Macrocyclic Ligand Design. Structure—Function Relationships Underlying the Interaction of Substituted Derivatives of Oxygen-Nitrogen Macrocycles with Selected Transition and Post Transition Metal Ions

1998 ◽  
Vol 51 (11) ◽  
pp. 985 ◽  
Author(s):  
Ian M. Atkinson ◽  
Karl A. Byriel ◽  
Peter S. K. Chia ◽  
Colin H. L. Kennard ◽  
Anthony J. Leong ◽  
...  
Keyword(s):  
Complex Cation ◽  
Macrocyclic Ligand ◽  
Binding Constants ◽  
Transition Metal Ions ◽  
Distorted Octahedral Geometry ◽  
Nickel Ion ◽  
Design Structure ◽  
Distorted Octahedral ◽  
Meso Form ◽  
Derivatives Of

The effect of methyl substitution on 15- and 17-membered macrocycles (incorporating N2O2- and N3O2-donors, respectively) on their interaction with cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) and lead(II) has been investigated. The results are compared with those obtained for the corresponding complexes of the unsubstituted (parent) rings. Binding constants for the formation of the metal complexes have been determined potentiometrically in 95% methanol (I = 0·1; Et4NClO4). An X-ray crystallographic study of [NiL(H2O)] (ClO4)2 (where L is the dimethyl derivative of a 17-membered, N3O2-donor macrocycle) confirms that the nickel ion is six-coordinate, with the complex cation exhibiting a distorted octahedral geometry defined by all five donor atoms of the O2N3-macrocycle (in its meso form) and the oxygen of the water molecule. In this structure the macrocyclic backbone incorporating the N3-donor fragment is arranged facially. Molecular mechanics modelling of this complex predicts that the observed facial configuration will be favoured over an alternative facial arrangement or a meridional one.

scholarly journals Bis[tetrakis(pyridin-2-yl)methane-κ3N,N′,N′′]cobalt(II) tetrakis(thiocyanato-κN)cobaltate(II) methanol monosolvate

2014 ◽  
Vol 70 (3) ◽  
pp. m96-m97 ◽  
Author(s):  
Yuya Tsunezumi ◽  
Kouzou Matsumoto ◽  
Shinya Hayami ◽  
Akira Fuyuhiro ◽  
Satoshi Kawata
Keyword(s):  
Complex Anion ◽  
Complex Cation ◽  
Solvent Molecule ◽  
Octahedral Geometry ◽  
Title Complex ◽  
Distorted Octahedral Geometry ◽  
Weak Hydrogen Bond ◽  
Tetrahedral Geometry ◽  
Distorted Tetrahedral Geometry ◽  
Distorted Octahedral

The title complex, [Co(C21H16N4)2][Co(NCS)4]·CH3OH, consists of one [Co{C(py)4}2]2+complex cation [C(py)4= tetrakis(pyridin-2-yl)methane], one [Co(NCS)4]2−complex anion and a methanol solvent molecule. In the cation, the CoIIatom is coordinated by six N atoms of two C(py)4ligands in a distorted octahedral geometry. In the anion, the CoIIatom is coordinated by the N atoms of four NCS−ligands in a distorted tetrahedral geometry. The methanol molecule is disordered and was modelled over three orientations (occupancies 0.8:0.1:0.1). There are two weak hydrogen-bond-like interactions between the methanol solvent molecule and NCS−ligands of the anion [O...S = 3.283 (3) and 3.170 (2) Å].

scholarly journals fac-Triaqua(2,2′-bipyridine-κ2 N,N′)(nitrato-κO)cobalt(II) chloride

IUCrData ◽  
2018 ◽  
Vol 3 (6) ◽  
Author(s):  
Mouhamadou Birame Diop ◽  
Libasse Diop ◽  
Sylvain Bernès
Keyword(s):  
Complex Cation ◽  
Three Dimensional ◽  
Chloride Ions ◽  
Chloride Anion ◽  
Octahedral Geometry ◽  
Distorted Octahedral Geometry ◽  
Water Molecules ◽  
Nitrate Anion ◽  
Asymmetric Unit ◽  
Distorted Octahedral

The asymmetric unit of the title complex, [Co(NO3)(C10H8N2)(H2O)3]Cl, consists of a chloride anion and a complex cation, which is built on a monodentate nitrate anion, three water molecules and one bidentate 2,2′-bipyridine molecule, coordinated to a CoII cation, in a distorted octahedral geometry. The water molecules are arranged in a facial geometry, and serve as donors for hydrogen bonding. Acceptor sites in the crystal are chloride ions and one O atom of the coordinating nitrate ion. A three-dimensional framework is formed, based on O—H...O and O—H...Cl contacts.

