scholarly journals Stereochemical Geometries and Photoluminescence in Pseudo-Halido-Zinc(II) Complexes. Structural Comparison between the Corresponding Cadmium(II) Analogs

Inorganics ◽  
2021 ◽  
Vol 9 (7) ◽  
pp. 53
Author(s):  
Franz A. Mautner ◽  
Roland C. Fischer ◽  
Ana Torvisco ◽  
Nahed M. H. Salem ◽  
Amber R. Dugas ◽  
...  

Six pseudohalide zinc(II) containing a variety of N-donor auxiliary amines were structurally characterized. These include two mononuclear trigonal bipyramidal [Zn(NTB)(N3)]ClO4·½H2O (3) and [Zn(TPA)(NCS)]ClO4 (4), two distorted octahedral [Zn(1,8-damnph)2(dca)2] (5) and [Zn(8-amq)2(dca)2] (6a) as well as two 1D polymeric chains catena-[Zn(isq)2(μ1,5-dca)2] (7) and catena-[Zn(N,N-Me2en)2(μ1,5-dca)]dca (8), where NTB = tris(2-benzimidazolylmethyl)amine, TPA = tris(2-pyridylmethyl)amine, 1,8-damnph = 1,8-diaminonaphthalene, 8-amq = 8-amino-quinoline, isq = isoquinoline (isq) and N,N-Me2en = N,N-dimethylethylenediamine. In general, with the exception of 6 and 8, the complexes exhibited luminescence emission in MeOH associated with red shift of the emission maxima, and the strongest visible fluorescence peak was detected at 421 nm (λex = 330 nm) in the case of Complex 5.

2017 ◽  
Vol 73 (12) ◽  
pp. 1977-1980
Author(s):  
Volodymyr M. Hiiuk ◽  
Diana D. Barakhty ◽  
Sergiu Shova ◽  
Ruslan A. Polunin ◽  
Il'ya A. Gural'skiy

In the title polymeric complex, {[Fe(C12H10N2)2(H2O)4](CH3C6H4SO3)2·2CH3OH}n, the FeIIcation, located on an inversion centre, is coordinated by four water molecules in the equatorial positions and two 1,2-bis(pyridin-4-yl)ethene molecules in the axial positions. This results in a distorted octahedral geometry for the [N2O4] coordination polyhedron. The 1,2-bis(pyridin-4-yl)ethene molecules bridge the FeIIcations, forming polymeric chains running along thea-axis direction. Stabilization of the crystal structure is provided by O—H...O hydrogen bonds; these are formed by coordinated water molecules as donors towards the O atoms of the methanol molecules and tosylate anions as acceptors of protons, leading to the formation of a three-dimensional supramolecular network. Weak C—H...O hydrogen bonds are also observed in the crystal.


IUCrData ◽  
2020 ◽  
Vol 5 (10) ◽  
Author(s):  
Rafael A. Adrian ◽  
Diego R. Hernandez ◽  
Hadi D. Arman

The central copper(II) atom of the title salt, {[Cu(CF3SO3)(CH3CN)2(C12H12N2O2)](CF3SO3)} n or [[Cu(CH3CN)2(diOMe-bpy)(CF3SO3)](CF3SO3)] n where diOMe-bpy is 4,4′-dimethoxy-2,2′-bipyridine, C12H12N2O2, is sixfold coordinated by the N atoms of the chelating bipyridine ligand, the N atoms of two acetonitrile molecules, and two trifluoromethanesulfonate O atoms in a tetragonally distorted octahedral shape. The formation of polymeric chains [Cu(CH3CN)2(diOMe-bpy)(CF3SO3)]+ n leaves voids for the non-coordinating trifluoromethanesulfonate anions that interact with the complex through weak hydrogen bonds. The presence of weakly coordinating ligands like acetonitrile and trifluoromethanesulfonate makes the title compound a convenient starting material for the synthesis of novel metal–organic frameworks.


1992 ◽  
Vol 47 (3) ◽  
pp. 301-304 ◽  
Author(s):  
Stefan Vogler ◽  
Kurt Dehnicke

The title compound has been prepared by the reaction o f [WCl4(NSeCl)]2 with PPh4Cl in CH2Cl2 solution. It forms red crystals, which were characterized by an X-ray structure determination. Space group P21/c, Z = 4, 3856 observed unique reflections, R = 0.073. Lattice dimensions at 25 °C: a = 2266.0(5), b = 1121.0(2), c = 2013.0(4) pm, β = 109.66(3)°. The structure consists o f PPh4+ ions and anions [WCl5(NSeCl2)]2-, in which the tungsten atom is surrounded in a distorted octahedral way by five chlorine atoms and by the nitrogen atom of the (NSeCl2)3- ligand. The W = N = SeCl2 group is characterized by WN and SeN double bonds; the selenium atom has a pseudo trigonal-bipyramidal coordination with the N atom and two lone pairs in equatorial and the chlorine atoms in axial positions.


