AgI Centers Research Articles

Structural Modulation and Properties of Silver(I) Coordination Frameworks with Benzenedicarboxyl Tectons and trans-1-(2-Pyridyl)-2-(4-pyridyl)ethylene Spacer

A series of silver(I) coordination polymers have been synthesized by the combination of an extended 2,4′-bipyridyl linker trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene (bpe) and different benzenedicarboxyl tectons, including isophthalic acid (H2ip), 5-sulfoisophthalic acid (H3sip), terephthalic acid (H2tp), 2-aminoterephthalic acid (H2ata), and 2-bromoterephthalic acid (H2bta). Single-crystal X-ray diffraction indicates that the structural patterns of these polymeric complexes diversify from two-dimensional (2-D) (3,4,5)-connected (for 2) or 63 (for 3 and 4) layers to three-dimensional (3-D) (10,3)-b (for 1) or 8-nodal self-penetrating (for 5) networks. Interestingly, the AgI centers can show various coordination spheres such as linear, trigonal, tetrahedral, and square-pyramidal geometries. The results clearly reveal that the dicarboxyl building blocks with different dispositions of the carboxyl sites and uncoordinated substituent groups, are the crucial factors for structural assemblies of such extended frameworks. Solid-state properties for these crystalline materials have also been investigated, which display modest thermal stability and strong fluorescent emission at room temperature.

Poly[bis(μ2-2-aminopyrazine-κ2N1:N4)(μ2-nitrato-κ2O:O)(nitrato-κ2O,O′)disilver(I)]: an achiral two-dimensional coordination polymer forming chiral crystals

The solution reaction of AgNO(3) and 2-aminopyrazine (apyz) in a 1:1 ratio gives rise to the title compound, [Ag(2)(NO(3))(2)(C(4)H(5)N(3))(2)](n), (I), which possesses a chiral crystal structure. In (I), both of the crystallographically independent Ag(I) cations are coordinated in tetrahedral geometries by two N atoms from two apyz ligands and two O atoms from nitrate anions; however, the Ag(I) centers show two different coordination environments in which one is coordinated by two O atoms from two different symmetry-related nitrate anions and the second is coordinated by two O atoms from a single nitrate anion. The crystal structure consists of one-dimensional Ag(I)-apyz chains, which are further extended by mu(2)-kappa(2)O:O nitrate anions into a two-dimensional (4,4) sheet. N-H...O and C(apyz)-H...O hydrogen bonds connect neighboring sheets to form a three-dimensional supramolecular framework.

Bis[μ-1-(2-pyridylmethyl)-1H-benzotriazole]disilver(I) bis(perchlorate)

In the title centrosymmetric binuclear AgI complex, [Ag2(C12H10N4)2](ClO4)2, each AgI center is two-coordinated by one pyridine and one benzotriazole N-donor atom of two inversion-related 1-(2-pyridylmeth­yl)-1H-benzotriazole (L) ligands. This forms a unique box-like cyclic dimer with an intra­molecular Ag⋯Ag separation of 4.479 (2) Å. Inter­molecular C—H⋯O hydrogen-bonding inter­actions, involving uncoordinated ClO4 − ions, link the binuclear units, forming a two-dimensional network parallel to (10).

Catena-Poly[silver(I)-μ2-4,4′-bipyridine-κ2N:N′-μ3-chlorido]: self-assembly of a two-dimensional bilayer silver(I) coordination polymer from AgCl and a bipodal spacer

The title compound, [AgCl(C(10)H(8)N(2))](n), was synthesized by reaction of silver(I) chloride with 4,4'-bipyridine (bipy) under ammoniacal conditions. The crystal structure reveals that the Ag and Cl atoms lie on twofold axes, while the bipy ligands also sit across twofold axes. The Ag(I) center is five-coordinated by three Cl atoms and two N atoms from two symmetry-related bipy ligands in a distorted square-pyramidal geometry. The complex contains one-dimensional Ag(I)-bipy chains, which are further linked by rarely formed T-frame mu(3)-Cl to form a two-dimensional bilayer structure.

Bis(1,10-phenanthroline-5,6-dione-κ2N,N′)silver(I) tetrafluoridoborate

In the structure of the title compound, [Ag(C12H6N2O2)2]BF4 or [AgL 2]BF4 (L = phendione), the Ag and B atoms are located on twofold rotation axes. The dihedral angle between the two phendione ligands is 36.7 (2)°. The coordination about the AgI center is distorted tetra­hedral (τ4 = 0.546). The crystal structure is consolidated by weak C—H⋯O(phendione) and C—H⋯F(BF4 −) inter­actions. The BF4 − counter-anion is strongly disordered and was modelled with two sets of idealized F atoms.

