Design and synthesis of methyl 2-{[4-phenyl-5-(pyridin-2-yl)-4H-1,2,4-triazol-3-yl]sulfanyl}acetate (phpy2NS) as a ligand for complexes of Group 12 elements: structural assessment and hydrogen-bonded supramolecular assembly analysis

2019 ◽  
Vol 75 (7) ◽  
pp. 891-903 ◽  
Author(s):  
Alfonso Castiñeiras ◽  
Isabel García-Santos ◽  
Manuel Saa
Keyword(s):  
Crystal Packing ◽  
Noncovalent Interactions ◽  
Three Dimensional ◽  
Supramolecular Assembly ◽  
Chloroacetic Acid ◽  
Structural Diversity ◽  
Coordination Geometry ◽  
Metal Centre ◽  
Design And Synthesis ◽  
Cadmium Bromide

The reaction of 2-cyanopyridine with N-phenylthiosemicarbazide afforded 2-[amino(pyridin-2-yl)methylidene]-N-phenylhydrazine-1-carbothioamide (Ham4ph) and crystals of 4-phenyl-5-(pyridin-2-yl)-2,4-dihydro-3H-1,2,4-triazole-3-thione (pyph3NS, 1, C13H10N4S). Crystals of methyl 2-{[4-phenyl-5-(pyridin-2-yl)-4H-1,2,4-triazol-3-yl]sulfanyl}acetate (phpy2NS, 2, C16H14N4O2S), derived from 1, were obtained by the reaction of Ham4ph with chloroacetic acid, followed by the acid-catalyzed esterification of the carboxylic acid with methyl alcohol. Crystals of bis(methanol-κO)bis(methyl 2-{[4-phenyl-5-(pyridin-2-yl)-4H-1,2,4-triazol-3-yl-κ2 N 1,N 5]sulfanyl}acetato)zinc(II)/cadmium(II) hexabromidocadmate(II), [Zn0.76Cd0.24(C16H14N4O2S)2(CH3OH)2][Cd2Br6] or [Zn0.76Cd0.24(phpy2NS)2(MeOH)2][Cd2Br6], 3, and dichlorido(methyl 2-{[4-phenyl-5-(pyridin-2-yl)-4H-1,2,4-triazol-3-yl-κ2 N 1,N 5]sulfanyl}acetato)mercury(II), [HgCl2(C16H14N4O2S)] or [Hg(phpy2NS)Cl2], 4, were synthesized using ligand 2 and CdBr2 or HgCl2, respectively. The molecular and supramolecular structures of the compounds were studied by X-ray diffractometry. The asymmetric unit of 3 is formed from CdBr3 and M(phpy2NS)(MeOH) units, where the metal centre M has a 76% occupancy of ZnII and 24% of CdII. The M 2+ centre of the cation, located on a crystallographic inversion centre, is hexacoordinated and appears as a slightly distorted octahedral [MN4O2]2+ cation. The Cd centre of the anion is coordinated by two terminal bromide ligands and two bridging bromide ligands that generate [Cd2Br6]2− cadmium–bromide clusters. These clusters display crystallographic inversion symmetry forming two edge-shared tetrahedra and serve as agents that direct the structure in the formation of supramolecular assemblies. In mononuclear complex 4, the coordination geometry around the Hg2+ ion is distorted tetrahedral and comprises two chloride ligands and two N-atom donors from the phpy2NS ligand, viz. one pyridine N atom and the other from triazole. In the crystal packing, all four compounds exhibit weak intermolecular interactions, which facilitate the formation of three-dimensional architectures. Along with the noncovalent interactions, the structural diversity in the complexes can be attributed to the metal centre and to the coordination geometry, as well as to its ionic or neutral character.

