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.     

Polymeric (3‐amino‐2‐chloropyridine)nitratosilver(I)

In the title compound {alternative name: poly­[silver(I)‐μ‐(3‐­amino‐2‐chloro­pyridine)‐μ‐nitr­ato]}, [Ag(NO₃)(C₅H₅ClN₂)]_n the Ag^I atom is in an irregular AgN₂O₃ geometry, surrounded by one pyridyl N atom [Ag—N 2.283 (5) Å], one amine N atom [Ag—N 2.364 (6) Å] and three O atoms from different nitrate ions [Ag—O 2.510 (6)–2.707 (6) Å]. The Ag ions are bridged by the 3‐amino‐2‐chloro­pyridine ligands into helical chains. Adjacent uniform chiral chains are further interlinked through the NO₃ bridges into an interesting two‐dimensional coordination network in the solid.     

Poly[μ2‐(N‐hydroxypyridine‐2‐carboxamidine)‐μ2‐nitrato‐silver(I)]

In the title complex, [Ag(NO₃)(C₆H₇N₃O)]_n or [Ag(NO₃)(pyaoxH₂)] (pyaoxH₂ is N‐hydroxypyridine‐2‐carboxamidine), the Ag⁺ ion is bridged by the pyaoxH₂ ligands and nitrate anions, giving rise to a two‐dimensional molecular structure. Each pyaoxH₂ ligand coordinates to two Ag⁺ ions using its pyridyl and carboxamidine N atoms, and the OH and the NH₂ groups are uncoordinated. Each nitrate anion uses two O atoms to coordinate to two Ag⁺ ions. The Ag...Ag separation via the pyaoxH₂ bridge is 2.869 (1) Å, markedly shorter than that of 6.452 (1) Åvia the nitrate bridge. The two‐dimensional structure is fishscale‐like, and can be described as pyaoxH₂‐bridged Ag₂ nodes that are further linked by nitrate anions. Hydrogen bonding between the amidine groups and the nitrate O atoms connects adjacent layers into a three‐dimensional network.     

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)‐μ₃‐3‐[4‐(2‐thienyl)‐2H‐cyclopenta[d]pyridazin‐1‐yl]benzonitrile] perchlorate methanol solvate], {[Ag(C₁₈H₁₁N₃S)](ClO₄)·CH₃OH}_n, there is only one type of Ag^I center, which lies in an {AgN₂Sπ} coordination environment. Two unsymmetric multidentate 3‐[4‐(2‐thienyl)‐2H‐cyclopenta[d]pyridazin‐1‐yl]benzonitrile (L) ligands link two Ag^I atoms through π–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.     

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.     

Constructing mixed‐metal coordination polymers from copper(II)–pyridinedicarboxylate metalloligands

In the mixed‐metal complex catena‐poly[bis[diaquasilver(I)] [bis[aquacopper(II)]‐μ₃‐pyridine‐2,5‐dicarboxylato‐2′:1:1′κ⁵N,O²:O⁵:O⁵,O^5′‐μ‐pyridine‐2,5‐dicarboxylato‐2:1κ⁴N,O²:O⁵,O^5′‐disilver(I)‐μ₃‐pyridine‐2,5‐dicarboxylato‐1:1′:2′′κ⁵O⁵,O^5′:O⁵:N,O²‐μ‐pyridine‐2,5‐dicarboxylato‐1′:2′′′κ⁴O⁵,O^5′:N,O²] hexahydrate], {[Ag(H₂O)₂][AgCu(C₇H₃NO₄)₂(H₂O)]·3H₂O}_n, a square‐pyramidal Cu^II center is coordinated by two N atoms and two O atoms from two pyridine‐2,5‐dicarboxylate (2,5‐pydc) ligands and a water molecule, forming a [Cu(2,5‐pydc)₂(H₂O)]²⁻ metalloligand. One Ag^I center is coordinated by five O atoms from three 2,5‐pydc ligands and, as a result, the [Cu(2,5‐pydc)₂(H₂O)]²⁻ metalloligands act as linkers in a unique μ₃‐mode connecting Ag^I centers into a one‐dimensional anionic double chain along the [101] direction. The other Ag^I center is coordinated by two water molecules, forming an [Ag(H₂O)₂]⁺ cation. Four adjacent Ag^I centers are associated by Ag...Ag interactions [3.126 (1) and 3.118 (1) Å], producing a Z‐shaped Ag₄ unit along the [010] direction and connecting the anionic chains into a two‐dimensional layer structure. This study offers information for engineering mixed‐metal complexes based on copper(II)–pyridinedicarboxylate metalloligands.     

