Three-dimensional Supramolecular Network Research Articles

Three-dimensional organic-inorganic hybrid sodium halide perovskite: C4H12N2·NaI3 and a hydrogen-bonded supramolecular three-dimensional network in 3C4H12N2·NaI4·3I·H2O.

The rational selection of ligands is vitally important in the construction of new organic-inorganic hybrid three-dimensional perovskite complexes. As part of an exploration of perovskite-type materials, two new Na-I compounds based on the piperazine ligand, namely poly[piperazinediium [tri-μ-iodido-sodium]], {(C4H12N2)[NaI3]}n, 1, and catena-poly[tris(piperazinediium) [[triiodidosodium]-μ-iodido] triiodide monohydrate], {(C4H12N2)3[NaI4]I3·H2O}n, 2, have been synthesized by adjusting the stoichiometric ratio of sodium iodide and piperazine, and were characterized by single-crystal X-ray diffraction. In the crystal structures of 1 and 2, each NaI cation is linked to six I atoms, but the compounds show completely different configurations. In 1, the structure includes a perovskite-like array of vertex-sharing NaI6 octahedra stretching along the direction of the three axes, and each piperazinediium dication is enclosed in the NaI3 perovskite cage. However, in 2, each NaI atom bridges a single I atom to form a one-dimensional linear chain, and complex intermolecular hydrogen bonds connect these one-dimensional chains into a three-dimensional supramolecular network.

Crystal structures and properties of two Cu(I) complexes based on Keggin-type clusters and diethyl 4,4′-dicarboxy-2,2′-biquinoline acid

Two proton-conductive Cu(I) complexes based on Keggin-type clusters, [Cu(debqdc)2]2[HPW12O40]·4H2O (1), and [Cu(debqdc)2]2[HPW12O40]·debqdc·4H2O (2), where debqdc is diethyl 4,4′-dicarboxy-2,2′-biquinoline, were simply synthesized at room temperature. The products were structurally characterized by elemental analyses, infrared spectroscopy, and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that both complexes crystallized in the triclinic space group P−1 and presented two three-dimensional supramolecular networks with one-dimensional hydrophilic channels via hydrogen-bonding interactions and π–π stacking interactions between the aromatic rings. In the [Cu(debqdc)2]+ ion, debqdc acts as a bidentate nitrogen donor ligand in the chelating fashion. The bulky debqdc ligand constrains the Cu(I) metal center within such a rigid environment in a tetrahedral geometry. The two complexes exhibit good proton conductivities (10−5 ~ 10−4 S cm−1) at 100 °C in the relative humidity range 35 ~ 98%. The luminescence behaviors of these complexes in the solid state at room temperature have also been investigated. Upon excitation at 285 nm, both 1 and 2 display three main emission peaks centered at 470, 520, and 568 nm, respectively.

1-Methoxy-1,1-diphenylbut-2-yne

In the title compound, C17H16O, the phenyl rings are twisted relative to each other at an angle of 85.9 (1)°. The crystal structure features weak C—H...π interactions, which connect the molecules into a three-dimensional supramolecular network.

3,4-Dibromo-2,2,5,5-tetraphenyl-2,5-dihydrofuran

The crystal structure of the title compound, C28H20Br2O, was solved in the orthorhombic space group P212121 with one molecule in the asymmetric unit. The phenyl rings are nearly planar and inclined at angles of 67.7 (1), 68.8 (1), 79.3 (1) and 62.3 (1)° to the plane of the 2,5-dihydrofuran ring. The crystal structure features C—H...π and Br...Br interactions, which connect the molecules to a three-dimensional supramolecular network.

Two new CoII coordination polymers with multifunctional 5-amino-2,4,6-tribromoisophthalic acid and flexible isomeric bis(imidazole) ligands: preparation, crystal structure and characterization.

