Argentophilic Interactions in Two AgI Complexes of 3-(2-(Pyridin-4-yl)ethyl)pentane-2,4-dione, a Promising Ditopic Ligand

Crystals ◽  
2019 ◽  
Vol 9 (8) ◽  
pp. 414
Author(s):  
Steven van Terwingen ◽  
Ulli Englert
Keyword(s):  
Supramolecular Structure ◽  
Silver Complexes ◽  
Bridging Ligands ◽  
Counter Ions ◽  
Additional Coordination ◽  
Enol Tautomer ◽  
Argentophilic Interactions ◽  
Interionic Interactions ◽  
Linear Coordination ◽  
Ditopic Ligand

Reactions of 3-(2-(pyridin-4-yl)ethyl)pentane-2,4-dione (HacacPyen) with AgPF6 and AgBF4 afforded cationic silver complexes [Ag(HacacPyen)2]+ with essentially linear coordination of the Ag I cation by two pyridine N atoms. Rather unexpectedly, the HacacPyen ligands in the PF6- salt 1 adopt the diketo form, in contrast to the uncoordinated HacacPyen molecule, whereas the corresponding BF4- salt 2 and the majority of 3-substituted acetylacetones crystallizes as the enol tautomer. In both compounds 1 and 2, complex cations aggregate via short Ag...Ag interactions to pairs. These contacts amount to 3 . 21 Å in 1 and 3 . 26 Å or 3 . 31 Å in 2. As they are unsupported by any additional bridging ligands and correspond to the closest interionic interactions between neighbouring complex cations, they may be addressed as argentophilic interactions. The PF6- anions in 1 and the BF4- counter ions in 2 are involved in long and presumably electrostatic Ag...F contacts of ca. 2 . 9 Å. Additional coordination between Ag I and keto O atoms of symmetry-equivalent ligands occurs in 1 and leads to an extended two-periodic supramolecular structure.

Synthesis and Crystal Structures of Silver Thianthrene Complexes with Weakly Coordinating Anions

2007 ◽  
Vol 62 (10) ◽  
pp. 1291-1297 ◽  
Author(s):  
Rachmat Triandi ◽  
Johannes Beck
Keyword(s):  
Sulfur Dioxide ◽  
Silver Complexes ◽  
Molecular Symmetry ◽  
Bridging Ligands ◽  
Liquid Sulfur ◽  
Structure Selection ◽  
Weakly Coordinating Anions ◽  
Secondary Bonds ◽  
Weakly Coordinating ◽  
Selection Of

Two novel silver complexes with thianthrene (TA) as a ligand have been synthesized in the poorly coordinating solvent liquid sulfur dioxide, using silver salts with weakly coordinating anions [BF4]− and [SbF6]−. Both colorless compounds contain discrete molecular entities and SO2 molecules included in the crystal structure. Selection of crystals and the diffraction data collection were performed at low temperatures (123 K). The tris(μ-thianthrene-κ2S)disilver(I) bis(hexafluoroantimonate) sulfur dioxide solvate [Ag2(TA)3][SbF6]2·5SO2 (1) (monoclinic, P21/c, a = 21.644(3), b = 12.4216(4), c = 21.934(3) Å , β = 115.04(1)°, Z = 4) is made up of complexes bearing three TA units acting as bridging ligands with both S atoms towards two Ag+ ions with d(Ag+-Ag+) = 2.911 Å giving the [Ag2(TA)3]2+ unit approximately D3h molecular symmetry. The bis(μ-thianthrene-κ2S)disilver(I) bis(tetrafluoroborate) sulfur dioxide solvate [Ag2(TA)2][BF4]2・3SO2 (2) (monoclinic, C2/c, a = 21.0045(6), b = 7.4553(2), c = 22.6024(6) A° , β = 109.65(0)°, Z = 4) is made up of [Ag2(TA)2]2+units with two bridging TA units coordinating two Ag+ ions with d(Ag+-Ag+) = 2.925 Å giving the complexes approximately D2h molecular symmetry. Weak, secondary bonds between Ag+ and the F atoms of the anions, such as Ag···F-SbF5 = 2.862(4) Å in 1 or Ag···F-BF3 = 2.773(2) Å in 2, and with O atoms of SO2 molecules link the complexes with the anions and the solvate molecules, respectively.