The heterometallic cadmium–silver complex cis‐bis[dicyanidoargentato(I)‐κN]bis(5,5′‐dimethyl‐2,2′‐bipyridyl‐κ2N,N′)cadmium(II) monohydrate

In the title complex, [Ag₂Cd(CN)₄(C₁₂H₁₂N₂)₂]·H₂O or cis‐[Cd{Ag(CN)₂}₂(5,5′‐dmbpy)₂]·H₂O, where 5,5′‐dmbpy is 5,5′‐dimethyl‐2,2′‐bipyridyl, the asymmetric unit consists of a discrete neutral [Cd{Ag(CN)₂}₂(5,5′‐dmbpy)₂] unit and a solvent water molecule. The Cd^II cation is coordinated by two bidentate chelate 5,5′‐dmbpy ligands and two monodentate [Ag^I(CN)₂]⁻ anions, which are in a cis arrangement around the Cd^II cation, leading to an octahedral CdN₆ geometry. The overall structure is stabilized by a combination of intermolecular hydrogen bonding, and Ag^I...Ag^I and π–π interactions, forming a three‐dimensional supramolecular network.     

(μ‐2,11‐Dithia­[3.3]paracyclo­phane‐κ2S:S′)bis­[(6‐carboxy­pyridine‐2‐carboxylato‐κ2N,O6)silver(I)]: a mixed‐ligand silver‐based dinuclear compound

In the title complex, [Ag₂(C₇H₄NO₄)₂(C₁₆H₁₆S₂)], each Ag^I atom is trigonally coordinated by one S atom of a 2,11‐dithia­[3.3]paracyclo­phane (dtpcp) ligand, and by one N and one O atom of a 6‐carboxy­pyridine‐2‐carboxylate ligand. Dtpcp acts as a bidentate ligand, bridging two inversion‐related Ag^I atoms to give a dinuclear silver(I) compound. The dinuclear moieties are inter­connected via O—H·O hydrogen bonds to form a two‐dimensional zigzag sheet. Two such sheets are inter­woven viaπ–π inter­actions between pyridine rings, affording an inter­woven bilayer network.     

A one‐dimensional silver(I) coordination polymer based on 5‐methyl‐1,3,4‐thiadiazol‐2‐amine and pyridine‐2,3‐dicarboxylate

The bifunctional pyridine‐2,3‐dicarboxylic acid (H₂pdc) ligand has one N atom and four O atoms, which could bind more than one Ag^I centre with diverse binding modes. A novel infinite one‐dimensional Ag^I coordination polymer, namely catena‐poly[[silver(I)‐(μ₂‐pyridine‐2,3‐dicarboxylato‐κ²N :O ³)‐silver(I)‐tris(μ₂‐5‐methyl‐1,3,4‐thiodiazol‐2‐amine‐κ²N :N ′)] monohydrate ethanol monosolvate], {[Ag₂(C₇H₃NO₄)(C₃H₅N₃S)₃]·H₂O·C₂H₅OH}_n , has been synthesized using H₂pdc and 5‐methyl‐1,3,4‐thiadiazol‐2‐amine (tda), and characterized by single‐crystal X‐ray diffraction. One Ag^I atom is located in a four‐coordinated AgN₄ tetrahedral geometry and the other Ag^I atom is in a tetrahedral AgN₃O geometry. A dinuclear Ag^I cluster formed by three tda ligands with a paddelwheel configuration is bridged by the dianionic pdc²⁻ ligand into a one‐dimensional coordination polymer. Interchain N—H…O hydrogen bonds extend the one‐dimensional chains into an undulating two‐dimensional sheet. The sheets are further packed into a three‐dimensional supramolecular framework by interchain N—H…O hydrogen bonds.     

