High‐Nuclearity Silver Thiolate Clusters Constructed with Phosphonates

The n‐butylphosphonate ligand has been employed to construct three new silver(I) thiolate compounds. Single‐crystal X‐ray analysis revealed that complexes 1 and 2 are Ag₄₈ and Ag₅₁ coordination chain polymers, while 3 contains a discrete Ag₄₈ cluster, in which three different kinds of silver(I) thiolate cluster shells enclose three different phosphonate‐functionalized silver(I) cluster cores, respectively. The structures of clusters in 1 – 3 feature three three‐shell arrangements, S@Ag₁₂@(nBuPO₃)₉@Ag₃₆S₂₃, S@Ag₁₁@(nBuPO₃)₇(MoO₄)₂ @Ag₄₀S₂₇ and MoO₄@Ag₁₂@(nBuPO₃)₈S₆ @Ag₃₆S₂₄, respectively.     

Different Silver Nanoparticles in One Crystal: Ag210(iPrPhS)71(Ph3P)5Cl and Ag211(iPrPhS)71(Ph3P)6Cl

Two pure silver nanoparticles (Ag₂₁₀(ⁱPrPhS)₇₁(Ph₃P)₅Cl and Ag₂₁₁(ⁱPrPhS)₇₁(Ph₃P)₆Cl labeled as SD/Ag210 and SD/Ag211 (SD=SunDi), were found to co‐crystallize in forming compound 1 . Single‐crystal X‐ray diffraction (SCXRD) revealed that they differ by only one Ag(PPh₃). Their four‐shell nanoparticles consist of three pure Ag metal shells (Ag₁₉@Ag₅₂@Ag₄₅) shielded by a silver‐organic Ag₈₉(ⁱPrPhS)₇₁Cl[Ag(Ph₃P)]_n outermost shell. The number (n) of Ag(Ph₃P) is five for SD/Ag210 and six for SD/Ag211. The pseudo‐fivefold symmetric Ag nanoparticles exhibit surface plasmon absorption similar to a true metallic state but at the nanoscale. This work exemplifies the important effects of phosphine in stabilizing large silver nanoparticles; and offers a platform to investigate the origin of differences in nanoscale metal materials, even differing by only one metal atom; it also sheds light on the regioselective binding of auxiliary Ph₃P on the surface of silver nanoparticles.     

A Sodalite‐Type Silver Orthophosphate Cluster in a Globular Silver Nanocluster

The synthesis and structure of a giant 102‐silver‐atom nanocluster (NC) 1 is presented. X‐ray structural analysis reveals that 1 features a multi‐shelled metallic core of Ag₆@Ag₂₄@Ag₆₀@Ag₁₂. An octahedral Ag₆ core is encaged by a truncated octahedral Ag₂₄ shell. The Ag₂₄ shell is composed of a hitherto unknown sodalite‐type silver orthophosphate cluster (SOC) {(Ag₃PO₄)₈}, reminiscent of the Ag₃PO₄ photocatalyst. The SOC is capped by six interstitial sulfur atoms, giving a unique anionic cluster [Ag₆@{(Ag₃PO₄)₈}S₆]^6?, which functions as an intricate polyhedral template with abundant surface O and S atoms guiding the formation of a rare rhombicosidodecahedral Ag₆₀ shell. An array of 6 linear Ag₂ staples further surround this Ag₆₀ shell. [Ag₆@{(Ag₃PO₄)₈}S₆]^6? is an unusual Ag‐based templating anion to induce the assembly of a SOC within silver NC. This finding provides molecular models for bulk Ag₃PO₄, and offers a fresh template strategy for the synthesis of silver NCs with high symmetry.     

Silver Thiolate Nano‐sized Molecular Clusters and Their Supramolecular Covalent Frameworks: An Approach Toward Pre‐templated Synthesis