Influence of N-heteroaromatic π–π stacking on supramolecular assembly and coordination geometry; effect of a single-atom change in the ligand

2015 ◽  
Vol 44 (12) ◽  
pp. 5488-5502 ◽  
Author(s):  
Hamid Reza Khavasi ◽  
Bahareh Mir Mohammad Sadegh
Keyword(s):  
Coordination Compounds ◽  
Crystal Packing ◽  
Supramolecular Assembly ◽  
Single Atom ◽  
Coordination Geometry ◽  
Geometry Effect ◽  
Π Interactions ◽  
Π Stacking ◽  
Nitrogen Heteroatom ◽  
Aromatic Systems

A study on how the polarization of aromatic systems, through the introduction of a nitrogen heteroatom, affects the π–π interactions and crystal packing of mercury coordination compounds.

scholarly journals Crystal structure of catena-poly[[[bis(3-oxo-1,3-diphenylprop-1-enolato-κ2 O,O′)zinc(II)]-μ2-tris[4-(pyridin-3-yl)phenyl]amine-κ2 N:N′] tetrahydrofuran monosolvate]

2019 ◽  
Vol 75 (10) ◽  
pp. 1432-1435
Author(s):  
Yukiyasu Kashiwagi ◽  
Koji Kubono ◽  
Toshiyuki Tamai
Keyword(s):  
Coordination Polymer ◽  
Crystal Packing ◽  
Three Dimensional ◽  
Polymer Chains ◽  
Coordination Geometry ◽  
Asymmetric Unit ◽  
One Dimensional ◽  
Π Interactions ◽  
Dimensional Network ◽  
Sheet Structure

The reaction of bis(3-oxo-1,3-diphenylprop-1-enolato-κ2 O,O′)zinc(II), [Zn(dbm)2], with tris[4-(pyridin-3-yl)phenyl]amine (T3PyA) in tetrahydrofuran (THF) afforded the title crystalline coordination polymer, {[Zn(C15H11O2)2(C33H24N4)]·C4H8O} n . The asymmetric unit contains two independent halves of Zn(dbm)2, one T3PyA and one THF. Each ZnII atom is located on an inversion centre and adopts an elongated octahedral coordination geometry, ligated by four O atoms of two dbm ligands in equatorial positions and by two N atoms of pyridine moieties from two different bridging T3PyA ligands in axial positions. The crystal packing shows a one-dimensional polymer chain in which the two pyridyl groups of the T3PyA ligand bridge two independent Zn atoms of Zn(dbm)2. In the crystal, the coordination polymer chains are linked via C—H...π interactions into a sheet structure parallel to (010). The sheets are cross-linked via further C—H...π interactions into a three-dimensional network. The solvate THF molecule shows disorder over two sets of atomic sites having occupancies of 0.631 (7) and 0.369 (7).

scholarly journals Crystal structure and Hirshfeld surface analysis of 2,2′-{(1E,1′E)-[ethane-1,2-diylbis(azanylylidene)]bis(methanylylidene)}bis[4-(trifluoromethoxy)phenol]copper(II) hydroquinone hemisolvate

2019 ◽  
Vol 75 (11) ◽  
pp. 1729-1733
Author(s):  
Sevgi Kansiz ◽  
Seher Meral ◽  
Necmi Dege ◽  
Aysen Alaman Agar ◽  
Igor O. Fritsky
Keyword(s):  
Surface Analysis ◽  
Crystal Packing ◽  
Three Dimensional ◽  
Hirshfeld Surface ◽  
Title Complex ◽  
Hirshfeld Surface Analysis ◽  
Dimensional Structure ◽  
Coordination Geometry ◽  
Open Chain ◽  
Square Planar

In the title complex, [Cu(C18H12F6N2O4)]·0.5C6H6O2, the CuII ion has a square-planar coordination geometry, being ligated by two N and two O atoms of the tetradentate open-chain Schiff base ligand 6,6′-{(1E,1′E)-[ethane-1,2-diylbis(azanylylidene)]bis(methanylylidene)}bis[2-(trifluoromethoxy)phenol]. The crystal packing is stabilized by intramolecular O—H...O and intermolecular C—H...F, C—H...O and C—H...π hydrogen bonds. In addition, weak π–π interactions form a three-dimensional structure. Hirshfeld surface analysis and two-dimensional fingerprint plots were performed and created to analyze the intermolecular interactions present in the crystal, indicating that the most important contributions for the crystal packing are from F...H/H...F (25.7%), H...H (23.5%) and C...H/H...C (12.6%) interactions.

scholarly journals Crystal structure of poly[{μ-N,N′-bis[(pyridin-4-yl)methyl]oxalamide}-μ-oxalato-cobalt(II)]