1986 ◽  
Vol 41 (1-2) ◽  
pp. 211-214 ◽  
Author(s):  
Igor M. Lazarev ◽  
Gennadii V. Dolgushin ◽  
Valentin P. Feshin ◽  
Michail G. Voronkov

SnCl4 Complexes with methylaryl ethers and their 35Cl NQR spectra have been obtained. All these complexes, except SnCl4 · 1,2-(CH3O)2C6H4, have a trigonal-bipyramidal structure. The latter compound has an essentially distorted octahedral structure. One of the ligand oxygen atoms takes part in the formation of the SnCl4 complex with 1,3-, 1,4-(CH3O)2C6H4 and RNO2. These complexes have a trigonal-bipyramidal structure too.


1987 ◽  
Vol 42 (2) ◽  
pp. 195-202 ◽  
Author(s):  
W. S. Sheldrick ◽  
P. Bell

Abstract The reaction of 8-aza-and 7-deaza-8-aza-purines with Cu2+ cations in acid solution has been studied. At a pH value of 2, the 8-azaadenine complex [Cu(H2O)4(AAdH)2](NO3)2 (1), which displays Cu-N9 coordination, may be isolated from solution. The reaction of CuCl2 with 8-aza-hypoxanthine in concentrated HCl solution leads to ring opening at C2 of the azapurine with subsequent formation of dichlorobis[(5-amino-4-carboxamide)[1 - 3]triazole] copper(II) dihydrate 2, in which the triazole ligands display a chelating function, coordinating the metal via N7 and O6. The results for 1 and 2 suggest that copper coordination of the azapurine base is not a prerequisite for opening of the pyrimidine ring. Respectively N9-and N8-coordinated complexes [CUCl3(AllH3)]n 3 and [CuCl2(H2O)(MAllH)]n (4) of allopurinol (AllH2) and 9-methylallopurinol (MAllH) may be prepared by the reaction of CuCl2 with the respective bases in HCl solution. In contrast, with the analogous 1-methyl-4-aminopyrazolo[3,4-d]pyrimidine MAPP, only the salt (MAPPH)4(CU2Cl8) (5) could be isolated under similar conditions, indicating that N8 is less attractive as a binding site in this 7-deaza-8-azaadenine derivative. The structures of 1-5 have been established by X-ray structural analysis. A distorted octahedral [4+2]geometry is found for the copper atoms in 1 and 2. Chlorine bridged polymeric chain structures are adopted by the complexes 3 and 4. An intermediate coordination geometry between trigonal bipyramidal and square-pyramidal is observed for the metal atoms in 3, a distorted square-pyramidal geometry in 4.


2018 ◽  
Vol 2018 ◽  
pp. 1-10
Author(s):  
Ting Liu ◽  
Yi-An Wang ◽  
Qing Zang ◽  
Guo-Qing Zhong

A Cu(II) complex [Cu(bipy)(H2O)2(SO4)]n (bipy = 2,2′-bipyridine) was synthesized by hydrothermal method and characterized structurally by elemental analyses, single crystal X-ray diffraction, infrared spectra, and thermogravimetry and differential scanning calorimetry. The Cu(II) was hexacoordinated by two N atoms from bipy, two O atoms from different sulfate radical anions, and two O atoms from two water molecules, forming a slightly distorted octahedral geometry, and bridged by sulfato groups into polymeric chains. Under the condition of physiological pH, the interaction mechanism between the complex and hsDNA was explored with acridine orange as a fluorescence probe by spectroscopic methods. The binding modes between the complex and hsDNA were the electrostatic and embedded modes.


1987 ◽  
Vol 40 (2) ◽  
pp. 347 ◽  
Author(s):  
P Osvath ◽  
NF Curtis ◽  
DC Weatherburn

The preparations of the pentaazamacrocyclic ligands 1,4,7,10,13-pentaazacyclopentadecane, cpad , l,4,7,l0,13-pentaazacyclohexadecane, ched , l,4,7,l0,14-pentaazacycloheptadecane, chad , 1,4,7,11,14-pentaazacycloheptadecane, cnad , 1,4,7,11,15-pentaazacyclooctadecane, cnad , 1,4,8,11,15-pentaazacyclooctadecane, cnad , 1,4,8,12,16-pentaazacyclononadecane, cnad , and 1,5,9,13,17-pentaazacycloeicosane, ceic , as well as the new linear pentaamine N-(3-aminopropy1)- N'-[3-[(3-aminopropyl)amino] propyl ]propane-1,3-diamine, tpah , are described. Copper(II) and nickel(II) complexes of the above ligands have been prepared and characterized. The nickel(II) complexes of the smaller macrocycles and the linear pentaamine contain NiII in a tetragonally distorted octahedral environment in the presence of coordinating anions or in aqueous solution but the [Ni( cnad )]2+ and [Ni( ceic )]2+ cations are five-coordinate both in the solid state and in aqueous solution. The copper(II) complexes of the macrocyclic pentaamines appear to be square-pyramidal on the basis of their electronic spectra, whereas the complex [cu( tpah )]2+ is probably trigonal- bipyramidal.