A series of seven new complexes including silver‐thiolate molecular clusters and their covalent supramolecular frameworks have been assembled from the silver carbide precursor Ag₂C₂ using a C₂²⁻ pre‐templated approach. Herein, two prototype clusters Ag₁₄(SR)₆ and CO₃@Ag_m (SR)₁₀ (R=isopropyl, cyclohexyl or tert ‐butyl; m= 18 or 20) are employed to construct cluster‐based metal–organic frameworks of different dimensions. In particular, both new ellipsoidal tetradecanuclear molecular cluster compounds, namely, Ag₁₄(S‐i Pr)₆(CO₂CF₃)₈⋅(DMSO)₆ (two polymorphic forms 1 , 2 ) and [Ag₁₄(S‐Cy)₆(CO₂CF₃)₈(DMSO)₄]⋅(DMSO)₃ ( 3 ), and a cluster‐based metal–organic framework {Ag₃[Ag₁₄(S‐i Pr)₆(CO₂CF₃)₁₁(H₂O)₃CH₃OH]⋅(H₂O)_2.5}_n ( 4 ) have been isolated and structurally characterized. Furthermore, increased acidity of the reaction mixture afforded three carboxylate‐templated cluster based frameworks: a chain‐like compound {[HN(CH₃)₂CO]⋅[CO₃@Ag₁₈(S‐t Bu)₁₀(NO₃)₇(DMF)₄]⋅DMF}_n ( 5 ), as well as two layer‐type compounds, namely, {Ag[CO₃@Ag₂₀(S‐i Pr)₁₀(CO₂CF₃)₉(CO₂HCF₃)(CH₃OH)₂]}_n ( 6 ) and {Ag₂[CO₃@Ag₂₀(S‐Cy)₁₀(CO₂CF₃)₁₀(CO₂HCF₃)₂(H₂O)₂]⋅(H₂O)₃⋅(CH₃OH)₃}_n ( 7 ) exhibiting sql ‐net characteristics. It is demonstrated that the C≡C²⁻ pre‐template, which draws several Ag⁺ ions together to form the C₂@Ag_n entity, plays an indispensable role in the syntheses of these compounds. Furthermore, covalent linkage of these nano‐sized silver thiolate clusters from one‐ to three‐dimensions revealed enormous potential for the future development of silver cluster‐based frameworks.     

An Atomically Precise Alkynyl‐Protected PtAg42 Superatom Nanocluster and Its Structural Implications

The synthesis and structure determination of an alkynyl‐protected Pt‐doped Ag superatom nanocluster, [PtAg₄₂(C≡CC₆H₄CH₃)₂₈](SbF₆)₆ (1) , are reported. The metallic core of this cluster can be viewed as a concentric three‐shell Russian doll comprising Pt@Ag₁₂@Ag₃₀, in which the missing icosidodecahedral Ag₃₀ shell and a new structural unit, M₄₃, have been observed. On the surface of 1 , 28 alkynyl groups and 4 SbF₆⁻ anions were found co‐protecting it. The protective role of SbF₆⁻ in nanoclusters is unprecedented. Moreover, of the 28 alkynyl ligands, 12 are connected not only with the outermost Ag₃₀ shell, but also the inner Ag₁₂ shell through the twelve pentagonal faces of the outermost icosidodecahedral Ag₃₀ shell. Overall, by determining the crystal structure of 1 , we discovered the missing icosidodecahedral Ag₃₀ shell and the protective effect of SbF₆⁻ anions and demonstrated a novel M₄₃ structural unit and the unique penetrability of pentagonal faces.     

Beyond Clusters: Supramolecular Networks Self‐Assembled from Nanosized Silver Clusters and Inorganic Anions

Assembly of small clusters into rigid bodies with precise shape and symmetry has been witnessed by the significant advances in cluster‐based metal–organic frameworks (MOFs), however, nanosized silver cluster based MOFs remain largely unexplored. Herein, two anion‐templated silver clusters, CO₃@Ag₂₀ and SO₄@Ag₂₂, were ingeniously incorporated into a 2D sql lattice ( 1 , [CO₃@Ag₂₀(iPrS)₁₀(NO₃)₈(DMF)₂]_n) and an unprecedented 3D two‐fold interpenetrated dia network ( 2 , [SO₄@Ag₂₂(iPrS)₁₂(NO₃)₆ ? 2 NO₃]_n), respectively, under mild solvothermal conditions. Their atomically precise structures were confirmed by single‐crystal X‐ray diffraction analysis and further consolidated by IR spectroscopy, thermogravimetric analysis (TGA), and elemental analysis. Each drum‐like CO₃@Ag₂₀ cluster is extended by twelve NO₃^? ions to form the 2D sql lattice of 1 , whereas each ball‐shaped SO₄@Ag₂₂ cluster with a twisted truncated tetrahedral geometry is pillared by four [Ag₆(NO₃)₃] triangular prisms to form the 3D interpenetrated dia network of 2 . Notably, 2 is the first interpenetrated 3D MOF constructed from silver clusters. These results demonstrate the dual role of the anions, which not only internally act as anion templates to induce the formation of silver thiolate clusters but also externally extend the cluster units into the rigid networks. The photoluminescent and electrochemical properties of 2 are discussed in detail.     