A two-dimensional network formed by self-associating silver(I) perchlorate with 3-[4-(2-thienyl)-2H-cyclopenta[d]pyridazin-1-yl]benzonitrile

In the organometallic silver(I) supramolecular complex poly[[silver(I)-mu(3)-3-[4-(2-thienyl)-2H-cyclopenta[d]pyridazin-1-yl]benzonitrile] perchlorate methanol solvate], {[Ag(C(18)H(11)N(3)S)](ClO(4)).CH(3)OH}(n), there is only one type of Ag(I) center, which lies in an {AgN(2)Spi} coordination environment. Two unsymmetric multidentate 3-[4-(2-thienyl)-2H-cyclopenta[d]pyridazin-1-yl]benzonitrile (L) ligands link two Ag(I) atoms through pi-Ag(I) interactions into an organometallic box-like unit, from which two 3-cyanobenzoyl arms stretch out in opposite directions and bind two Ag(I) atoms from neighboring box-like building blocks. This results in a novel two-dimensional network extending in the crystallographic bc plane. These two-dimensional sheets stack together along the crystallographic a axis to generate parallelogram-like channels. The methanol solvent molecules and the perchlorate counter-ions are located in the channels, where they are fixed by intermolecular hydrogen-bonding interactions. This architecture may provide opportunities for host-guest chemistry, such as guest molecule loss and absorption or ion exchange. The new fulvene-type multidentate ligand L is a good candidate for the preparation of Cp-Ag(I)-containing (Cp is cyclopentadienyl) organometallic coordination polymers or supramolecular complexes.

Bis{μ-3-[3-(2-pyridyl)pyrazol-1-ylmethyl]pyridine}disilver(I) bis(trifluoromethanesulfonate): effect of counter-anions on the self-assembly of coordination complexes

As part of a study on the effect of different counter-anions on the self-assembly of coordination complexes, a new dinuclear Ag(I) complex, [Ag(2)(C(14)H(12)N(4))(2)](CF(3)SO(3))(2), with the 3-[3-(2-pyridyl)pyrazol-1-ylmethyl]pyridine (L) ligand was obtained through the reaction of L with AgCF(3)SO(3). In this complex, each Ag(I) center in the centrosymmetric dinuclear complex cation is coordinated by two pyridine and one pyrazole N-atom donor of two inversion-related L ligands in a trigonal planar geometry. This forms a unique box-like cyclic dimer with an intramolecular nonbonding Ag...Ag separation of 6.379 (7) A. Weak Ag...CF(3)SO(3) and C-H...X (X = O and F) hydrogen-bonding interactions, together with pi-pi stacking interactions, link the complex cations along the [001] and [1\overline{1}0] directions, respectively, generating two different one-dimensional chains and then an overall two-dimensional network of the complex running parallel to the (110) plane. Comparison of the structural differences with previous findings suggests that the presence of different counter-anions plays an important role in the construction of such supramolecular frameworks.

Bis[μ-1,2-bis(1H-imidazol-1-ylmethyl)benzene-κ2N3:N3′]disilver(I) bis(4-amino-2,5-dichlorobenzenesulfonate) tetrahydrate

The asymmetric unit of the title compound, [Ag2(C14H14N4)2](C6H4Cl2NO3S)2·4H2O, contains one-half of each of two independent dicationic units, two 4-amino-2,5-dichloro­benzene­sulfonate anions and four water mol­ecules. Each centrosymmetric dicationic unit has a dinuclear structure in which two AgI atoms are bridged by two 1,2-bis­(1H-imidazol-1-yl­meth­yl)benzene ligands in a slightly distorted linear coordination geometry. The 4-amino-2,5-dichloro­benzene­sulfonate anion does not coordinate with the AgI center, acting only as a counteranion. In the crystal structure, inter­molecular O—H⋯O and N—H⋯O hydrogen bonds form a three-dimensional network.

Synthesis and Structure of a Silver(I) Complex {[Ag5(L)2(NO3)4](NO3)(CHCl3)2}n [L = 2,3-bis(pyrimidine-2-thiomethyl)quinoxaline