Two new CoII coordination polymers (CPs), namely, catena-poly[[[(5-amino-2,4,6-tribromobenzene-1,3-dicarboxylato-κO)aquacobalt(II)]-bis[μ-1,3-bis(imidazol-1-ylmethyl)benzene-κ2N:N']] 4.75-hydrate], {[Co(C8H2Br3NO4)(C14H14N4)2(H2O)]·4.75H2O}n, (1), and poly[(μ-5-amino-2,4,6-tribromobenzene-1,3-dicarboxylato-κ2O1:O3)[μ-1,2-bis(imidazol-1-ylmethyl)benzene-κ2N:N']cobalt(II)], [Co(C8H2Br3NO4)(C14H14N4)]n, (2), have been synthesized successfully by the assembly of multifunctional 5-amino-2,4,6-tribromoisophthalic acid (H2ATBIP) and CoII ions in the presence of the flexible isomeric bis(imidazole) ligands 1,3-bis(imidazol-1-ylmethyl)benzene (mbix) and 1,2-bis(imidazol-1-ylmethyl)benzene (obix). The isomeric mbix and obix ligands have a big influence on the structures of CPs (1) and (2). CP (1) is composed of chains of nanometre-sized elliptical rings, in which the CoII atom exhibits a distorted octahedral coordination geometry and ATBIP2- acts as a monodentate ligand. Two adjacent chains are interlinked by π-π stacking interactions and hydrogen bonds, resulting in a supramolecular double chain. Hydrogen-bonded R86(16) rings extend adjacent supramolecular double chains into a two-dimensional supramolecular layer. Halogen bonding and a hydrogen-bonded R42(8) ring further link the two-dimensional supramolecular layers, leading to the formation of a three-dimensional supramolecular network. The CoII ion in CP (2) is tetracoordinated, exhibiting a distorted tetrahedral configuration. The ATBIP2- ligand exhibits a bis(monodentate) coordination bridging mode, linking adjacent CoII ions into zigzag chains, which are further bridged by the auxiliary bridging obix ligand, resulting in a two-dimensional (4,4) topological network. Interlayer hydrogen and halogen-halogen bonding further extend the two-dimensional layers into a three-dimensional supramolecular network. A detailed analysis of the solid-state UV-Vis-NIR diffuse-reflectance spectra of (1) and (2) indicates that a wide optical band gap exists in both (1) and (2). CP (1) exhibits an irreversible dehydration-rehydration behaviour.

Crystal structure and luminescence properties of a new dinuclear bismuth(III) coordination polymer containing three types of ligands

Abstract A new dinuclear bismuth(III) coordination polymer {[Bi(H2O)]2(C7H3NO4)2(C12H8N2)2(N3)2·2H2O} n (1) containing three types of ligands has been synthesized using a solvothermal method and characterized by infrared (IR) spectroscopy, energy-dispersive X-ray spectroscopy, and X-ray single-crystal structural analysis. The compound can be viewed as a three-dimensional supramolecular network that is constructed by Bi3+ cations, N3 − anions, pyridine-2,5-dicarboxylate (2,5-pdc2−), and 1,10-phenanthroline (phen) ligands. Moreover, the luminescence properties, quantum yield, luminescence decay, and thermal stabilities of 1 were also investigated.

Exploiting Dimensional Variability in Cu Paddle-Wheel Secondary Building Unit Based Mixed Valence Cu(II)/Cu(I) Frameworks from a Bispyrazole Ligand by Solvent/pH Variation

Four coordination polymers, [CuII(L)H2O]·2DMF (1), [CuICuII2L2(H2O)(pyridine)2]·(NO3)·4DMF·3H2O (2), [CuICuII2L2(pyridine)3]·(NO3)·DMF·4H2O (3), and [CuII2L(μ-O)(DMF)]·4DMF·5H2O (4), have been synthesized under solvothermal conditions using a single methylene-bispyrazole based carboxylic acid ligand, L, and Cu(NO3)2. All the compounds were comprised of copper paddle wheel secondary building units (SBUs). The structural differences in 1–4 arise due to different compositions of the solvent system as well as pH of the medium. Compound 1 exhibited a one-dimensional (1D) double chain structure with a porous three-dimensional (3D) supramolecular network, while 2 and 3 represent mixed Cu(II)/Cu(I) based porous frameworks. MOFs 2 and 3 were obtained by systematic binding of pyridine molecules on the axial positions of Cu paddle-wheel SBU, having a rare topology, sur; bbf-3,4-Cccm and a new topology, respectively. MOF 4 is a 3D porous network containing a Cu2(μ-O)2 moiety and exhibits a 3,4,4-c net. It contains op...

Crystal structure and Hirshfeld surface analysis of di-aqua-bis-(N,N-di-ethyl-nicotinamide-κN1)bis-(2,4,6-tri-methyl-benzoato-κO)manganese(II).