1983 ◽  
Vol 36 (1) ◽  
pp. 183 ◽  
Author(s):  
EJ O'Reilly ◽  
G Smith ◽  
CHL Kennard ◽  
AH White

The crystal structures of two copper(II) complexes of the herbicide Picloram (4-amino-3,5,6-trichloro- pyridine-2-carboxylic acid) have been determined by single-crystal X-ray diffractometry. Bis(4-amino- 3,5,6-trichloropyridine-2-carboxylato)aquacopper(II) dihydrate (1) is monoclinic, space group C2/c, with Z 4 in a cell of dimensions a 15.593(6), b 7.940(6), c 16.983(6) �, β 107.58(3)�. The structure was refined to a residual R 0.046 for 905 'observed' reflections. Complex (1) is trigonal bipyramidal with the trigonal plane consisting of oxygens from two picolinate ligands [Cu-O 1.995(5) �] and a water molecule [Cu-O 2.080(5) �]. The apical positions are occupied by pyridine ring nitrogens from the Picloram ligands [Cu-N 2.021(5) �]. Bis(4-amino-3,5,6-trichloropyridine- 2-carboxylato)bis(pyrimidin-2-amine)copper(II) (2) is monoclinic, space group P2,/c, with Z 4 in a cell of dimensions a 12.3 11(5), b 15.435(5), c 15.320(6) �, β 115.95(3)�, and gave a final R 0.059 for 2429 'observed' reflections. In complex (2), the copper(II) atom has a tetragonally distorted octahedral stereochemistry with the Picloram ring nitrogens once again occupying the two axial positions [Cu-N 2.586(7) and 2.611(7) �]. The square plane consists of two carboxylato oxygens [Cu-O 1.941(6) and 1.960(7) �] and two hetero-nitrogens from pyrimidin-2-amine ligands [Cu-N 2.048(6) and 2.054(6) �].


2014 ◽  
Vol 70 (12) ◽  
pp. 1101-1104 ◽  
Author(s):  
Eduard B. Coropceanu ◽  
Ana Dreab ◽  
Lilia Croitor

Two new mononuclear coordination compounds, bis{4-[(hydroxyimino)methyl]pyridinium} diaquabis(pyridine-2,5-dicarboxylato-κ2N,O2)zincate(II), (C6H7N2O)2[Zn(C7H3NO4)2(H2O)2], (1), and (pyridine-2,6-dicarboxylato-κ3O2,N,O6)bis[N-(pyridin-4-ylmethylidene-κN)hydroxylamine]zinc(II), [Zn(C7H3NO4)(C6H6N2O)2], (2), have been synthesized and characterized by single-crystal X-ray diffractometry. The centrosymmetric ZnIIcation in (1) is octahedrally coordinated by two chelating pyridine-2,5-dicarboxylate ligands and by two water molecules in a distorted octahedral geometry. In (2), the ZnIIcation is coordinated by a tridentate pyridine-2,6-dicarboxylate dianion and by twoN-(pyridin-4-ylmethylidene)hydroxylamine molecules in a distortedC2-symmetric trigonal bipyramidal coordination geometry.


2014 ◽  
Vol 70 (7) ◽  
pp. i33-i33 ◽  
Author(s):  
Kewen Sun ◽  
Angela Möller

Dimanganese(II) hydroxide vanadate was obtained from hydrothermal reactions. The crystal structure of the title compound is isotypic with that of Zn2(OH)[VO4]. Three crystallographically independent Mn2+ions are present, one (site symmetry .m.) with a distorted trigonal-bipyramidal and two (site symmetries .m. and 1) with distorted octahedral coordination spheres. These polyhedra are linked through common edges, forming a corrugated layer-type of structure extending parallel to (100). A three-dimensional framework resultsviaadditional Mn—O—V—O—Mn connectivities involving the two different tetrahedral [VO4] units (each with point-group symmetry .m.). O—H...O hydrogen bonds (one bifurcated) between the OH functions (both with point-group symmetry .m.) and the [VO4] units complete this arrangement.


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