Two new CoII coordination polymers with multifunctional 5-amino-2,4,6-tribromoisophthalic acid and flexible isomeric bis(imidazole) ligands: preparation, crystal structure and characterization

2018 ◽  
Vol 74 (4) ◽  
pp. 504-512
Author(s):  
Chang-Kai Su ◽  
Kou-Lin Zhang

Two new CoII coordination polymers (CPs), namely, catena-poly[[[(5-amino-2,4,6-tribromobenzene-1,3-dicarboxylato-κO)aquacobalt(II)]-bis[μ-1,3-bis(imidazol-1-ylmethyl)benzene-κ2 N:N′]] 4.75-hydrate], {[Co(C8H2Br3NO4)(C14H14N4)2(H2O)]·4.75H2O} n , (1), and poly[(μ-5-amino-2,4,6-tribromobenzene-1,3-dicarboxylato-κ2 O 1:O 3)[μ-1,2-bis(imidazol-1-ylmethyl)benzene-κ2 N:N′]cobalt(II)], [Co(C8H2Br3NO4)(C14H14N4)] n , (2), have been synthesized successfully by the assembly of multifunctional 5-amino-2,4,6-tribromoisophthalic acid (H2ATBIP) and CoII ions in the presence of the flexible isomeric bis(imidazole) ligands 1,3-bis(imidazol-1-ylmethyl)benzene (mbix) and 1,2-bis(imidazol-1-ylmethyl)benzene (obix). The isomeric mbix and obix ligands have a big influence on the structures of CPs (1) and (2). CP (1) is composed of chains of nanometre-sized elliptical rings, in which the CoII atom exhibits a distorted octahedral coordination geometry and ATBIP2− acts as a monodentate ligand. Two adjacent chains are interlinked by π–π stacking interactions and hydrogen bonds, resulting in a supramolecular double chain. Hydrogen-bonded R 8 6(16) rings extend adjacent supramolecular double chains into a two-dimensional supramolecular layer. Halogen bonding and a hydrogen-bonded R 4 2(8) ring further link the two-dimensional supramolecular layers, leading to the formation of a three-dimensional supramolecular network. The CoII ion in CP (2) is tetracoordinated, exhibiting a distorted tetrahedral configuration. The ATBIP2− ligand exhibits a bis(monodentate) coordination bridging mode, linking adjacent CoII ions into zigzag chains, which are further bridged by the auxiliary bridging obix ligand, resulting in a two-dimensional (4,4) topological network. Interlayer hydrogen and halogen–halogen bonding further extend the two-dimensional layers into a three-dimensional supramolecular network. A detailed analysis of the solid-state UV–Vis–NIR diffuse-reflectance spectra of (1) and (2) indicates that a wide optical band gap exists in both (1) and (2). CP (1) exhibits an irreversible dehydration–rehydration behaviour.

2012 ◽  
Vol 68 (4) ◽  
pp. m362-m363
Author(s):  
Songwuit Chanthee ◽  
Tongchai Saesong ◽  
Watcharin Saphu ◽  
Kittipong Chainok ◽  
Samroeng Krachodnok

In the title inorganic–organic hybrid compound, [Cu2V4O12(C3H4N2)8]n, the VVion is tetracoordinated by four O atoms and the CuIIion is hexacoordinated by four N atoms from four imidazole ligands and two O atoms from two tetrahedral vanadate (VO4) units in a distorted octahedral geometry. The structure consists of two-dimensional sheets constructed from centrosymmetric cyclic [V4O12]4−anions covalently bound through O to [Cu(imidazole)4]2+cations. Adjacent sheets are linked by N—H...O hydrogen bonds and weak C—H...π interactions (H...centroid distances = 2.59, 2.66, 2.76, 2.91 and 2.98 Å into a three-dimensional supramolecular network.