The reaction of the dithioether ligand, 2,3-bis(pyrimidine-2-thiomethyl)quinoxaline (L) with AgNO3, leads to the formation of a novel complex {[Ag5(L)2(NO3)4](NO3)(CHCl3)2}n 1, which has been characterized by single-crystal X-ray diffraction analysis: monoclinic, space group C2/c, with a = 34.741(7), b = 9.930(2), c = 17.004(4) A, β = 106.497(6)° and V = 5625(2) A3.Complex 1 consists of 2D {[Ag5(L)2(NO3)4]+}n cations, uncoordinated $$ {\text{NO}}^{ - }_{{\text{3}}} $$ anions and CHCl3 solvent molecules. In 1, there exist three crystallographic independent AgI centers, which adopt different coordination geometries. There exist π–π stacking interactions in the complex and these weak interactions further stabilize the crystal structure in the solid state. The coordination feature of the ligand has been investigated by DFT calculations. Synthesis and Structure of a Silver(I) Complex {[Ag5(L)2(NO3)4](NO3)(CHCl3)2}n [L = 2,3-bis(pyrimidine-2-thiomethyl)quinoxaline] Chao-Yan Zhang, Qian Gao, Ya-Bo Xie*, and Jian-Bo Feng The crystal structure of complex {[Ag5(L)2(NO3)4](NO3)(CHCl3)2}n (L = 2,3-bis(pyrimidine-2-thiomethyl)quinoxaline) consists of 2D {[Ag5(L)2(NO3)4]+}n cations, uncoordinated $$ {\text{NO}}^{ - }_{{\text{3}}} $$ anions and CHCl3 solvent molecules. There exist three crystallographic independent AgI centers, which adopt different coordination geometries. The coordination feature of the ligand has been investigated by DFT calculations.

Poly[[(μ2-2-amino-4,5-dimethybenzenesulfonato-κ2N:O)(μ2-2-methylpyrazine-κ2N:N′)silver(I)] monohydrate

In the title compound, {[Ag(C8H10NO3S)(C7H6N2)]·H2O}n, each AgI cation is four-coordinated by three N atoms from two different 2-methyl­pyrazine ligands and one –NH2 group of a 2-amino-4,5-dimethybenzene­sulfonate ligand, and by one sulfonate O atom, in a distorted tetra­hedral coordination geometry. The AgI centres are bridged by both types of ligands, forming a two-dimensional network. N—H⋯O hydrogen bonds and O⋯O inter­actions complete the structure.

Catena-Poly[[(6-aminonaphthalene-1-sulfonato-κO)silver(I)]-μ-2,3,5,6-tetramethylpyrazine-κ2N:N′

In the title compound, [Ag(C10H8NO3S)(C8H12N2)]n, the Ag+ cation is three-coordinated by two N atoms from two 2,3,5,6-tetra­methyl­pyrazine ligands and one O atom from a 7-aminona­phthalene-1-sulfonate anion. The 2,3,5,6-tetra­methyl­pyrazine ligand acts as a bridging bidentate ligand, linking the AgI centres into a one-dimensional chain. The chains are inter­connected via inter­molecular N—H⋯O hydrogen bonds and C—H⋯π inter­actions, resulting in the formation of a three-dimensional framework.

Catena-Poly[[[bis(triphenylphosphine)silver(I)]-μ-6-aminonaphthalene-1-sulfonato-κ2O:N] monohydrate

In the title compound, {[Ag(C10H8NO3S)(C18H15P)2]·H2O}n, each AgI cation is four coordinated by two P atoms from two different triphenyl­phosphine ligands, and by one N atom and one sulfonate O atom from different 6-aminona­phthalene-1-sulfonate anions in a distorted tetra­hedral geometry. Each 6-aminona­phthalene-1-sulfonate ligand bridges two AgI centers, resulting in the formation of polymeric chains parallel to the a axis. Inter­molecular O—H⋯O and N—H⋯O hydrogen bonds contribute to the crystal packing stability. One phenyl ring is disordered over two positions; the site occupancies are 0.68 and 0.32.

(2,9-Dimethoxy-1,10-phenanthroline-κ2N,N′)nitratosilver(I)

In the crystal structure of the title compound, [Ag(NO3)(C14H12N2O2)], the AgI centre is three-coordinated by two N atoms from 2,9-dimeth­oxy-1,10-phenanthroline and one O atom of the nitrate anion. The Ag—N bond lengths are almost identical, and O—Ag—N bond angles are larger than the bite angle N—Ag—N. In the main ligand, the O and C atoms of the meth­oxy groups lie almost in the plane defined by the phenanthroline ring system. Based on the extended delocal­ized π system of phenanthroline and the d10 electronic configuration of the metal centre, the title complex is expected to produce strong luminescent emission when properly excited.

Catena-Poly[silver(I)-μ-2-phenylimidazolato-κ2N:N′

The asymmetric unit of the title compound, [Ag(C9H7N2)]n, contains two independent AgI ions and two 2-phenyl­imidazolate (L) ligands. Each AgI centre is linearly coordinated by two N atoms [Ag—N 2.092 (3)–2.097 (3) Å]. Ligands L bridge AgI ions into polymeric chains parallel to the c axis, with Ag⋯Ag separations of 6.232 (2) and 6.254 (2) Å. No inter­actions between the Ag centres from neighbouring chains are observed.