scholarly journals Crystal structure oftrans-bis(ethane-1,2-diamine-κ2N,N′)bis(thiocyanato-κN)chromium(III) perchlorate from synchrotron data

2015 ◽  
Vol 71 (6) ◽  
pp. 650-653 ◽  
Author(s):  
Dohyun Moon ◽  
Jong-Ha Choi
Keyword(s):  
Crystal Structure ◽  
Rotation Axis ◽  
Complex Cation ◽  
Octahedral Geometry ◽  
Distorted Octahedral Geometry ◽  
Inversion Symmetry ◽  
Asymmetric Unit ◽  
Intermolecular Hydrogen Bonds ◽  
Distorted Octahedral ◽  
Cl Atom

The structure of the title compound, [Cr(NCS)2(C2H8N2)2]ClO4, has been determined from synchroton data. The asymmetric unit consists of one half of a centrosymmetric CrIIIcomplex cation and half of a perchlorate anion with the Cl atom on a twofold rotation axis. The CrIIIion is coordinated by the four N atoms of two ethane-1,2-diamine (en) ligands in the equatorial plane and two N-bound thiocyanate (NCS−) anions in atrans-axial arrangement, displaying a slightly distorted octahedral geometry with crystallographic inversion symmetry. The Cr—N(en) bond lengths are in the range 2.053 (16)–2.09 (2) Å, while the Cr—N(thiocyanate) bond length is 1.983 (2) Å. The five-membered en rings are disordered over two sites, with occupancy ratios of 0.522 (16):0.478 (16). Each ClO4−anion is disordered over two sites with equal occupancy. The crystal structure is stabilized by intermolecular hydrogen bonds involving the en NH2groups as donors and perchlorate O and thiocyanate S atoms as acceptors.

scholarly journals Crystal structure of bis[trans-(1,4,8,11-tetraazacyclotetradecane-κ4N)bis(thiocyanato-κN)chromium(III)] tetrachloridozincate from synchrotron data

2015 ◽  
Vol 71 (5) ◽  
pp. 540-543 ◽  
Author(s):  
Dohyun Moon ◽  
Keon Sang Ryoo ◽  
Jong-Ha Choi
Keyword(s):  
Crystal Packing ◽  
Rotation Axis ◽  
Complex Cation ◽  
Distorted Octahedral Geometry ◽  
Asymmetric Unit ◽  
Tetrahedral Geometry ◽  
Distorted Tetrahedral Geometry ◽  
Hydrogen Bonding Interactions ◽  
Distorted Octahedral ◽  
The Mean

The structure of the title compound, [Cr(NCS)2(cyclam)]2[ZnCl4] (cyclam = 1,4,8,11-tetraazacyclotetradecane, C10H24N4), has been determined from synchrotron data. The asymmetric unit contains two independent halves of the CrIIIcomplex cations and half of a tetrachloridozincate anion. In each complex cation, the CrIIIatom is coordinated by the four N atoms of the cyclam ligand in the equatorial plane and by two N-bound NCS−anions in atransaxial arrangement, displaying a distorted octahedral geometry with crystallographic inversion symmetry. The mean Cr—N(cyclam) and Cr—N(NCS) bond lengths are 2.065 (4) and 1.995 (6) Å, respectively. The macrocyclic cyclam moieties adopt centrosymmetrictrans-III configurations with six- and five-membered chelate rings in chair andgaucheconfigurations, respectively. The [ZnCl4]2−anion, which lies about a twofold rotation axis, has a slightly distorted tetrahedral geometry. The crystal packing is stabilized by hydrogen-bonding interactions between the N—H groups of the cyclam ligands, the S atoms of the NCS−groups and the Cl−ligands of the anion.

scholarly journals The first structural characterization of the protonated azacyclam ligand in catena-poly[[[(perchlorato)copper(II)]-μ-3-(3-carboxypropyl)-1,5,8,12-tetraaza-3-azoniacyclotetradecane] bis(perchlorate)]

2019 ◽  
Vol 75 (11) ◽  
pp. 1700-1704
Author(s):  
Liudmyla V. Tsymbal ◽  
Vladimir B. Arion ◽  
Yaroslaw D. Lampeka
Keyword(s):  
Carboxylic Acid ◽  
Metal Ion ◽  
Macrocyclic Ligand ◽  
Acid Group ◽  
Distorted Octahedral Geometry ◽  
Equatorial Orientation ◽  
Carboxylic Acid Group ◽  
Bond Lengths ◽  
Distorted Octahedral