catena‐Poly[[[(iminodiacetato‐κO)silver(I)]‐μ3‐2‐aminopyrimidine‐κ3N1:N2:N3] monohydrate]: a one‐dimensional silver(I) coordination polymer with mixed ligands

The title compound, {[Ag(C₄H₆NO₄)(C₄H₅N₃)]·H₂O}_n, was synthesized by the reaction of silver(I) nitrate with 2‐aminopyrimidine and iminodiacetic acid. X‐ray analysis reveals that the crystal structure contains a one‐dimensional ladder‐like Ag^I coordination polymer and that N—H...O and O—H...O hydrogen bonding results in a three‐dimensional network. The Ag^I centre is four‐coordinated by three N atoms from three different 2‐aminopyrimidine ligands and one O atom from one iminodiacetate ligand. Comparison of the structural features with previous findings suggests that the existence of a second ligand plays an important role in the construction of such polymer frameworks.     

catena‐Poly­[[(di‐2‐pyridyl­amine)­silver(I)]‐μ‐nicotinato] and catena‐poly­[[(di‐2‐pyridyl­amine)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato]

In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐nico­tinato‐κ²N:O], [Ag(C₆H₄NO₂)(C₁₀H₉N₃)]_n, the Ag^I atom is tetracoordinated by two N atoms from the di‐2‐pyridyl­amine (BPA) ligand [Ag—N = 2.3785 (18) and 2.3298 (18) Å] and by one N atom and one carboxyl­ate O atom from nicotinate ligands [Ag—N = 2.2827 (15) Å and Ag—O = 2.3636 (14) Å]. Bridging by nicotinate N and O atoms generates a polymeric chain structure, which extends along [100]. The carboxyl O atom not bonded to the Ag atom takes part in an intrachain C—H⋯O hydrogen bond, further stabilizing the chain. Pairs of chains are linked by N—H⋯O hydrogen bonds to generate ribbons. There are no π–π interactions in this complex. In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato‐κ²O¹:O²], [Ag(C₇H₅O₄)(C₁₀H₉N₃)]_n, the Ag^I atom has a distorted tetrahedral coordination, with three strong bonds to two pyridine N atoms from the BPA ligand [Ag—N = 2.286 (5) and 2.320 (5) Å] and to one carboxyl­ate O atom from the 2,6‐di­hydroxy­benzoate ligand [Ag—O = 2.222 (4) Å]; the fourth, weaker, Ag‐atom coordination is to one of the phenol O atoms [Ag⋯O = 2.703 (4) Å] of an adjacent moiety, and this interaction generates a polymeric chain along [100]. Pairs of chains are linked about inversion centers by N—H⋯O hydrogen bonds to form ribbons, within which there are π–π interactions. The ribbons are linked about inversion centers by pairs of C—H⋯O hydrogen bonds and additional π–π interactions between inversion‐related pairs of 2,6‐di­hydroxy­benzoate ligands to generate a three‐dimensional network.     