Anion directed control of supramolecular structure in silver complexes through weak interactions

CrystEngComm ◽  
2012 ◽  
Vol 14 (17) ◽  
pp. 5394 ◽  
Author(s):  
Jayne L. Gulbransen ◽  
Christopher M. Fitchett
Keyword(s):  
Supramolecular Structure ◽  
Weak Interactions ◽  
Silver Complexes

Three Novel Silver Complexes with Ligand-Unsupported Argentophilic Interactions and Their Luminescent Properties

2006 ◽  
Vol 45 (9) ◽  
pp. 3679-3685 ◽  
Author(s):  
Xi Liu ◽  
Guo ◽  
Ming-Lai Fu ◽  
Xue-Hui Liu ◽  
Ming-Sheng Wang ◽  
...  
Keyword(s):  
Luminescent Properties ◽  
Silver Complexes ◽  
Argentophilic Interactions

Synthese und Kristallstruktur von tetramerem N,N'-Diphenylformamidinato-gold(I), [Au(PhNCH NPh)]4/Synthesis and Structure of Tetrameric N,N'-Diphenylformamidinato Gold(I), [Au(PhNCHNPh)]4

1989 ◽  
Vol 44 (1) ◽  
pp. 1-4 ◽  
Author(s):  
Edmund Hartmann ◽  
Joachim Strähle
Keyword(s):  
Solid State ◽  
Liquid Ammonia ◽  
Bridging Ligands ◽  
Space Group ◽  
Lattice Constants ◽  
And Function ◽  
Tetrameric Complex ◽  
Linear Coordination

Abstract N.N'-Diphenylformamidinato gold(I) (1) is obtained from Na(PhNCH NPh) and Aul in liquid ammonia. It can be recrystallized from toluene/n-heptane to form colorless monoclinic crystals, the space group C 2/c, with the lattice constants a = 1781.7(7), b = 1159.0(5), c = 2518.7(8) pm, β = 99.06(3)°. 1 is tetrameric in solution and in the solid state. In the tetrameric complex with the symmetry C2 the four Au atoms form a planar rhombus with Au -Au distances between 295,7 and 322.7 pm. The amidinato ligands are arranged alternatively above and below the Au4-rhombus and function as bridging ligands for neighbouring Au atoms, which thereby reach a linear coordination with distances A u -N between 200.0 and 202.4 pm.

Coordination polymers built from metal tripyrrin units

2008 ◽  
Vol 12 (12) ◽  
pp. 1242-1249 ◽  
Author(s):  
Martin Bröring
Keyword(s):  
Hydrogen Bonding ◽  
Coordination Chemistry ◽  
Transition Metal ◽  
Metal Ions ◽  
Coordination Polymers ◽  
Transition Metal Ions ◽  
Bridging Ligands ◽  
Secondary Interactions ◽  
Coordination Bonds ◽  
Linear Coordination

This account summarizes recent advances in the coordination chemistry of tripyrrins and related ligands with a special emphasis on the structural chemistry of coordination polymers with such ligands. The tripyrrin ligand is unique in supporting the formation of 1D- and 3D-supramolecular structures from pentacoordinate transition metal ions due to an effective blockage of their sixth coordination site. Linear coordination polymers have been observed with a multitude of bidentate and tridentate bridging ligands like trifluoroacetate, azide, thio- and selenocyanate, and higher order pseudohalides. Homo- and heterodimetallic species have been obtained by the use of cyanometallates and could be characterized structurally in two cases. Besides the covalent coordination bonds, several secondary interactions like hydrogen bonding and π-stacking were found to support these coordination polymers and are demonstrated to allow the preparation of species with functionalized inner surfaces.

scholarly journals Synthesis and Structural Characterization of a Silver(I) Pyrazolato Coordination Polymer

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 1015
Author(s):  
Kiyoshi Fujisawa ◽  
Takuya Nemoto ◽  
Yui Morishima ◽  
Daniel B. Leznoff
Keyword(s):  
Solid State ◽  
Coordination Polymer ◽  
Emission Spectra ◽  
Supramolecular Assembly ◽  
Luminescent Properties ◽  
Spectroscopic Properties ◽  
Coinage Metal ◽  
Argentophilic Interactions ◽  
Linear Coordination