Catena-Poly[silver(I)-μ-4-aminobenzenesulfonato-μ-2,3-diethylpyrazine

In the title compound, [Ag(C6H6NO3S)(C8H8N2)], the AgI cation is four-coordinated by three N atoms from two different 2,3-diethylpyrazine ligands and one –NH2 group of a 4-aminobenzenesulfonate ligand, and one sulfonate O atom in a distorted tetrahedral coordination geometry. The AgI centers are doubly bridged by both types of ligands, forming a one-dimensional chain. N—H...O hydrogen bonds complete the structure.

Catena-Poly[[silver(I)-μ-1,2-bis[(1H-imidazol-1-yl)methyl]benzene-κ2 N 3:N 3′] 2-amino-3,5-dimethylbenzenesulfonate

The title compound, {[Ag(C14H14N2)](C8H10NO3S)} n , adopts a polymeric chain structure, where each AgI cation binds two N atoms from two different 1,2-bis[(1H-imidazol-1-yl)methyl]benzene (IBI) ligands in a linear coordination geometry. Each IBI ligand bridges two neighbouring AgI atoms to form the polymer chain. The 2-amino-3,5-dimethylbenzenesulfonate counter-ion does not coordinate to the AgI centre but forms an intramolecular N—H...O hydrogen bond.

Catena-Poly[bis[μ-1,4-bis(2-pyrimidinylthio)butane-κ2N:N′]disilver(I) diperchlorate chloroform sesquisolvate

The crystal structure of the title complex, {[Ag2(C12H14N4S2)2](ClO4)2·1.5CHCl3}n, consists of [Ag2(C12H14N4S2)2]n2n+ one-dimensional chain cations, ClO4− anions and solvent chloro­form mol­ecules. There are two crystallographically independent AgI centers. The ligand coordinates to the AgI centers in an N,N′-bidentate bridging mode in an anti conformation, resulting in infinite corrugated chains. The one-dimensional chains are linked to form a two-dimensional framework by weak Ag⋯S inter­actions [3.052 (4) and 3.348 (5) A]. One of the perchlorate ions and all of the solvent chloroform molecules are disordered.

{1,3-Bis[3-(2-pyridyl)-1H-pyrazol-1-yl]propan-2-ol}silver(I) perchlorate

In the title compound, [Ag(C19H18N6O)]ClO4, the cation and anion both lie on crystallographic twofold rotation axes. The hydroxyl group of the cation is disordered across the twofold rotation axis. The AgI centre is four-coordinated by four N atoms from the 1,3-bis­[3-(2-pyrid­yl)-1H-pyrazole]propan-2-ol ligand in a distorted tetra­hedral coordination environment. O—H⋯O and weak C—H⋯O hydrogen-bonding inter­actions link adjacent mononuclear AgI units and perchlorate ions, forming a chain.

Bis[μ-N-(1,3,4-thiadiazol-2-yl)pyridine-3-carboxamide-κ2N1,N3]disilver(I) bis(perchlorate)

In the title compound, [Ag2(C8H6N4OS)2](ClO4)2, each AgI center in the centrosymmetric dinuclear complex cation is coordinated by one pyridine N and a thia­diazole N atom of two inversion-related N-(1,3,4-thia­diazol-2-yl)pyridine-3-carboxamide ligands in an almost linear geometry [Ag—N = 2.187 (3) and 2.172 (3) A, and N—Ag—N = 171.8 (1)°]. Weak Ag⋯Ag and Ag–perchlorate inter­actions, together with π–π stacking inter­actions, link the complex cations along the a axis to form a ribbon.

One-dimensional silver(i) coordination polymers containing cyclodiphosphazane, cis-{(o-MeOC6H4O)P(µ-NtBu)}2

The 1:1 reaction between the cyclodiphosphazane cis-{(o-MeOC(6)H(4)O)P(mu-N(t)Bu)}(2) (1) and AgOTf afforded one-dimensional Ag(I) coordination polymer [Ag{mu-OTf-kappaO,kappaO}{mu-(o-MeOC(6)H(4)O)P(mu-N(t)Bu)-kappaP,kappaP}(2)](infinity) (2) containing bridging cyclodiphosphazane and trifluoromethanesulfonate (OTf) ligands. The 2:1 reaction of and AgOTf leads to the formation of simple mononuclear complex [Ag{OTf-kappaO,kappaO}({(o-MeOC(6)H(4)O)P(mu-N(t)Bu)-kappaP}(2))(2)] (3) in quantitative yield. Reaction of 1 with AgCN produces a strain-free zig-zag coordination polymer [({(o-MeOC(6)H(4)O)P(mu-N(t)Bu)-kappaP,kappaP}(2))(2)Ag(NCAgCN)](infinity) (4) irrespective of reaction stoichiometry and conditions. In complexes 3 and 4 cyclodiphosphazanes coordinate to Ag(I) centers in a monodentate fashion. Single crystal structures were established for the Ag(I) polymers 2 and 4.