Three AgI,CuI and CdII coordination polymers based on the new asymmetrical ligand 2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole: syntheses,characterization and emission properties

The new asymmetrical organic ligand 2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole ( L , C₁₇H₁₃N₅O), containing pyridine and imidazole terminal groups, as well as potential oxdiazole coordination sites, was designed and synthesized. The coordination chemistry of L with soft Ag^I, Cu^I and Cd^II metal ions was investigated and three new coordination polymers (CPs), namely, catena‐poly[[silver(I)‐μ‐2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole] hexafluoridophosphate], {[Ag( L )]PF₆}_n, catena‐poly[[copper(I)‐di‐μ‐iodido‐copper(I)‐bis(μ‐2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole)] 1,4‐dioxane monosolvate], {[Cu₂I₂( L )₂]·C₄H₈O₂}_n, and catena‐poly[[[dinitratocopper(II)]‐bis(μ‐2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole)]–methanol–water (1/1/0.65)], {[Cd( L )₂(NO₃)₂]·2CH₄O·0.65H₂O}_n, were obtained. The experimental results show that ligand L coordinates easily with linear Ag^I, tetrahedral Cu^I and octahedral Cd^II metal atoms to form one‐dimensional polymeric structures. The intermediate oxadiazole ring does not participate in the coordination interactions with the metal ions. In all three CPs, weak π–π interactions between the nearly coplanar pyridine, oxadiazole and benzene rings play an important role in the packing of the polymeric chains.     

Bis(4‐aminopyridine)silver(I) nitrate and tris(2,6‐diaminopyridine)silver(I) nitrate

The bis(4‐aminopyridine)silver(I) cation in [Ag(C₅H₆N₂)₂]NO₃ has the Ag atom on a twofold axis and displays an N—Ag—N angle of 174.43 (15)° and an Ag—N distance of 2.122 (3) Å. The two ligands are planar and the angle between the two ligand planes is 79.45 (9)°. The pyridine rings are stacked in piles with an interplanar distance of 3.614 (5) Å, a distance that strongly suggests that pyridine π–π interactions have an appreciable importance with respect to the non‐bonded crystal organization. The tris(2,6‐diaminopyridine)­silver(I) cation in [Ag(C₅H₇N₃)₃]NO₃ has Ag—N distances of 2.243 (2), 2.2613 (17) and 2.4278 (18) Å, and N—Ag—N angles of 114.33 (7), 134.91 (7) and 114.33 (7)°. The Ag⁺ ion is situated 0.1531 (2) Å from the plane defined by the three pyridine N atoms.     

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 AgNO₃ and 2‐aminopyrazine (apyz) in a 1:1 ratio gives rise to the title compound, [Ag₂(NO₃)₂(C₄H₅N₃)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 μ₂‐κ²O: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.     

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.     

A tetrahedrally coordinated AgI and NiII complex with a two‐dimensional framework containing one‐dimensional helical chains

The title complex, poly[bis(μ₆‐pyridine‐2,6‐dicarboxylato N‐oxide)nickel(II)disilver(I)], [Ag₂Ni(C₇H₃NO₅)₂]_n or [Ag₂Ni(pydco)₂]_n (H₂pydco = pyridine‐2,6‐dicarboxylic acid N‐oxide), has a two‐dimensional sheet structure. The two carboxylate groups adopt two coordination modes. The Ni^II ion displays a distorted octahedral geometry, bonded to two carboxylate O atoms of two different pydco ligands and four O donors from another two ligands, i.e. two carboxylate O atoms and two N‐oxide O atoms. The Ag^I ion adopts a tetrahedral coordination, linked by three O atoms of three different carboxylate groups and an N‐oxide O atom.     

