Nitrate Counterions Research Articles

Insights into the Origin of Cooperative Effects in the Spin Transition of [Fe(NH2trz)3](NO3)2: the Role of Supramolecular Interactions Evidenced in the Crystal Structure of [Cu(NH2trz)3](NO3)2·H2O

The thermally induced hysteretic spin transition (ST) that occurs in the polymeric chain compound [Fe(NH(2)trz)(3)](NO(3))(2) (1) above room temperature (T(c)(upward arrow) = 347 K, T(c)(downward arrow) = 314 K) has been tracked by (57)Fe Mössbauer spectroscopy, SQUID magnetometry, differential scanning calorimetry (DSC), and X-ray powder diffraction (XPRD) at variable temperatures. From the XRPD pattern indexation, an orthorhombic primitive cell was observed with the following cell parameters: a = 11.83(2) A, b = 9.72(1) A, c = 6.361(9) A at 298 K (low-spin state) and a = 14.37(2) A, b = 9.61(4) A, c = 6.76(4) A at 380 K (high-spin state). The enthalpy and entropy variation associated to the ST of 1, have been evaluated by DSC as DeltaH = 23(1) kJ mol(-1) and DeltaS = 69.6(1) J mol(-1) K(-1). These thermodynamic data were used within a two-level Ising like model for the statistical analysis of First Order Reversal Curve (FORC) diagram that was recorded for 1, in the cooling mode. Strong intramolecular cooperative effects are witnessed by the derived interaction parameter of J = 496 K. The crystal structure of [Cu(NH(2)trz)(3)](NO(3))(2).H(2)O (2) was obtained thanks to high quality single crystals prepared by slow evaporation after hydrothermal pretreatment. The catena poly[mu-tris(4-amino-1,2,4-triazole-N1,N2) copper(II)] dinitrate monohydrate (2) crystallizes in the monoclinic space group C2/c, with a = 16.635(6) A, b = 13.223(4) A, c = 7.805(3) A, beta = 102.56(3) degrees, Z = 4. Complex 2 is a 1D infinite chain containing triple N1,N2-1,2,4-triazole bridges with an intra-chain distance of Cu...Cu = 3.903(1) A. A dense H-bonding network with the nitrate counteranion involved in intra-chain and inter-chain interactions is observed. Such a supramolecular network could be at the origin of the unusually large hysteresis loop displayed by 1 (DeltaT approximately 33 K), as a result of an efficient propagation of elastic interactions through the network. This hypothesis is strengthened by the crystal structure of 2 and by the absence of crystallographic phase transition for 1 over the whole temperature range of investigation as shown by XRPD.

Hydrogen-bonded supramolecular networks ofN,N′-bis(4-pyridylmethyl)oxalamide and 4,4′-{[oxalylbis(azanediyl)]dimethylene}dipyridinium dinitrate

The molecule of N,N'-bis(4-pyridylmethyl)oxalamide, C(14)H(14)N(4)O(2), (I) or 4py-ox, has an inversion center in the middle of the oxalamide group. Adjacent molecules are then linked through intermolecular N-H...N and C-H...O hydrogen bonds, forming an extended supramolecular network. 4,4'-{[Oxalylbis(azanediyl)]dimethylene}dipyridinium dinitrate, C(14)H(16)N(4)O(2)(2+).2NO(3)(-), (II), contains a diprotonated 4py-ox cation and two nitrate counter-anions. Each nitrate ion is hydrogen bonded to four 4py-ox cations via intermolecular N-H...O and C-H...O interactions. Adjacent 4py-ox cations are linked through weak C-H...O hydrogen bonding between an alpha-pyridinium C atom and an oxalamide O atom, forming a two-dimensional extended supramolecular network.

Intercalation of Ethylene Glycol into Yttrium Hydroxide Layered Materials

Intercalation of ethylene glycol into layered yttrium hydroxide containing nitrate counterions was accomplished by heating the reagents in a methanol solution of sodium methoxide under autogenous pressure at 413 K for 20 h. The resulting crystalline material had an expanded interlayer distance of 10.96 A, confirming the intercalation of an ethylene glycol derived species. Characterization of the material by FT-IR spectroscopy, thermogravimetric analysis, and the catalytic transesterification of tributyrin with methanol was consistent with direct bonding of ethylene glycolate anions (O(2)C(2)H(5)(-)) to the yttrium hydroxide layers, forming Y-O-C bonds. The layers of the material are proposed to be held together by H-bonding between the hydroxyls of grafted ethylene glycol molecules attached to adjacent layers. Glycerol can also be intercalated into yttrium hydroxide layered materials by a similar method.