2014 ◽  
Vol 70 (9) ◽  
pp. m307-m308
Author(s):  
Hengye Zou ◽  
Yanjuan Qi
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Title Compound ◽  
Crystal Packing ◽  
Three Dimensional ◽  
Coordination Geometry ◽  
Distorted Octahedral Coordination ◽  
Distorted Octahedral Coordination Geometry ◽  
Distorted Octahedral ◽  
A Chain

In the polymeric title compound, [Co(C2O4)(C14H14N4O2)]n, the CoIIatom is six-coordinated by two N atoms from symmetry-related bis[(pyridin-4-yl)methyl]oxalamide (BPMO) ligands and four O atoms from two centrosymmetric oxalate anions in a distorted octahedral coordination geometry. The CoIIatoms are linked by the oxalate anions into a chain running parallel to [100]. The chains are linked by the BPMO ligands into a three-dimensional architecture. In addition, N—H...O hydrogen bonds stabilize the crystal packing.

scholarly journals Aquatris[1-(2,4-dioxo-2H-1-benzopyran-3-ylidene)ethan-1-olato]ethanolgadolinium(III) ethanol monosolvate

IUCrData ◽  
2019 ◽  
Vol 4 (4) ◽  
Author(s):  
Laura Gasque ◽  
Óscar Guzmán-Méndez ◽  
Sylvain Bernès
Keyword(s):  
Hydrogen Bonds ◽  
Water Molecule ◽  
Hydroxy Group ◽  
Title Compound ◽  
Three Dimensional ◽  
Coordination Geometry ◽  
Metal Centre ◽  
Anionic Ligands ◽  
Trigonal Prismatic ◽  
Main Ligand

The title compound, [Gd(C11H7O4)3(C2H5OH)(H2O)]·C2H5OH, was crystallized from ethanol, affording a solvate. The main ligand in the complex results from deprotonation of the hydroxy group in 3-acetyl-4-hydroxycoumarin (C11H8O4) and the resulting anionic ligands chelate the GdIII centre. Three anions, one ethanol and one water molecule are bonded to the lanthanide, giving an eight-coordinate metal centre with a slightly distorted trigonal–prismatic square-face-bicapped coordination geometry. All water and ethanol molecules participate in an intricate three-dimensional framework of hydrogen bonds. The complex is isostructural to the Tb and Dy compounds reported previously [Guzmán-Méndez et al. (2018). Inorg. Chem. 57, 908–911].

scholarly journals Bis[2-(4,5-diphenyl-1H-imidazol-2-yl)-4-nitrophenolato]copper(II) dihydrate: crystal structure and Hirshfeld surface analysis

2019 ◽  
Vol 75 (11) ◽  
pp. 1664-1671 ◽  
Author(s):  
Sailesh Chettri ◽  
Dhiraj Brahman ◽  
Biswajit Sinha ◽  
Mukesh M. Jotani ◽  
Edward R. T. Tiekink
Keyword(s):  
Chelate Ring ◽  
Three Dimensional ◽  
Hirshfeld Surface ◽  
Molecular Structures ◽  
Coordination Geometry ◽  
Bidentate Ligands ◽  
Metal Centre ◽  
Hirshfeld Surfaces ◽  
Square Planar ◽  
Intermolecular Contacts

The crystal and molecular structures of the title CuII complex, isolated as a dihydrate, [Cu(C21H14N3O3)2]·2H2O, reveals a highly distorted coordination geometry intermediate between square-planar and tetrahedral defined by an N2O2 donor set derived from two mono-anionic bidentate ligands. Furthermore, each six-membered chelate ring adopts an envelope conformation with the Cu atom being the flap. In the crystal, imidazolyl-amine-N—H...O(water), water-O—H...O(coordinated, nitro and water), phenyl-C—H...O(nitro) and π(imidazolyl)–π(nitrobenzene) [inter-centroid distances = 3.7452 (14) and 3.6647 (13) Å] contacts link the components into a supramolecular layer lying parallel to (101). The connections between layers forming a three-dimensional architecture are of the types nitrobenzene-C—H...O(nitro) and phenyl-C—H...π(phenyl). The distorted coordination geometry for the CuII atom is highlighted in an analysis of the Hirshfeld surface calculated for the metal centre alone. The significance of the intermolecular contacts is also revealed in a study of the calculated Hirshfeld surfaces; the dominant contacts in the crystal are H...H (41.0%), O...H/H...O (27.1%) and C...H/H...C (19.6%).

