chelating mode, three O‐donor atoms from three other bpdc2− anions and one O atom from a coordinated water molecule in an octahedral coordination environment. Two crystallographically equivalent CdII cations are bridged by one O atom of the 2‐carboxylate group of one bpdc2− ligand and by both O atoms of the 4‐carboxylate group of a second bpdc2− ligand to form a binuclear [(Cd)2(O)(OCO)] secondary building unit. Adjacent secondary building units are interlinked to form a one‐dimensional [Cd(OCO)2]n chain. The bpdc2− ligands link these rod‐shaped chains to give rise to a complex two‐dimensional [Cd(bpdc)]n framework with a 4,4‐connected binodal net topology of point symbol {43.62.8}. The compound exhibits a strong fluorescence emission and typical ferroelectric behaviour in the solid state at room temperature.  相似文献   

20.
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   

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