More examples of the 15-crown-5...H2O—M—OH2...15-crown-5 motif, M = Al3+, Cr3+ and Pd2+

Five structures of co-crystals grown from aqueous solutions equimolar in 15-crown-5 (or 15C5) and [M(H(2)O)(6)](NO(3))(n), M = Al(3+), Cr(3+) and Pd(2+), are reported. The hydrogen-bonding patterns in all are similar: metal complexes including the fragment trans-H(2)O-M-OH(2) alternate with 15C5 molecules, to which they are hydrogen bonded, to form stacks. A literature survey shows that this hydrogen-bonding pattern is very common. In each of the two polymorphs of the compound [Al(H(2)O)(6)](NO(3))(3).15C5.4H(2)O there are two independent cations; one forms hydrogen bonds directly to the 15C5 molecules adjacent in the stack, while the other cation is hydrogen-bonded to two water molecules that act as spacers in the stack. These stacks are then crosslinked by hydrogen bonds formed by the three nitrate counterions and the three lattice water molecules. The hydrogen-bonded stacks in [Cr(H(2)O)(5)(NO(3))](NO(3))(2).1.5(15C5).H(2)O are discrete rather than infinite; each unit contains two Cr(3+) complex cations and three 15C5 molecules. These units are again crosslinked by the uncoordinated nitrate ions and a lattice water molecule. In [Pd(H(2)O)(2)(NO(3))(2)].15C5 the infinite stacks are electrically neutral and are not crosslinked. In [Pd(H(2)O)(2)(NO(3))(2)].2(15C5).2H(2)O.2HNO(3) a discrete, uncharged unit containing one Pd complex and two 15C5 molecules is ;capped off' at either end by a lattice water molecule and an included nitric acid molecule. In all five structures the infinite stacks or discrete units form an array that is at least approximately hexagonal.

Polishing Treatment of Molasses Wastewater with Iron Salts: the Role of Counter‐ions

The effect of counter-ions on the coagulation of biologically treated molasses wastewater using iron-based coagulants was investigated. Parameters such as removals of chemical oxygen demand (COD) and color, and residual turbidity, were measured to evaluate coagulation performance. Experimental results showed that ferric chloride and ferric nitrate were more effective than ferric sulfate at optimal dosages, achieving 89 to 90% and 98 to 99% of COD and color removals, respectively, with residual turbidity of less than 5 NTU. High-performance size exclusion chromatography (HPSEC) results revealed differences in the removal of the molecular weight fraction of organic compounds using iron salts. Scanning electron microscopy (SEM) showed randomly formed coagulated flocs characterized with irregular, sheet-like shapes. Nitrate and chloride counter-ions had similar effects on coagulation performance compared to sulfate. Both FeCl3 and Fe(NO3)3 yielded better results than Fe(SO4)2 under underdosed and optimum dosage conditions. Coagulation efficiency was less adversely affected in the overdosed regions, however, if sulfate rather than chloride or nitrate was present.

Synthesis and Magnetic Properties of Dual-Ligand Divalent Copper Coordination Polymers with Rhomboid Layer, Archimedean Grid, and Self-Penetrated Network Topologies

Four divalent copper coordination polymers containing both 1,2-phenylenediacetate (1,2-phda) and dipyridyl-type coligands have been prepared and structurally characterized by single-crystal X-ray diffraction. {[Cu(1,2-phda)(dpa)]·H2O}n (1, dpa = 4,4′-dipyridylamine) possesses a simple (4,4) rhomboid polymeric grid structure but can be considered a (4,6)-connected binodal supramolecular lattice with (4462)(446108) fsc topology. Use of a longer dipyridyl ligand afforded [Cu2(1,2-phda)2(dpp)]n (2, dpp = 1,3-di(4-pyridyl)propane), which manifests a rare self-penetrated rob lattice (48668 topology) built from the linkage of copper dicarboxylate layers through crossed dpp tethers. [Cu(1,2-phda)(H2O)(4-bpmp)0.5]n (3, 4-bpmp = bis(4-pyridylmethyl)piperazine) forms a 5-connected Archimedean cem layer with 334453 topology. The topology of 3 can be alternately described as a 3,4-connected binodal layer with a V2O5-type network. Incorporation of nitrate counterions led to formation of {[Cu(1,2-phda)(H2O)(H4-bpmp)] (N...