Rhombicuboctahedral Ag100: Four‐Layered Octahedral Silver Nanocluster Adopting the Russian Nesting Doll Model

Precise atomic structure of metal nanoclusters (NCs) is fundamental for elucidating the structure–property relationships and the inherent size‐evolution principles. Reported here is the largest known FCC‐based (FCC=face centered cubic) silver nanocluster, [Ag₁₀₀(SC₆H₃^3,4F₂)₄₈(PPh₃)₈]^?: the first all‐octahedral symmetric nesting Ag nanocluster with a four‐layered Ag₆@Ag₃₈@Ag₄₈S₂₄@Ag₈S₂₄P₈ structure, consistent symmetry elements, and a unique rhombicuboctahedral morphology distinct from theoretical predictions and previously reported FCC‐based Ag clusters. DFT studies revealed extensive interlayer interactions and degenerate frontier orbitals. The FCC‐based Russian nesting doll model constitutes a new platform for the study of the size‐evolution principles of Ag NCs.     

A Three-dimensional Heteronuclear Polymer of [Ag2Fe（SCN）5（DMF）]n Containing Channels and One-dimensional Ag2S2-S-Ag2S2 Chains with Ag…Ag Interaction

Introduction So far, considerable attention has been paid to mag-netic interaction between two different metal ions.1-3 As a potential bridging ligand, thiocyanate can coordinate to a harder metal center with N atom and softer ones with S atom at the same time, resulting in the formation of small ferromagnetic coupling.2 On the other hand, the Fe(III) atom is a good candidate as a hard acid and Ag(I) is a good candidate as a soft acid, so that the Fe(III) centers could be expected to conn…     

A novel three‐dimensional AgI coordination polymer based on mixed naphthalene‐1,5‐disulfonate and aminoacetate ligands

The three‐dimensional coordination polymer poly[[bis(μ₃‐2‐aminoacetato)di‐μ‐aqua‐μ₃‐(naphthalene‐1,5‐disulfonato)‐hexasilver(I)] dihydrate], {[Ag₆(C₁₀H₆O₆S₂)(C₂H₄NO₂)₄(H₂O)₂]·2H₂O}_n, based on mixed naphthalene‐1,5‐disulfonate (L1) and 2‐aminoacetate (L2) ligands, contains two Ag^I centres (Ag1 and Ag4) in general positions, and another two (Ag2 and Ag3) on inversion centres. Ag1 is five‐coordinated by three O atoms from one L1 anion, one L2 anion and one water molecule, one N atom from one L2 anion and one Ag^I cation in a distorted trigonal–bipyramidal coordination geometry. Ag2 is surrounded by four O atoms from two L2 anions and two water molecules, and two Ag^I cations in a slightly octahedral coordination geometry. Ag3 is four‐coordinated by two O atoms from two L2 anions and two Ag^I cations in a slightly distorted square geometry, while Ag4 is also four‐coordinated by two O atoms from one L1 and one L2 ligand, one N atom from another L2 anion, and one Ag^I cation, exhibiting a distorted tetrahedral coordination geometry. In the crystal structure, there are two one‐dimensional chains nearly perpendicular to one another (interchain angle = 87.0°). The chains are connected by water molecules to give a two‐dimensional layer, and the layers are further bridged by L1 anions to generate a novel three‐dimensional framework. Moreover, hydrogen‐bonding interactions consolidate the network.     

Tandem Silver Cluster Isomerism and Mixed Linkers to Modulate the Photoluminescence of Cluster‐Assembled Materials

Silver chalcogenolate cluster assembled materials (SCAMs) are a category of promising light‐emitting materials the luminescence of which can be modulated by variation of their building blocks (cluster nodes and organic linkers). The transformation of a singly emissive [Ag₁₂(SBu^t)₈(CF₃COO)₄(bpy)₄]_n (Ag₁₂bpy, bpy=4,4′‐bipyridine) into a dual‐emissive [(Ag₁₂(SBu^t)₆(CF₃COO)₆(bpy)₃)]_n (Ag₁₂bpy‐2) via cluster‐node isomerization, the critical importance of which was highlighted in dictating the photoluminescence properties of SCAMs. Moreover, the newly obtained Ag₁₂bpy‐2 served to construct visual thermochromic Ag₁₂bpy‐2/NH₂ by a mixed‐linker synthesis, together with dichromatic core–shell Ag₁₂bpy‐2@Ag₁₂bpy‐NH₂‐2 via solvent‐assisted linker exchange. This work provides insight into the significance of metal arrangement on physical properties of nanoclusters.     