scholarly journals Diaquabis(1H-imidazole-4-carboxylato-κ2N3,O)cobalt(II)

2013 ◽  
Vol 69 (2) ◽  
pp. m94-m94 ◽  
Author(s):  
Beñat Artetxe ◽  
Leire San Felices ◽  
Aroa Pache ◽  
Santiago Reinoso ◽  
Juan M. Gutiérrez-Zorrilla
Keyword(s):  
Crystal Packing ◽  
Rotation Axis ◽  
Three Dimensional ◽  
Water Molecules ◽  
Coordination Geometry ◽  
Carboxylate Ligands ◽  
Dimensional Network ◽  
Centroid Distance ◽  
Distorted Octahedral Coordination Geometry ◽  
Distorted Octahedral

The title compound, [Co(C4H3N2O2)2(H2O)2], contains a CoIIcation on a twofold rotation axis, exhibiting a distorted octahedral coordination geometry. The equatorial plane is formed by twoN,O-bidentate 1H-imidazole-4-carboxylate ligands and the axial positions are occupied by water molecules. The crystal packing consists of a three-dimensional network stabilized by O—H...O and N—H...O hydrogen bonds, together with weak π–π interactions [centroid–centroid distance = 3.577 (2) Å] between the imidazole rings.

Three novel topologically different metal–organic frameworks built from 3-nitro-4-(pyridin-4-yl)benzoic acid

2019 ◽  
Vol 75 (2) ◽  
pp. 150-160 ◽  
Author(s):  
Tao Qin ◽  
Shunlin Zhang ◽  
Yixiong Wang ◽  
Tianjiao Hou ◽  
Dunru Zhu ◽  
...  
Keyword(s):  
Benzoic Acid ◽  
Gas Adsorption ◽  
Metal Organic Frameworks ◽  
Three Dimensional ◽  
Crystal Structure Analysis ◽  
Coordination Geometry ◽  
Design And Synthesis ◽  
Connected Node ◽  
Metal Organic ◽  
3D Framework

The design and synthesis of metal–organic frameworks (MOFs) have attracted much interest due to the intriguing diversity of their architectures and topologies. However, building MOFs with different topological structures from the same ligand is still a challenge. Using 3-nitro-4-(pyridin-4-yl)benzoic acid (HL) as a new ligand, three novel MOFs, namely poly[[(N,N-dimethylformamide-κO)bis[μ2-3-nitro-4-(pyridin-4-yl)benzoato-κ3 O,O′:N]cadmium(II)] N,N-dimethylformamide monosolvate methanol monosolvate], {[Cd(C12H7N2O4)2(C3H7NO)]·C3H7NO·CH3OH} n , (1), poly[[(μ2-acetato-κ2 O:O′)[μ3-3-nitro-4-(pyridin-4-yl)benzoato-κ3 O:O′:N]bis[μ3-3-nitro-4-(pyridin-4-yl)benzoato-κ4 O,O′:O′:N]dicadmium(II)] N,N-dimethylacetamide disolvate monohydrate], {[Cd2(C12H7N2O4)3(CH3CO2)]·2C4H9NO·H2O} n , (2), and catena-poly[[[diaquanickel(II)]-bis[μ2-3-nitro-4-(pyridin-4-yl)benzoato-κ2 O:N]] N,N-dimethylacetamide disolvate], {[Ni(C12H7N2O4)2(H2O)2]·2C4H9NO} n , (3), have been prepared. Single-crystal structure analysis shows that the CdII atom in MOF (1) has a distorted pentagonal bipyramidal [CdN2O5] coordination geometry. The [CdN2O5] units as 4-connected nodes are interconnected by L − ligands to form a fourfold interpenetrating three-dimensional (3D) framework with a dia topology. In MOF (2), there are two crystallographically different CdII ions showing a distorted pentagonal bipyramidal [CdNO6] and a distorted octahedral [CdN2O4] coordination geometry, respectively. Two CdII ions are connected by three carboxylate groups to form a binuclear [Cd2(COO)3] cluster. Each binuclear cluster as a 6-connected node is further linked by acetate groups and L − ligands to produce a non-interpenetrating 3D framework with a pcu topology. MOF (3) contains two crystallographically distinct NiII ions on special positions. Each NiII ion adopts an elongated octahedral [NiN2O4] geometry. Each NiII ion as a 4-connected node is linked by L − ligands to generate a two-dimensional network with an sql topology, which is further stabilized by two types of intermolecular OW—HW...O hydrogen bonds to form a 3D supramolecular framework. MOFs (1)–(3) were also characterized by powder X-ray diffraction, IR spectroscopy and thermogravimetic analysis. Furthermore, the solid-state photoluminescence of HL and MOFs (1) and (2) have been investigated. The photoluminescence of MOFs (1) and (2) are enhanced and red-shifted with respect to free HL. The gas adsorption investigation of MOF (2) indicates a good separation selectivity (71) of CO2/N2 at 273 K (i.e. the amount of CO2 adsorption is 71 times higher than N2 at the same pressure).