Bis(ethylenediamine-κ2N,N′)(nitrato-κ2O,O′)cobalt(III) hydroxide nitrate

The Co ion in the title salt, [Co(NO3)(H2NCH2CH2NH2)2](OH)(NO3), has oxidation state + III and is coordinated by four N atoms from two ethyl­enediamine mol­ecules and two O atoms from a nitrate anion in a distorted octa­hedral geometry. The charge of the complex cation is balanced by a hydroxide anion and a nitrate anion. The cations and anions are connected by N—H⋯O and O—H⋯O hydrogen bonds, resulting in a three-dimensional supra­molecular framework. There are two independent ion pairs with similar configurations in the unit cell. Both uncoordinated nitrate counter-anions are disordered.

{4-[(Carbamimidoylhydrazono)methyl-κ2N1,N4]-5-hydroxymethyl-2-methylpyridinium-3-olate-κO}(methanol-κO)copper(II) dinitrate

The title compound, [Cu(C(9)H(13)N(5)O(2))(CH(4)O)](NO(3))(2), consists of square-planar cationic complex units where the Cu(II) centre is coordinated by an N,N',O-tridentate pyridoxal-aminoguanidine Schiff base adduct and a methanol molecule. The tridentate ligand is a zwitterion exhibiting an almost planar conformation. The dihedral angles between the mean planes of the pyridoxal ring and the six- and five-membered chelate rings are all less than 2.0 degrees. The charge on the complex cation is neutralized by two nitrate counter-ions. Extensive N-H...O and C-H...O hydrogen bonding connects these ionic species and leads to the formation of layers. The pyridoxal hydroxy groups are the only fragments that deviate significantly from the flat layer structure; these groups are involved in O-H...O hydrogen bonding, connecting the layers into a three-dimensional crystal structure.

2,5-Dimethylanilinium nitrate

In the title salt, C8H12N+·NO3 −, all non-H atoms of the cation lie on mirror planes. The nitrate counteranion has m symmetry and acts as a hydrogen-bond acceptor of N—H⋯O hydrogen bonds, connecting the cations and anions into layers running parallel to the ab plane.

Nonanuclear Coordination Compounds Featuring {M9L12}6+ Cores (M = NiII, CoII, or ZnII; L = 1,2,3‐Benzotriazolate)

AbstractSyntheses, characterization, and magnetic properties of three nonanuclear coordination compounds with the molecular formulae [Ni9(bta)12(NO3)6(MeOH)6]·4THF (1) (btaH = 1,2,3‐benzotriazole; THF = tetrahydrofuran), [Co9(bta)12(MeOH)18][(NO3)6]·9C6H6 (C6H6 = benzene) (2), and [Zn9(Me2bta)12(CH3COO)6]·3DMF (Me2btaH = 5,6‐dimethyl‐1,2,3‐benzotriazole; DMF = N,N′‐dimethylformamide) (3) are presented. The solid‐state structures of all the compounds were determined by single‐crystal X‐ray structure analysis revealing the presence of structurally similar {M9L12}6+ cores (M = NiII, CoII, or ZnII; L = 1,2,3‐benzotriazolate) in which the metal centers are bridged by μ3‐benzotriazolates. The charges of the cationic {M9L12}6+ moieties in 1 and 3 are balanced by six nitrate and acetate anions coordinated to the peripheral metal atoms, respectively, whereas 2 is a cationic metal complex with six noncoordinated nitrate counterions in the crystal lattice. All the metal centers in each compound are hexacoordinate, except for the peripheral metal centers in 3 which are pentacoordinate. The nonanuclear cores can be formally subdivided into two metallosupramolecular tetrahedra which bear five metal ions each, and share a common apex. All compounds have been prepared by using excess of ligand, which acts as an auxiliary base, serving to abstract protons from the coordinated benzotriazole ligand. Magnetic susceptibility studies (2–290 K) show net antiferromagnetic intramolecular coupling for 2, while 1 displays both ferro‐ and antiferromagnetic coupling contributions. Both compounds exhibit strong ligand field effects in their magnetic properties. Phase purity of the compounds was ascertained by X‐ray powder diffraction (XRPD) analysis, IR spectroscopy, and elemental analysis.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Divalent metal complexes of formylhydrazine: Syntheses and crystal structures of M(CH4N2O)2(H2O)2·2NO3 (M=Zn, Co)

Abstract The syntheses and crystal structures of Zn(CH4N2O)2(H2O)2·2(NO3) (1) and Co(CH4N2O)2(H2O)2·2(NO3) (2), the first well-characterised metal complexes of formylhydrazine (fh), are described. In both compounds, the fh acts as an N,O-bidentate ligand in a centrosymmetric [M(fh)2(H2O)2]2+ cation, with charge balance supplied by nitrate counter ions. The packing for the two compounds are quite different: in 1, chains of [Zn(fh)2(H2O)2]2+ units are seen in the triclinic unit cell, whereas in the monoclinic structure of 2, sheets of cations occur. This might arise because the conformations of the five-membered chelate rings for the ligands are slightly different, with that for 2 showing a greater degree of puckering.