The asymmetric unit of the title compound, catena-poly[[[(perchlorato-κO)copper(II)]-μ-3-(3-carboxypropyl)-1,5,8,12-tetraaza-3-azoniacyclotetradecane-κ4 N 1,N 5,N 8,N 12] bis(perchlorate)], {[Cu(C13H30N5O2)(ClO4)](ClO4)2} n , (I), consists of a macrocyclic cation, one coordinated perchlorate anion and two perchlorate ions as counter-anions. The metal ion is coordinated in a tetragonally distorted octahedral geometry by the four secondary N atoms of the macrocyclic ligand, the mutually trans O atoms of the perchlorate anion and the carbonyl O atom of the protonated carboxylic acid group of a neighbouring cation. The average equatorial Cu—N bond lengths [2.01 (6) Å] are significantly shorter than the axial Cu—O bond lengths [2.379 (8) Å for carboxylate and average 2.62 (7) Å for disordered perchlorate]. The coordinated macrocyclic ligand in (I) adopts the most energetically favourable trans-III conformation with an equatorial orientation of the substituent at the protonated distal 3-position N atom in a six-membered chelate ring. The coordination of the carboxylic acid group of the cation to a neighbouring complex unit results in the formation of infinite chains running along the b-axis direction, which are crosslinked by N—H...O hydrogen bonds between the secondary amine groups of the macrocycle and O atoms of the perchlorate counter-anions to form sheets lying parallel to the (001) plane. Additionally, the extended structure of (I) is consolidated by numerous intra- and interchain C—H...O contacts.

scholarly journals Crystal structure ofcis-aquachlorido(rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ4N)chromium(III) tetrachloridozincate trihydrate from synchrotron data

2015 ◽  
Vol 71 (9) ◽  
pp. 1054-1057
Author(s):  
Dohyun Moon ◽  
Jong-Ha Choi
Keyword(s):  
Crystal Packing ◽  
Complex Cation ◽  
Macrocyclic Ligand ◽  
Three Dimensional ◽  
Chloride Ion ◽  
Water Molecules ◽  
Bond Lengths ◽  
Dimensional Network ◽  
Distorted Octahedral ◽  
Additional Water

The structure of the title compound,cis-[CrCl(cycb)(H2O)][ZnCl4]·3H2O (cycbisrac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane; C16H36N4), has been determined from synchrotron data. In the complex cation, the CrIIIion is bound by four N atoms from the tetradentate cycbligand, a chloride ion and one water molecule in acisarrangement, displaying a distorted octahedral coordination geometry. The distorted tetrahedral [ZnCl4]2−anion and three additional water molecules remain outside the coordination sphere. The Cr—N(cycb) bond lengths are in the range of 2.0837 (14) to 2.1399 (12) Å while the Cr—Cl and Cr—(OH2) bond lengths are 2.2940 (8) and 2.0082 (13) Å, respectively. The crystal packing is stabilized by hydrogen-bonding interactions between the N—H groups of the macrocyclic ligand, the O—H groups of the water molecules and the Cl atoms of the tetrachloridozincate anion, leading to the formation of a three-dimensional network.

scholarly journals Crystal structure, electrochemical and spectroscopic investigation of mer-tris[2-(1H-imidazol-2-yl-κN 3)pyrimidine-κN 1]ruthenium(II) bis(hexafluoridophosphate) trihydrate

2018 ◽  
Vol 74 (7) ◽  
pp. 874-877 ◽  
Author(s):  
Naheed Bibi ◽  
Renan Barrach Guerra ◽  
Luis Enrique Santa Cruz Huamaní ◽  
André Luiz Barboza Formiga
Keyword(s):  
Crystal Structure ◽  
Complex Cation ◽  
Three Dimensional ◽  
Bidentate Ligand ◽  
Distorted Octahedral Geometry ◽  
Water Molecules ◽  
Hydrogen Atoms ◽  
Counter Ions ◽  
Ligand Charge Transfer ◽  
Distorted Octahedral

The crystal structure of the title compound, [Ru(C7H6N4)3](PF6)2·3H2O, a novel RuII complex with the bidentate ligand 2-(1H-imidazol-2-yl)pyrimidine, comprises a complex cation in the meridional form exclusively, with a distorted octahedral geometry about the ruthenium(II) cation. The Ru—N bonds involving imidazole N atoms are comparatively shorter than the Ru—N bonds from pyrimidine because of the stronger basicity of the imidazole moiety. The three-dimensional hydrogen-bonded network involves all species in the lattice with water molecules interacting with both counter-ions and NH hydrogen atoms from the complex. The supramolecular structure of the crystal also shows that two units of the complex bind strongly through a mutual N—H...N bond. The electronic absorption spectrum of the complex displays an asymmetric band at 421 nm, which might point to the presence of two metal-to-ligand charge-transfer (MLCT) bands. Electrochemical measurements show a quasi-reversible peak referring to the RuIII/RuII reduction at 0.87 V versus Ag/AgCl.