catena-Poly[bis(μ-2,2′-bipyridin-6-olato)-κ3N,N′:O;O:N,N′-dicopper(I,II) [[tetrafluoridoniobium(V)]-μ-oxido]]

2013 ◽  
Vol 69 (8) ◽  
pp. 833-836 ◽  
Author(s):  
Zhi-Guo Zhong ◽  
Yu-Quan Feng ◽  
Ping Zhang
Keyword(s):  
Three Dimensional ◽  
Coordination Shell ◽  
Stacking Interactions ◽  
Coordination Geometry ◽  
X Ray Diffraction ◽  
Metal Centre ◽  
X Ray ◽  
Centroid Distance ◽  
Shell Forming ◽  
Infinite Linear

A novel copper–niobium oxyfluoride, {[Cu2(C10H7N2O)2][NbOF4]}n, has been synthesized by a hydrothermal method and characterized by elemental analysis, EDS, IR, XPS and single-crystal X-ray diffraction. The structural unit consists of oneC2-symmetric [NbOF4]−anion and one centrosymmetric coordinated [Cu2(obpy)2]+cation (obpy is 2,2′-bipyridin-6-olate). In the [NbOF4]−anion, each NbVmetal centre is five-coordinated by four F atoms and one O atom in the first coordination shell, forming a square-pyramidal coordination geometry. These square pyramids are then further connected to each othervia transO atoms [Nb—O = 2.187 (3) Å], forming an infinite linear {[NbOF4]−}npolyanion. In the coordinated [Cu2(obpy)2]+cation, the oxidation state of each Cu site is disordered, which is confirmed by the XPS results. The disordered Cu sites are coordinated by two N atoms and one O atom from two different obpy ligands. The [NbOF4]−and [Cu2(obpy)2]+units are assembledviaweak C—H...F hydrogen bonds, resulting in the formation of a three-dimensional supramolecular structure. π–π stacking interactions between the pyridine rings [centroid–centroid distance = 3.610 (2) Å] may further stabilize the crystal structure.

Coordination Polymers Constructed from TCNQ2– Anions and Chelating Ligands

2014 ◽  
Vol 67 (12) ◽  
pp. 1871 ◽  
Author(s):  
Brendan F. Abrahams ◽  
Robert W. Elliott ◽  
Richard Robson
Keyword(s):  
Coordination Polymers ◽  
3D Structure ◽  
Three Dimensional ◽  
Binding Mode ◽  
Coordination Geometry ◽  
Chelating Ligands ◽  
Metal Centre ◽  
3D Network ◽  
2D And 3D ◽  
Dianionic Form

Coordination polymers containing tetracyanoquinodimethane (TCNQ) in its dianionic form, TCNQ–II, have been formed by combining the acid form of the dianion, TCNQH2, with divalent metal centres in the presence of chelating ligands such as 2,2′-bipyridine (bipy) and 1,10-phenanthroline (phen). When MnII or CdII is employed, two-dimensional (2D) corrugated sheet structures with the formula MII(TCNQ–II)L (M = Mn, Cd; L = bipy, phen) are obtained. In contrast, when CoII is used as the metal centre a complex three-dimensional (3D) structure of composition [CoII(TCNQ–II)(phen)] is formed. Despite the significant differences between the 2D and 3D network structures, the metal coordination geometry and the binding mode of the TCNQ dianion are very similar in all cases.

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