Supramolecular Architectures and Magnetic Properties of Self‐Assembled Windmill‐Like Dinuclear Copper(II) Complexes with Purine Ligands

AbstractThree new CuII compounds, [Cu2(μ‐ade)4(H2O)2]·(bpa)·8H2O (1), [Cu2(μ‐Hade)4(H2O)2](NO3)4·2[Cu(pic)2(H2O)]·6H2O (2) and [Cu2(μ‐6Clpur)4(H2O)2]·~6H2O (3) [in which ade = adeninate anion, Hade = 7H‐adenine, 6Clpur = 6‐chloropurinate anion, bpa = 1,2‐bis(4‐pyridyl)ethane, pic = 2‐pyridinecarboxylate anion], are reported. Their crystal structures consist of dinuclear copper(II) units, in which four ligands arranged in a windmill‐like fashion bridge the metal ions through a nonlinear NCN group. Supramolecular crystal building of compound 1 is essentially maintained by an extensive network of hydrogen‐bonding interactions that involves direct contacts between the nucleobases. In contrast, in compound 2 there is no evidence for direct interactions between the nucleobases, but the hydrogen bonds among the nucleobases and nitrate counteranions are especially relevant. Compound 3 is mainly built up from T‐shaped noncovalent Cl···N interactions and hydrogen‐bonding interactions involving the crystallization solvent molecules. Magnetic susceptibility measurements indicate the presence of strong intradimeric antiferromagnetic interactions with large singlet–triplet splittings of –222 (for 1), –288 (for 2) and –255 (for 3) cm–1. DFT calculations were carried out to evaluate the dependence of the magnetic coupling value as a function of some key structural parameters: the Cu–N basal plane distance, the axial Cu–Ow distance and the Cu···Cu distance. DFT calculations also revealed that the nature of the bridging ligand is a crucial factor. In this way, the strength to transmit the magnetic interaction of the different bridging ligands is explained on the basis of the number of electron lone pairs.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

New Polymeric Composites Based on Poly(ϵ-caprolactone) and Layered Double Hydroxides Containing Antimicrobial Species

Benzoate (Bz), 2,4-dichlorobenzoate (BzDC), and p- and o-hydroxybenzoate (p- and o-BzOH) anions with antimicrobial activity have been intercalated into [Zn(0.65)Al(0.35)(OH)(2)](NO(3))(0.35).0.6H(2)O, layered double hydroxide (LDH), via anion-exchange reactions. The composition of the obtained intercalation compounds, determined by chemical, thermogravimetric, and ion chromatographic analyses, indicates that benzoate and benzoate derivative anions replace the nitrate counteranions, almost completely. Information on the interactions of the intercalated anions with the inorganic layer have been obtained from Fourier transform IR absorption spectroscopy and powder X-ray diffraction of the samples. It has been found that both the nature and the position of the aromatic ring substituents affect the value of the basal distance and the host-guest hydrogen bond network. Knowledge of the chemical composition, basal distance, and van der Waals dimensions of the guests has finally allowed the proposal of structural models of the intercalation compounds that have been used as fillers of poly(caprolactone), a biodegradable polymer. Films of polymeric composites were obtained by hot-pressing the powders of polymer and filler previously milled by a high-energy ball milling procedure. X-ray diffraction analysis and optical and scanning electron microscopy of the composites indicate that the LDH samples containing BzDC anions are delaminated into the polymeric matrix, whereas those containing p-BzOH anions maintain for the most part the crystal packing and give rise to microcomposites. Intermediate behavior was found for LDH modified with Bz and o-BzOH anions because exfoliated and partly intercalated composites were obtained. Preliminary antimicrobial tests indicate that the composites are able to inhibit the Saccharomyces cerevisiae growth of 40% in comparison with the growth in a pure culture medium. The composites can be studied as the model for "active packaging" systems because of the antimicrobial properties of the anions anchored to the LDH layer.