catena‐Poly[[silver(I)‐μ‐[9,10‐bis(1H‐benzimidazol‐1‐ylmethyl)anthracene]‐κ2N3:N3′] bis(nitrato‐κO)silver(I)]

Yellow needle‐shaped crystals of the title compound, {[Ag(C₃₀H₂₂N₄)][Ag(NO₃)₂]}_n, were obtained by the reaction of AgNO₃ and 9,10‐bis(benzimidazol‐1‐ylmethyl)anthracene (L) in a 2:1 ratio. The asymmetric unit consists of two Ag^I cations, one half L ligand and one nitrate anion. One Ag^I cation occupies a crystallographic inversion centre and links two N‐atom donors of two distinct L ligands to form an infinite one‐dimensional coordination polymer. The second Ag^I cation lies on a crystallographic twofold axis and is coordinated by two O‐atom donors of two nitrate anions to form an [Ag(NO₃)₂]⁻ counter‐ion. The polymeric chains are linked into a supramolecular framework via weak Ag...O [3.124 (5) Å] and Ag...π (2.982 Å) interactions (π is the centroid of an outer anthracene benzene ring). The π interactions contain two short Ag...C contacts [2.727 (6) and 2.765 (6) Å], which can be considered to define Ag–η²‐anthracene bonding interactions. In comparison with a previously reported binuclear Ag^I complex [Du, Hu, Zhang, Zeng & Bu (2008). CrystEngComm, 10 , 1866–1874], this new one‐dimensional coordination polymer was obtained by changing the metal–ligand ratio during the synthesis.     

A Temperature‐Sensitive Luminescent Ag42 Nanocluster Supported by TertButyl Thiol Ligands

Compound [Ag₄₂S₅(StBu)₂₅(CF₃COO)₄(CO₃)](CO₃)_0.5?CH₂Cl₂?4CH₃OH?9DMF ( 1 ) has been obtained and well defined. It consists of a multi‐shell structure involving two Ag centres, one Ag₅S₅ pentagram, two Ag₅S₅ pentagons and one Ag₂₅S₁₅ shell. Compound 1 has been characterized by XPS, FT‐IR, PXRD, TGA, NMR, MS, UV/Vis spectrum, TEM and cyclic voltammetry. Temperature‐sensitive luminescent property of 1 has also been investigated.     

A cyclic tetramer of [Ag(1,4,7‐trithiacyclononane)]+, cyclo‐tetrakis(μ‐1,4,7‐trithiacyclononane‐κ3S1,S4,S7:κS1)tetrasilver(I) tetrakis(trifluoromethanesulfonate) nitromethane disolvate

(1,4,7‐Tri­thia­cyclo­nonane)silver tri­fluoro­methane­sulfonate crystallizes in a tetrameric form from nitro­methane, to give the title compound, [Ag₄(C₆H₁₂S₃)₄](CF₃SO₃)₄·2CH₃NO₂. The complex cation consists of four [AgL]⁺ units (L is 1,4,7‐tri­thia­cyclo­nonane), with four Ag—S—Ag bridges forming a cyclic tetramer. The almost planar Ag₄S₄ ring takes an octagonal form.     

Anion‐directed Silver(I) Coordination Assemblies Based on 1‐(2‐Pyridyl)‐2‐(4‐pyridyl)‐1,2,4‐triazolewith Diverse Supramolecular Networks and Dichromate Removal Capabilities