Chiral one‐ and two‐dimensional silver(I)–biotin coordination polymers

Reaction of biotin {C₁₀H₁₆N₂O₃S, HL; systematic name: 5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoic acid} with silver acetate and a few drops of aqueous ammonia leads to the deprotonation of the carboxylic acid group and the formation of a neutral chiral two‐dimensional polymer network, poly[[{μ₃‐5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}silver(I)] trihydrate], {[Ag(C₁₀H₁₅N₂O₃S)]·3H₂O}_n or {[Ag(L)]·3H₂O}_n, (I). Here, the Ag^I cations are pentacoordinate, coordinated by four biotin anions via two S atoms and a ureido O atom, and by two carboxylate O atoms of the same molecule. The reaction of biotin with silver salts of potentially coordinating anions, viz. nitrate and perchlorate, leads to the formation of the chiral one‐dimensional coordination polymers catena‐poly[[bis[nitratosilver(I)]‐bis{μ₃‐5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}] monohydrate], {[Ag₂(NO₃)₂(C₁₀H₁₆N₂O₃S)₂]·H₂O}_n or {[Ag₂(NO₃)₂(HL)₂]·H₂O}_n, (II), and catena‐poly[bis[perchloratosilver(I)]‐bis{μ₃‐5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}], [Ag₂(ClO₄)₂(C₁₀H₁₆N₂O₃S)₂]_n or [Ag₂(ClO₄)₂(HL)₂]_n, (III), respectively. In (II), the Ag^I cations are again pentacoordinated by three biotin molecules via two S atoms and a ureido O atom, and by two O atoms of a nitrate anion. In (I), (II) and (III), the Ag^I cations are bridged by an S atom and are coordinated by the ureido O atom and the O atoms of the anions. The reaction of biotin with silver salts of noncoordinating anions, viz. hexafluoridophosphate (PF₆⁻) and hexafluoridoantimonate (SbF₆⁻), gave the chiral double‐stranded helical structures catena‐poly[[silver(I)‐bis{μ₂‐5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}] hexafluoridophosphate], {[Ag(C₁₀H₁₆N₂O₃S)₂](PF₆)}_n or {[Ag(HL)₂](PF₆)}_n, (IV), and catena‐poly[[[{5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}silver(I)]‐μ₂‐{5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}] hexafluoridoantimonate], {[Ag(C₁₀H₁₆N₂O₃S)₂](SbF₆)}_n or {[Ag(HL)₂](SbF₆)}_n, (V), respectively. In (IV), the Ag^I cations have a tetrahedral coordination environment, coordinated by four biotin molecules via two S atoms, and by two carboxy O atoms of two different molecules. In (V), however, the Ag^I cations have a trigonal coordination environment, coordinated by three biotin molecules via two S atoms and one carboxy O atom. In (IV) and (V), neither the ureido O atom nor the F atoms of the anion are involved in coordination. Hence, the coordination environment of the Ag^I cations varies from AgS₂O trigonal to AgS₂O₂ tetrahedral to AgS₂O₃ square‐pyramidal. The conformation of the valeric acid side chain varies from extended to twisted and this, together with the various anions present, has an influence on the solid‐state structures of the resulting compounds. The various O—H...O and N—H...O hydrogen bonds present result in the formation of chiral two‐ and three‐dimensional networks, which are further stabilized by C—H...X (X = O, F, S) interactions, and by N—H...F interactions for (IV) and (V). Biotin itself has a twisted valeric acid side chain which is involved in an intramolecular C—H...S hydrogen bond. The tetrahydrothiophene ring has an envelope conformation with the S atom as the flap. It is displaced from the mean plane of the four C atoms (plane B) by 0.8789 (6) Å, towards the ureido ring (plane A). Planes A and B are inclined to one another by 58.89 (14)°. In the crystal, molecules are linked via O—H...O and N—H...O hydrogen bonds, enclosing R₂²(8) loops, forming zigzag chains propagating along [001]. These chains are linked via N—H...O hydrogen bonds, and C—H...S and C—H...O interactions forming a three‐dimensional network. The absolute configurations of biotin and complexes (I), (II), (IV) and (V) were confirmed crystallographically by resonant scattering.     

catena‐Poly­[[(nitrato‐κ2O,O′)silver(I)]‐μ‐2,2′‐[1,4‐phenyl­enebis­(methyl­ene­thio)]­bis(5‐methyl‐1,3,4‐thia­diazo­le)‐κ2N3:N3′]

In the title complex, [Ag(NO₃)(C₁₄H₁₄N₄S₄)]_n, the Ag^I atom lies on a twofold axis and shows a distorted tetrahedral coordination, comprised of two N‐atom donors from two thia­diazole groups of separate ligands and two O‐atom donors from one nitrate ligand. Each bis­(thio­ether) ligand also lies on a twofold axis and bridges two adjacent Ag atoms to form an infinite chain along the c axis, with an Ag⋯Ag separation of 11.462 (4) Å. Adjacent one‐dimensional chains are further linked into double‐chain motifs through weak Ag⋯S and π–π stacking interactions.     