Synthesis and structural characterization of copper(II), cadmium(II) and zinc(II) complexes with 4,5-diazaspirobifluorene and bis-9-biphenyl-4,5-diazafluorenyl peroxide

The synthesis and structural chemistry of four new divalent transition metal complexes of the fluorene ligands 4,5-diazaspirobifluorene (L1) and bis-9-biphenyl-4,5-diazafluorenyl peroxide (L2), [Cu 3(L1) 4(NO 3) 6(H 2O) 2] · 2CH 3CN ( 1), [Cu(L1)(CH 3CO 2) 2(H 2O)] · 2H 2O ( 2), [Cd(L1) 2(NO 3) 2] · DMF ( 3) (DMF = N,N-dimethylformamide) and [Zn 2(L2)(μ-Cl) 2Cl 2] ∞ ( 4) are described. Single-crystal X-ray diffraction analysis reveal that the four complexes exhibit various frameworks due to diverse coordination modes and different conformations of ligands L1 or L2, as well as nitrate, acetate or chloro counterions. L1 in complexes 1, 2 and 3 present an asymmetric rigid bidentate ligand with two nitrogen atoms as the donor sites. Novel complex 4 was formed through complexation between conformationally bent shaped peroxide ligands and zinc(II) dichlorides that adopt a linear coordination geometry, which can also give rise to extended polymeric chains with a zigzag secondary structure.

Reactions of Hydrated Electrons with Pyridinium Salts in Aqueous Solutions

Rate coefficients for the reactions of the hydrated electron (e(aq)(-)) with pyridinium salts in aqueous solutions have been determined using pulse radiolysis techniques. The rate coefficients for pyridine, 1-hydropyridinium chloride, and 1-hydropyridinium nitrate were observed to be 1.4 x 10(10), 4.5 x 10(10), and 5.3 x 10(10) M(-1) s(-1), respectively. The e(aq)(-) was found to primarily attack the pyridine ring, the proton coordinated to the nitrogen atom, and the nitrate counterion, but not the chloride. Results for the corresponding dimer structures of 4,4'-dipyridyl, 1,1'-dihydro-4,4'-bipyridinium dichloride, and 1,1'-dihydro-4,4'-bipyridinium dinitrate had similar trends for e(aq)(-) attack sites. The rate coefficients for pyridinium salts were lower when the pyridinium nitrogen atom is coordinated to a methyl group rather than to a proton. This reduction is probably due to the increase in electron density of the pyridine ring due to the electron-donating methyl group. Pyridinium salts are not major contributors to the production of molecular hydrogen in the radiolysis of aqueous solutions and actually decrease molecular hydrogen yield due to scavenging reactions of the e(aq)(-). The yield of molecular hydrogen decreases from 0.45 to approximately 0.2 molecule/(100 eV) over the scavenging capacity range for the e(aq)(-) of 10(5)-10(9) s(-1). Absorption spectra of the transient species produced by the reactions of pyridinium salts with OH radical and H atom formed in water radiolysis were observed, and rate coefficients for these reactions were determined.

Hexa-μ2-acetato-κ12O:O′-μ3-oxido-tris[aquachromium(III)] nitrate acetic acid solvate

In the crystal structure of the title salt, [Cr3(C2H3O2)6O(H2O)3]NO3·CH3CO2H, the trinuclear [Cr3(CH3CO2)6O(H2O)3] cluster cation has an oxide O atom that is connected to three water-coordinated CrIII atoms, the three metal atoms forming the points of an equilateral triangle. Each of the six acetate carboxyl­ate groups bridges a Cr–O–Cr fragment. The cluster cation inter­acts with the nitrate counter-ion and solvent mol­ecules through O—H⋯O hydrogen bonds, forming a three-dimensional hydrogen-bonded network.

Bis{2-ethoxy-6-[2-(ethylammonio)ethyliminomethyl]phenolato}thiocyanatozinc(II) nitrate

The title complex, [Zn(NCS)(C13H20N2O2)2]NO3, consists of a complex mononuclear ZnII cation and a nitrate counter-anion. The ZnII ion is five-coordinate in a trigonal-bipyramidal geometry. The thio­cyanate N atom and two O atoms from two Schiff bases define the equatorial plane, and the two imine N atoms from the same two Schiff bases occupy the axial positions, with an N—Zn—N angle of 175.98 (7)°. The amine N atoms of the Schiff base ligands are protonated and are not involved in the coordination to the metal. The dihedral angle between the two substituted benzene rings is 87.7 (2)°. The nitrate counter-ions are linked to the cations through N—H⋯O hydrogen bonds.