Author(s):  
Olha Sereda ◽  
Helen Stoeckli-Evans

The title compounds,catena-poly[[[bis[(R)-propane-1,2-diamine-κ2N,N′]copper(II)]-μ-cyanido-κ2N:C-[tris(cyanido-κC)(nitroso-κN)iron(III)]-μ-cyanido-κ2C:N] monohydrate], {[Cu(Lpn)2][Fe(CN)5(NO)]·H2O}n, (I), and poly[[hexa-μ-cyanido-κ12C:N-hexacyanido-κ6C-hexakis[(R)-propane-1,2-diamine-κ2N,N′]dichromium(III)tricopper(II)] pentahydrate], {[Cu(Lpn)2]3[Cr(CN)6]2·5H2O}n, (II) [where Lpn = (R)-propane-1,2-diamine, C3H10N2], are new chiral cyanide-bridged bimetallic coordination polymers. The asymmetric unit of compound (I) is composed of two independent cation–anion units of {[Cu(Lpn)2][Fe(CN)5)(NO)]} and two water molecules. The FeIIIatoms have distorted octahedral geometries, while the CuIIatoms can be considered to be pentacoordinate. In the crystal, however, the units align to form zigzag cyanide-bridged chains propagating along [101]. Hence, the CuIIatoms have distorted octahedral coordination spheres with extremely long semicoordination Cu—N(cyanido) bridging bonds. The chains are linked by O—H...N and N—H...N hydrogen bonds, forming two-dimensional networks parallel to (010), and the networks are linkedviaN—H...O and N—H...N hydrogen bonds, forming a three-dimensional framework. Compound (II) is a two-dimensional cyanide-bridged coordination polymer. The asymmetric unit is composed of two chiral {[Cu(Lpn)2][Cr(CN)6]}−anions bridged by a chiral [Cu(Lpn)2]2+cation and five water molecules of crystallization. Both the CrIIIatoms and the central CuIIatom have distorted octahedral geometries. The coordination spheres of the outer CuIIatoms of the asymmetric unit can be considered to be pentacoordinate. In the crystal, these units are bridged by long semicoordination Cu—N(cyanide) bridging bonds forming a two-dimensional network, hence these CuIIatoms now have distorted octahedral geometries. The networks, which lie parallel to (10-1), are linkedviaO—H...O, O—H...N, N—H...O and N—H...N hydrogen bonds involving all five non-coordinating water molecules, the cyanide N atoms and the NH2groups of the Lpn ligands, forming a three-dimensional framework.


2014 ◽  
Vol 70 (2) ◽  
pp. 198-201 ◽  
Author(s):  
Ji Qi ◽  
Xiang-Sheng Zhai ◽  
Hong-Lin Zhu ◽  
Jian-Li Lin

A tetranuclear CoIIIoxide complex with cubane topology, tetrakis(2,2′-bipyridine-κ2N,N′)di-μ2-carbonato-κ4O:O′-tetra-μ3-oxido-tetracobalt(III) pentadecahydrate, [Co4(CO3)2O4(C10H8N2)4]·15H2O, with an unbounded hydrogen-bonded water layer, has been synthesized by reaction of CoCO3and 2,2′-bipyridine. The solvent water molecules form a hydrogen-bonded net with tetrameric and pentameric water clusters as subunits. The Co4O4cubane-like cores are sandwiched between the water layers, which are further stacked into a three-dimensional metallo-supramolecular network.


Author(s):  
Mwaffak Rukiah ◽  
Thaer Assaad

The title two-dimensional coordination polymer, [Na(C2H8NO6P2)]n, was characterized using powder X-ray diffraction data and its structure refined using the Rietveld method. The asymmetric unit contains one Na+cation and one (1-azaniumylethane-1,1-diyl)bis(hydrogen phosphonate) anion. The central Na+cation exhibits distorted octahedral coordination geometry involving two deprotonated O atoms, two hydroxy O atoms and two double-bonded O atoms of the bisphosphonate anion. Pairs of sodium-centred octahedra share edges and the pairs are in turn connected to each other by the biphosphonate anion to form a two-dimensional network parallel to the (001) plane. The polymeric layers are connected by strong O—H...O hydrogen bonding between the hydroxy group and one of the free O atoms of the bisphosphonate anion to generate a three-dimensional network. Further stabilization of the crystal structure is achived by N—H...O and O—H...O hydrogen bonding.<!?tpb=18.7pt>


2015 ◽  
Vol 71 (2) ◽  
pp. 93-96 ◽  
Author(s):  
Qiang Li ◽  
Hui-Ting Wang ◽  
Lin Zhou

A new tetrazole–metal supramolecular compound, di-μ-chlorido-bis(trichlorido{1-[(1H-tetrazol-5-yl-κN2)methyl]-1,4-diazoniabicyclo[2.2.2]octane}cadmium(II)), [Cd2(C8H16N6)2Cl8], has been synthesized and structurally characterized by single-crystal X-ray diffraction. In the structure, each CdIIcation is coordinated by five Cl atoms (two bridging and three terminal) and by one N atom from the 1-[(1H-tetrazol-5-yl)methyl]-1,4-diazoniabicyclo[2.2.2]octane ligand, adopting a slightly distorted octahedral coordination geometry. The bridging bicyclo[2.2.2]octane and chloride ligands link the CdIIcations into one-dimensional ribbon-like N—H...Cl hydrogen-bonded chains along thebaxis. An extensive hydrogen-bonding network formed by N—H...Cl and C—H...Cl hydrogen bonds, and interchain π–π stacking interactions between adjacent tetrazole rings, consolidate the crystal packing, linking the poymeric chains into a three-dimensional supramolecular network.