scholarly journals Crystal structure of a dinuclear CoIIcomplex with bridging fluoride ligands: di-μ-fluorido-bis{tris[(6-methylpyridin-2-yl)methyl]amine}dicobalt(II) bis(tetrafluoridoborate)

2014 ◽  
Vol 70 (11) ◽  
pp. m359-m360 ◽  
Author(s):  
Masataka Inomata ◽  
Yusaku Suenaga
Keyword(s):  
Crystal Structure ◽  
Complex Cation ◽  
Three Dimensional ◽  
High Spin State ◽  
Octahedral Geometry ◽  
Distorted Octahedral Geometry ◽  
Methyl Amine ◽  
Dimensional Network ◽  
Distorted Octahedral ◽  
Fluoride Ligands

Reaction of Co(BF4)2·6H2O with tris[(6-methylpyridin-2-yl)methyl]amiine in methanol results in a fluoride abstraction from BF4−, yielding the unexpected title compound, [Co2F2(C21H24N4)2](BF4)2. The complex cation consists of two inversion-related [Co(C21H24N4)]2+moieties bridged by a pair of fluoride ligands. The CoIIcation is six-coordinated in a distorted octahedral geometry and forms a +II high-spin state. In the crystal, the complex cation and the BF4−anion are connected by C—H...F hydrogen bonds, forming a three-dimensional network. An intramolecular C—H...F hydrogen bond is also observed.

scholarly journals Crystal structure oftrans-(1,8-dibutyl-1,3,6,8,10,13-hexaazacyclotetradecane-κ4N3,N6,N10,N13)bis(perchlorato-κO)copper(II) from synchrotron data

2015 ◽  
Vol 71 (2) ◽  
pp. 136-138 ◽  
Author(s):  
Dae-Woong Kim ◽  
Jong Won Shin ◽  
Dohyun Moon
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Bond Length ◽  
Macrocyclic Ligand ◽  
Three Dimensional ◽  
Distorted Octahedral Geometry ◽  
Inversion Center ◽  
Asymmetric Unit ◽  
Dimensional Network ◽  
Distorted Octahedral

The structure of the title compound, [Cu(ClO4)2(C16H38N6)] has been determined from synchrotron data, λ = 0.62988 Å. The asymmetric unit comprises one half of the CuIIcomplex as the CuIIcation lies on an inversion center. It is coordinated by the four secondary N atoms of the macrocyclic ligand and the mutuallytransO atoms of the two perchlorate ions in a tetragonally distorted octahedral geometry. The average equatorial Cu—N bond length is significantly shorter than the average axial Cu—O bond length [2.010 (4) and 2.569 (1) Å, respectively]. Intramolecular N—H...O hydrogen bonds between the macrocyclic ligand and uncoordinating O atoms of the perchlorate ligand stabilize the molecular structure. In the crystal structure, an extensive series of intermolecular N—H...O and C—H...O hydrogen bonds generate a three-dimensional network.

Unique Occurrence of Cationic and Anionic Bis-1,2-diaminocyclohexane Copper(II) Units in a Double Complex Salt

2016 ◽  
Vol 69 (5) ◽  
pp. 533
Author(s):  
Norman Kelly ◽  
Marco Wenzel ◽  
Thomas Doert ◽  
Kerstin Gloe ◽  
Jan J. Weigand ◽  
...  
Keyword(s):  
Complex Cation ◽  
Complex Salt ◽  
Distorted Octahedral Geometry ◽  
Double Complex ◽  
Coordination Environment ◽  
Double Complex Salt ◽  
Square Planar ◽  
Distorted Octahedral ◽  
Jahn Teller ◽  
Donor Coordination

The reaction of (±)-trans-diaminocyclohexane (dach) with copper(ii) sulfate in water resulted in the spontaneous formation of a double complex salt of type [Cu(dach)2(H2O)2][Cu(dach)2(SO4)2]·6H2O, whose X-ray structure confirmed the presence of the same square-planar Cu(dach)22+ coordination motif in both the complex cation and anion. Each copper centre adopts a Jahn–Teller-distorted octahedral geometry. Both axial positions of the metal centre in the complex cation are occupied by water molecules, whereas two monodentate sulfato ions occupy the corresponding sites in the complex anion, leading to a trans N4O2-donor coordination environment in each ion.

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