Influence of the metal-to-ligand ratio on the formation of metal organic complexes

Three copper(II) salts with a chloride, bromide or nitrate counterions in combination with the ditopic ligand 1,3-bis(imidazol-1-ylmethyl)benzene (L) were used to study the influence of the metal to ligand molar ratio on the formation of the final product. Single-crystal X-ray analysis revealed structural diversity of the products formed, ranging from discrete species to extended 1D and 2D coordination polymers. Similar types of 1D chains were formed for all counterions.

Counterion effect on the formation of coordination polymer networks between AgNO3 and L (2,2′-oxybis(ethane-2,1-diyl) diisonicotinate). Part 2

Herein we report the synthesis and characterization by single crystal X-ray diffraction of three new silver(I) complexes {[Ag2·L2](NO3)2(H2O)4} (1), {[Ag2·L2](NO3)2} (2) and {[Ag2·L2](NO3)2} (3). Whereas compounds 2 and 3 are polymorphs, compound 1 crystallizes as the pseudo-polymorphic form of 2 and 3. These compounds were obtained from the reaction of silver nitrate with the flexible ligand 2,2′-oxybis(ethane-2,1-diyl) diisonicotinate (L). The main structural motifs for complexes 1–3 are zero-dimensional metallacycles, in which two silver(I) cations are coordinated by two ligands L and their counterions. As a result of its unpredictable coordinating ability, the nitrate anion coordinates the Ag(I) cation in a μ1μ2-fashion in complex 1, in 2 it is coordinated in an asymmetrical μ2-mode, and in 3 the anion is strongly μ2-symmetrical coordinating. The coordination of the NO3− counterions to the metal cation affects the overall supramolecular interactions in the crystalline state of the complexes (e.g.Ag(I)⋯Ag(I), π⋯π, hydrogen bonds and C–H⋯π interactions). These interactions determine the physical properties of these compounds. On heating, the crystals of compound 3 are irreversibly transformed into compound 2. The conversion is supported by the change in the coordination mode of the nitrate counterion toward the Ag(I) cation. The solubility dependence of AgNO3 in the different organic solvents used for the reactions may determine the structural diversity in the supramolecular architecture for these complexes.

Ligand and Counterion Control of Ag(I) Architectures: Assembly of a {Ag8} Ring Cluster Mediated by Hydrophobic and Ag···Ag Interactions

A strategy combining ligand design and counterion variation has been used to investigate the assembly of silver(I) complexes. As a result, dinuclear, octanuclear, and polymeric silver(I) species have been synthesized by complexation of the rigid aliphatic amino ligands cis-3,5-diamino-trans-hydroxycyclohexane (DAHC), cis-3,5-diamino-trans-methoxycyclohexane (DAMC), and cis-3,5-diamino-trans-tert-butyldimethylsilylanyloxycyclohexane (DATC) with silver(I) triflate, nitrate, and perchlorate. The compositions of these aggregates, established by X-ray crystallography and elemental analysis, are [{Ag(DAHC)}2](CF3SO3)2 (1), [{Ag(DAMC)}2](CF3SO3)2 (2), [{Ag(DAMC)}2](NO3)2 (3), [{Ag(DATC)}6{Ag(DAHC)}2](NO3)8 (4), and [{Ag(DATC}n](NO3)n (5), where the DAHC present in 4 is formed by in situ hydrolysis of the acid labile silyl ether group. The type of aggregate formed depends both upon the noncoordinating O-substituent of the ligand and the (also noncoordinating) counterion, with the normal preference of the ligand topology for forming Ag2L2 structures being broken by introduction of the bulky, lipophilic O-tert-butyldimethylsilyl (TBDMS) group. Of particular note is the octanuclear silver ring structure 4, which is isolated only when both the O-TBDMS group and the nitrate counteranion are present and is formed from four Ag2L2 dimers connected by Ag...Ag and hydrogen-bonding interactions. Diffusion rate measurement of this {Ag8} complex by 1H NMR (DOSY) indicates dissociation in CD3OD and CD3CN, showing that this supramolecular ring structure is formed upon crystallization, and establishing a qualitative limit to the strength of Ag...Ag interactions in solution. When solutions of the {Ag8} cluster in methanol are kept for several days though, a new UV-vis absorption is observed at around 430 nm, consistent with the formation of silver nanoparticles.