2015 ◽  
Vol 71 (9) ◽  
pp. 763-767
Author(s):  
Hui-Ting Wang ◽  
Qiang Li ◽  
Lin Zhou

A cadmium–thiocyanate complex, poly[(1-cyanomethyl-4-aza-1-azoniabicyclo[2.2.2]octane-κ4N)octakis-μ2-thiocyanato-κ8N:S;κ8S:N-tricadmium(II)], [Cd3(C8H14N3)2(NCS)8]n, was synthesized by the reaction of 1-cyanomethyl-4-aza-1-azoniabicyclo[2.2.2]octane chloride, cadmium nitrate tetrahydrate and potassium thiocyanide in aqueous solution. In the crystal structure, there are two independent types of CdIIcation (one on a centre of inversion and one in a general position) and both are in distorted octahedral coordination environments, coordinated by N and S atoms from different ligands. Neighbouring CdIIcations are linked together by thiocyanate bridges to form a two-dimensional network. Hydrogen-bonding interactions are involved in the formation of a three-dimensional supramolecular network.


2014 ◽  
Vol 70 (8) ◽  
pp. 770-772 ◽  
Author(s):  
Xiao-Min Hao ◽  
Gang Chen ◽  
Chang-Sheng Gu ◽  
Ji-Wei Liu

In the title coordination polymer, [Cd2(SO4)2(C13H8N4)(H2O)2]n, there are two crystallographically independent CdIIcentres with different coordination geometries. The first CdIIcentre 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 CdIIcentre 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 monocappedanti-trigonal prismatic geometry. The symmetry-independent CdIIions 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.


2014 ◽  
Vol 70 (11) ◽  
pp. 1083-1087 ◽  
Author(s):  
Hou-Ting Liu ◽  
Jing Lu

A new CuII–azide complex, {(C4H12N2)[Cu5(N3)12]·4H2O}n, has been synthesized by the reaction of piperazine, Cu(OAc)2·2H2O (OAc is acetate) and NaN3. In the structure, μ2-1,1- and μ3-1,1,1-azide anions bridge five CuIIcations to form a linear pentanuclear cluster unit, which is further linked by μ2-1,1- and μ2-1,3-azide anions to form a two-dimensional condensed [Cu5(N3)12]nlayer. The diprotonated piperazine and the solvent water molecules are hydrogen bonded to the coordination layers to form a three-dimensional supramolecular network.


2015 ◽  
Vol 71 (9) ◽  
pp. 820-823
Author(s):  
Lin Zhou ◽  
Hui-Ting Wang

A cadmium–thiocyanate complex, poly[[bis(nicotinic acid-κN)di-μ-thiocyanato-κ2N:S;κ2S:N-cadmium(II)] monohydrate], {[Cd(NCS)2(C6H5NO2)2]·H2O}n, was synthesized by the reaction of nicotinic acid, cadmium nitrate tetrahydrate and potassium thiocyanide in aqueous solution. In the crystal structure, each CdIIcation is in a distorted octahedral coordination environment, coordinated by the N and S atoms of nicotinic acid and thiocyanate ligands. Neighbouring CdIIcations are linked together by thiocyanate bridges to form a two-dimensional network. Hydrogen-bond interactions between the uncoordinated solvent water molecules and the organic ligands result in the formation of the three-dimensional supramolecular network.


2014 ◽  
Vol 70 (5) ◽  
pp. 445-448 ◽  
Author(s):  
De-Hong Wu

The crystal structure of the title compound {(C5H14N2)2[Cd2Cl8]} n , (I), consists of hydrogen-bonded 2-methylpiperazinediium (H2MPPA2+) cations in the presence of one-dimensional polymeric {[CdCl3(μ3-Cl)]2−} n anions. The CdII centres are hexacoordinated by three terminal chlorides and three bridging chlorides and have a slightly distorted octahedral CdCl3(μ3-Cl)3 arrangement. The alternating CdCl6 octahedra form four-membered Cd2Cl2 rings by the sharing of neighbouring Cd–Cl edges to give rise to extended one-dimensional ladder-like chains parallel to the b axis, with a Cd...Cd distance of 4.094 (2) Å and a Cd...Cd...Cd angle of 91.264 (8)°. The H2MPPA2+ cations crosslink the [CdCl3(μ3-Cl)] n chains by the formation of two N—H...Cl hydrogen bonds to each chain, giving rise to one-dimensional ladder-like H2MPPA2+–Cl2 hydrogen-bonded chains [graph set R 4 2(14)]. The [CdCl3(μ3-Cl)] n chains are interwoven with the H2MPPA2+–Cl2 hydrogen-bonded chains, giving rise to a three-dimensional supramolecular network.


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