Coinage metal(I)···metal(I) interactions are widely of interest in fields such as supramolecular assembly and unique luminescent properties, etc. Only two types of polynuclear silver(I) pyrazolato complexes have been reported, however, and no detailed spectroscopic characterizations have been reported. An unexpected synthetic method yielded a polynuclear silver(I) complex [Ag(μ-L1Clpz)]n (L1Clpz− = 4-chloride-3,5-diisopropyl-1-pyrazolate anion) by the reaction of {[Ag(μ-L1Clpz)]3}2 with (nBu4N)[Ag(CN)2]. The obtained structure was compared with the known hexanuclear silver(I) complex {[Ag(μ-L1Clpz)]3}2. The Ag···Ag distances in [Ag(μ-L1Clpz)]n are slightly shorter than twice Bondi’s van der Waals radius, indicating some Ag···Ag argentophilic interactions. Two Ag–N distances in [Ag(μ-L1Clpz)]n were found: 2.0760(13) and 2.0716(13) Å, and their N–Ag–N bond angles of 180.00(7)° and 179.83(5)° indicate that each silver(I) ion is coordinated by two pyrazolyl nitrogen atoms with an almost linear coordination. Every five pyrazoles point in the same direction to form a 1-D zig-zag structure. Some spectroscopic properties of [Ag(μ-L1Clpz)]n in the solid-state are different from those of {[Ag(μ-L1Clpz)]3}2 (especially in the absorption and emission spectra), presumably attributable to this zig-zag structure having longer but differently arranged intramolecular Ag···Ag interactions of 3.39171(17) Å. This result clearly demonstrates the different physicochemical properties in the solid-state between 1-D coordination polymer and metalacyclic trinuclear (hexanuclear) or tetranuclear silver(I) pyrazolate complexes.

Solvent-Induced Structural Changes in Complexes of 1,2-Bis(3-(3-pyridyl)pyrazolyl)ethane

2009 ◽  
Vol 62 (2) ◽  
pp. 108 ◽  
Author(s):  
Yuniar P. Prananto ◽  
David R. Turner ◽  
Jinzhen Lu ◽  
Stuart R. Batten
Keyword(s):  
Structural Changes ◽  
Free Ligand ◽  
Radical Change ◽  
Variable Number ◽  
Pyridyl Nitrogen ◽  
Bridging Ligands ◽  
Thiocyanate Complex ◽  
One Dimensional ◽  
Metal Atoms ◽  
Ditopic Ligand

A series of complexes have been obtained using the flexible ditopic ligand 1,2-bis(3-(3-pyridyl)pyrazolyl)ethane (LEt) with M(SCN)2 (M = Co, Fe) and ZnCl2. The ligand is observed to exist in a variety of conformations with rotations around the ethane spacer and around the pyridyl/pyrazole bond. The bridging length of the ligand (i.e., distance between pyridyl nitrogen atoms) varies by 3.5 Å depending on its geometry. Three different cobalt(ii) complexes of the general form [Co(LEt)2(SCN)2]·Solv (where Solv is a variable number/type of non-coordinated solvent) have been structurally characterized and form a series of solvent dependant supramolecular isomers. When Solv = 2MeCN a (4,4)-sheet is formed (1), however, when Solv = H2O an alternate ‘collapsed’ (4,4)-sheet is observed (2). Changing the solvent to two molecules of N,N-dimethylformamide (DMF) leads to a radical change in structure with a one-dimensional (1D) polymer formed (3) that contains two bridging ligands between adjacent metal atoms (i.e., maintaining the same metal/ligand ratio as in the (4,4)-sheet structures). A monomeric thiocyanate complex [Fe(LEt)2(SCN)2(H2O)2] (4) is reported in which the bispyridyl ligands are terminal and partake in an extended hydrogen-bonded network. A 1D polymer [Zn(LEt)Cl2] (5) is also presented. The structures of the metal complexes are contrasted with that of the free ligand.

scholarly journals Kristallstruktur des „supramolekularen“ Silber(I)thiocyanat-Cyclam-Komplexes [Ag(SCN)·(C10H24N4)1/2] / Crystal Structure of the “Supramolecular” Silver(I)thiocyanate Cyclam Complex [Ag(SCN)·(C10H24N4)1/2]

1994 ◽  
Vol 49 (2) ◽  
pp. 211-214 ◽  
Author(s):  
Joachim Pickardt ◽  
Jing Shen
Keyword(s):  
Crystal Structure ◽  
Aqueous Solution ◽  
Supramolecular Structure ◽  
Three Dimensional ◽  
Bridging Ligands ◽  
Thiocyanate Complex ◽  
Space Group

Colourless crystals of the 1,4,8,11-tetraazacyclotetradecane (cyclam) silver(I) thiocyanate complex [Ag(SCN) · (C10H24N4)1/2] were obtained by diffusion of a solution of cyclam in ethanol into an aqueous solution of K[Ag(SCN)2], The crystals are tetragonal, space group P42/n, Z = 8, a = b - 1256.0(4), c = 1185.5(9) pm. The SCN groups act as μ3 ligands, the S atoms of two SCN groups bridge two neighbouring Ag ions, which are only 297.5 pm apart, forming butterfly-like Ag2S2 moieties, the N atoms of the SCN groups form bonds to Ag atoms of adjacent Ag2S2 moieties. Two Ag2S2 units are again connected by cyclam molecules which act as two-dentate bridging ligands. Thus a complicated three-dimensional “supramolecular” structure results.

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