A series of silver(I) supramolecular complexes, namely, {[Ag(L²⁴)](NO₃)}_n ( 1 ), [Ag₂(L²⁴)(NO₂)₂]_n ( 2 ), and {[Ag_1.25(L²⁴)(DMF)](PF₆)_1.25}_n ( 3 ) were prepared by the reactions of 1‐(2‐pyridyl)‐2‐(4‐pyridyl)‐1,2,4‐triazole (L²⁴) and silver(I) salts with different anions (AgNO₃, AgNO₂, AgPF₆). Single‐crystal X‐ray diffraction indicates that 1 – 3 display diverse supramolecular networks. The structure of dinuclear complex 1 is composed of a six‐membered Ag₂N₄ ring with the Ag ··· Ag distance of 4.4137(3) Å. In complex 2 , the adjacent Ag^I centers are interlinked by L²⁴ ligands into a 1D chain, the adjacent of which are further extended by the bridged nitrites to construct a 2D coordination architecture. Complex 3 shows a 3D (3,4)‐connected framework, which is generated by the linkage of L²⁴ ligands. All complexes were characterized by IR spectra, elemental analysis, and powder X‐ray diffraction. Notably, a structural comparison of the complexes demonstrates that their structures are predominated by the nature of anions. Additionally, 1 and 2 show efficient dichromate (Cr₂O₇^2–) capture in water system, which can be ascribed to the anion‐exchange.     

catena‐Poly[[disilver(I)(Ag—Ag)‐bis[μ‐1,1′‐(butane‐1,4‐diyl)diimidazole‐κ2N3:N3′]] bis(perchlorate)]: a double helix stabilized by ligand‐unsupported argentophilic interactions

The title compound, {[Ag₂(C₁₀H₁₄N₄)₂](ClO₄)₂}_n, is a one‐dimensional coordination polymer formed by Ag^I atoms linearly bridged by 1,1′‐(butane‐1,4‐diyl)diimidazole molecules. The chains have a helical arrangement and pairs of chains are held together by the rarely reported ligand‐unsupported Ag—Ag interaction [2.966 (1) Å], which results in a double‐helix structure. The double helix contains twisted 24‐membered metallomacrocycles, which are composed of four Ag atoms and two ligands. The Ag atoms lie on twofold axes.     

Polyaniline‐Modified Silver and Binary Silver‐Cobalt Catalysts for Oxygen Reduction Reaction

Novel dendrite‐like silver particles were electrodeposited on Ti substrates from a supporting electrolyte‐free 30 mmol L^?1 Ag(NH₃)₂⁺ solution, to synthesize the den‐Ag/Ti electrode. Binary Ag_xCo_y/Ti electrodes with different Ag:Co atomic ratios were further obtained by electrodeposition of Co particles on the den‐Ag/Ti electrode. Polyaniline (PANI) modified den‐Ag/Ti and Ag_xCo_y/Ti electrodes, PANI(n)‐den‐Ag/Ti and PANI(n)‐Ag_xCo_y/Ti, were also obtained by cyclic voltammetry at different numbers of cycles (n) in acidic and alkaline solutions containing aniline, respectively. All these electrodes exhibit high electroactivity for oxygen reduction reaction (ORR) in alkaline solution and their electroactivities follow the order: PANI(15)‐Ag₃₁Co₆₉/Ti>Ag₃₁Co₆₉/Ti>PANI(20)‐den‐Ag/Ti>den‐Ag/Ti. Among them, PANI(15)‐Ag₃₁Co₆₉/Ti displays the highest electrocatalytic activity for ORR with a much positive onset potential of 0 V (vs. Ag/AgCl) and a high ORR current density of 1.2 mA cm^?2 at ?0.12 V (vs. Ag/AgCl). The electrocatalysts are electrochemically insensitive to methanol and ethanol oxidation, and, as cathode electrocatalysts of direct alcohol fuel cells, can resist poisoning by the possible alcohol crossover from the anode.     

Silver(I) complexes of 2‐(2‐amino­eth­yl)pyridine: nitrate and perchlorate salts of bis­[μ‐2‐(2‐amino­eth­yl)pyridine‐κ2N:N′]disilver(I)

2‐(2‐Amino­eth­yl)pyridine (2‐aep, C₇H₁₀N₂) acts as a bridging ligand in bis­[μ‐2‐(2‐amino­eth­yl)pyridine‐κ²N:N′]disilver(I) dinitrate, [Ag₂(2‐aep)₂](NO₃)₂, and bis­[μ‐2‐(2‐amino­eth­yl)­pyridine‐κ²N:N′]disilver(I) diperchlorate, [Ag₂(2‐aep)₂](ClO₄)₂. Both salts contain the dinuclear [Ag₂(2‐aep)₂]²⁺ cation, which possesses a crystallographic inversion center. The Ag⋯Ag distance is 3.1163 (5) Å for the nitrate and 3.0923 (3) Å for the perchlorate salt, and may indicate a weak d¹⁰–d¹⁰ inter­action in each case. Essentially linear coordination of the Ag^I atom is perturbed by weak coordination to the anionic O atoms. These latter inter­actions organize the dinuclear cations into one‐dimensional polymeric chains in the crystals of the two salts.     