Anion Effects on the Formation of Silver(I) Complexes with the Flexible Ligand 4,4′‐Bis(1,2,4‐triazol‐1‐ylmethyl)biphenyl

The reaction of 4,4′‐bis(1,2,4‐triazol‐1‐ylmethyl)biphenyl (btmb) with silver(I) salts of BF₄^–, NO₃^– and N₃^– led to the formation of four new silver(I) coordination polymers {[Ag(btmb)]BF₄}_n ( 1 ), {[Ag₂(btmb)₃](NO₃)₂(H₂O)₅}_n ( 2 ), [Ag₂(btmb)(N₃)₂]_n ( 3 ), and [Ag(btmb)(N₃)]_n ( 4 ). Their coordination number varies from 2 (in 1 ) to 3 (in 2 ), 4 (in 3 ), and 5 (in 4 ). Different from the single chain structure of 1 , complex 2 displays a 1D ladder‐like double chain framework, whereas complex 3 exhibits a 2D layered architecture. Complex 4 has the same anion as complex 3 but shows a different metal‐to‐ligand ratio and a 1D double‐zigzag chain structure. Both 3 and 4 have Ag ··· Ag argentophilic interactions. The ligand btmb adopts both cis or trans configuration in the studied complexes. A trans‐ or cis‐btmb ligand link silver ions with Ag ··· Ag distances of ≈?18 and 13 Å, respectively. BF₄^– and NO₃^– are non‐coordinating anions in 1 and 2 . N₃^– is the bridging anion in 3 (1,3‐bridging fashion) and 4 (1,1‐bridging fashion). These findings suggest that the coordination numbers around the Ag^I ion correlate to the coordination abilities of anions and the btmb to silver ratio. In addition, the influence of anions on thermal stability were also investigated. This work is a good example that nicely supports the less explored field of anion‐dependent structures of complexes with non‐pyridyl ligands.     

Silver(I) sulfate coordination polymers with 4,4′‐bipyridazine and pyridazino[4,5‐d]pyridazine

Poly[[μ₄‐4,4′‐bipyridazine‐μ₅‐sulfato‐disilver(I)] monohydrate], {[Ag₂(SO₄)(C₈H₆N₄)]·H₂O}_n, (I), and poly[[aqua‐μ₄‐pyridazino[4,5‐d]pyridazine‐μ₃‐sulfato‐disilver(I)] monohydrate], {[Ag₂(SO₄)(C₆H₄N₄)(H₂O)]·H₂O}_n, (II), possess three‐ and two‐dimensional polymeric structures, respectively, supported by N‐tetradentate coordination of the organic ligands [Ag—N = 2.208 (3)–2.384 (3) Å] and O‐pentadentate coordination of the sulfate anions [Ag—O = 2.284 (3)–2.700 (2) Å]. Compound (I) is the first structurally examined complex of the new ligand 4,4′‐bipyridazine; it is based upon unprecedented centrosymmetric silver–pyridazine tetramers with tetrahedral AgN₂O₂ and trigonal–bipyramidal AgN₂O₃ coordination of two independent Ag^I ions. Compound (II) adopts a typical dimeric silver–pyridazine motif incorporating two kinds of square‐pyramidal AgN₂O₃ Ag^I ions. The structure exhibits short anion–π interactions involving noncoordinated sulfate O atoms [O...π = 3.041 (3) Å].