A stair‐like two‐dimensional silver(I) coordination polymer of N′‐(3‐cyanobenzylidene)nicotinohydrazide

The structure of the title compound, poly[[[μ₃‐N′‐(3‐cyanobenzylidene)nicotinohydrazide]silver(I)] hexafluoroarsenate], {[Ag(C₁₄H₁₀N₄O)](AsF₆)}_n, at 173 K exhibits a novel stair‐like two‐dimensional layer and a three‐dimensional supramolecular framework through C—H...Ag hydrogen bonds. The Ag^I cation is coordinated by three N atoms and one O atom from N′‐(3‐cyanobenzylidene)nicotinohydrazide (L) ligands, resulting in a distorted tetrahedral coordination geometry. The organic ligand acts as a μ₃‐bridging ligand through the pyridyl and carbonitrile N atoms and deviates from planarity in order to adapt to the coordination geometry. Two ligands bridge two Ag^I cations to construct a small 2+2 Ag₂L₂ ring. Four ligands bridge one Ag^I cation from each of four of these small rings to form a large grid. An interesting stair‐like two‐dimensional (3,6)‐net is formed through Ag^I metal centres acting as three‐connection nodes and through L molecules as tri‐linkage spacers.     

Nestlike Silver(I) Thiolate Clusters with Tunable Emission Color Templated by Heteroanions

Four silver thiolate clusters, [H₃O][(Ag₃S₃)(BF₄)@Ag₂₇(tBuS)₁₈(hfac)₆H₂O] ⋅ H₂O ( 1 ; hfac = hexafluoroacetylacetone), [(Ag₃S₃)(CF₃CO₂)@Ag₃₀(tBuS)₁₆(CF₃CO₂)₉(CH₃CN)₄] ⋅ CF₃CO₂ ⋅ 4 CH₃CN ( 2 ), [(Ag₃S₃)(MoO₄)@Ag₃₀(tBuS)₁₆(CF₃CO₂)₉(CH₃CN)₄] ⋅ 2 CH₃CN ( 3 ), and [(Ag₃S₃)(CrO₄)@Ag₃₀(tBuS)₁₆(CF₃CO₂)₉(CH₃CN)₄] ⋅ 4 CH₃CN ( 4 ), were isolated. They have similar nestlike structures assembled by an [Ag₃S₃]³⁻ template together with one of the BF₄⁻, CF₃CO₂⁻, MoO₄²⁻, or CrO₄²⁻ anions. Interestingly, the solid-state emissions of 2 – 4 are dependent on the templating anions and are tunable from green to orange and then to red by changing the template from CF₃CO₂⁻ to MoO₄²⁻ and to CrO₄²⁻, and this may be correlated to the charge transfer between these templates to metal atoms. This work helps to understand the templating role of heteroanions and the relationship between structure and properties.     

catena‐Poly[[silver(I)‐μ‐1,3‐bis(4‐pyridyl)propane] hemi(naphthalene‐1,5‐disulfonate) dihydrate]: a three‐dimensional metallo‐supramolecular sandwich lamellar network

The title compound, {[Ag(C₁₃H₁₄N₂)](C₁₀H₆O₆S₂)_0.5·2H₂O}_n, (I), features a three‐dimensional supramolecular sandwich architecture that consists of two‐dimensional cationic layers composed of polymeric chains of silver(I) ions and 1,3‐bis(4‐pyridyl)propane (bpp) ligands, linked by Ag...Ag and π–π interactions, alternating with anionic layers in which uncoordinated naphthalene‐1,5‐disulfonate (nds²⁻) anions and solvent water molecules form a hydrogen‐bonded network. The asymmetric unit consists of one Ag^I cation linearly coordinated by N atoms from two bpp ligands, one bpp ligand, one half of an nds²⁻ anion lying on a centre of inversion and two solvent water molecules. The two‐dimensional {[Ag(bpp)]⁺}_n cationic and {[(nds)·2H₂O]²⁻}_n anionic layers are assembled into a three‐dimensional supramolecular framework through long secondary coordination Ag...O interactions between the sulfonate O atoms and Ag^I centres and through nonclassical C—H...O hydrogen bonds.