In the title centrosymmetric complex, [Mn(C10H11O2)2(C10H14N2O)2(H2O)2], the MnII cation is located on an inversion centre. The four O atoms form a slightly distorted square-planar arrangement around the MnII cation, and the distorted octa-hedral coordination is completed by two pyridine N atoms at distances of 2.3289 (15) Å. The dihedral angle between the planar carboxyl-ate group and the adjacent benzene ring is 87.73 (16)°, while the benzene and pyridine rings are oriented at a dihedral angle of 43.03 (8)°. In the crystal, the water mol-ecules are involved in both intra-molecular (to the non-coordinating carboxyl-ate O atom) and inter-molecular (to the amide carbonyl O atom) O-H⋯O hydrogen bonds. The latter lead to the formation of layers parallel to (100). These layers are further linked via weak C-H⋯O hydrogen bonds, resulting in a three-dimensional supra-molecular network. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (70.0%), H⋯O/O⋯H (15.5%) and H⋯C/C⋯H (14.0%) inter-actions. One of the ethyl groups of the di-ethyl-nicotinamide ligand is disordered over two sets of sites, with an occupancy ratio of 0.282 (10):0.718 (10).

Polycatenated 2D Hydrogen-Bonded Binary Supramolecular Organic Frameworks (SOFs) with Enhanced Gas Adsorption and Selectivity.

Controlled assembly of two-dimensional (2D) supramolecular organic frameworks (SOFs) has been demonstrated through a binary strategy in which 1,4-bis-(4-(3,5-dicyano-2,6-dipyridyl)pyridyl)naphthalene (2), generated in situ by oxidative dehydrogenation of 1,4-bis-(4-(3,5-dicyano-2,6-dipyridyl)dihydropyridyl)naphthalene (1), is coupled in a 1:1 ratio with terphenyl-3,3′,4,4′-tetracarboxylic acid (3; to form SOF-8), 5,5′-(anthracene-9,10-diyl)diisophthalic acid (4; to form SOF-9), or 5,5′-bis-(azanediyl)-oxalyl-diisophthalic acid (5; to form SOF-10). Complementary O–H···N hydrogen bonds assemble 2D 63-hcb (honeycomb) subunits that pack as layers in SOF-8 to give a three-dimensional (3D) supramolecular network with parallel channels hosting guest DMF (DMF = N,N′-dimethylformamide) molecules. SOF-9 and SOF-10 feature supramolecular networks of 2D → 3D inclined polycatenation of similar hcb layers as those in SOF-8. Although SOF-8 suffers framework collapse upon guest removal, the polycatenated frameworks of SOF-9 and SOF-10 exhibit excellent chemical and thermal stability, solvent/moisture durability, and permanent porosity. Moreover, their corresponding desolvated (activated) samples SOF-9a and SOF-10a display enhanced adsorption and selectivity for CO2 over N2 and CH4. The structures of these activated compounds are well described by quantum chemistry calculations, which have allowed us to determine their mechanical properties, as well as identify their soft deformation modes and a large number of low-energy vibration modes. These results not only demonstrate an effective synthetic platform for porous organic molecular materials stabilized solely by primary hydrogen bonds but also suggest a viable means to build robust SOF materials with enhanced gas uptake capacity and selectivity.

Two novel alkaline earth coordination polymers constructed from cinnamic acid and 1,10-phenanthroline: synthesis and structural and thermal properties.

In coordination chemistry and crystal engineering, many factors influence the construction of coordination polymers and the final frameworks depend greatly on the organic ligands used. The diverse coordination modes of N-donor ligands have been employed to assemble metal-organic frameworks. Carboxylic acid ligands can deprotonate completely or partially when bonding to metal ions and can also act as donors or acceptors of hydrogen bonds; they are thus good candidates for the construction of supramolecular architectures. We synthesized under reflux or hydrothermal conditions two new alkaline earth(II) complexes, namely poly[(1,10-phenanthroline-κ2N,N')bis(μ-3-phenylprop-2-enoato-κ3O,O':O)calcium(II)], [Ca(C10H7O2)2(C10H8N2)]n, (1), and poly[(1,10-phenanthroline-κ2N,N')(μ3-3-phenylprop-2-enoato-κ4O:O,O':O')(μ-3-phenylprop-2-enoato-κ3O,O':O)barium(II)], [Ba(C10H7O2)2(C10H8N2)]n, (2), and characterized them by FT-IR and UV-Vis spectroscopies, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction analysis, as well as by powder X-ray diffraction (PXRD) analysis. Complex (1) features a chain topology of type 2,4 C4, where the Ca atoms are connected by O and N atoms, forming a distorted bicapped trigonal prismatic geometry. Complex (2) displays chains of topology type 2,3,5 C4, where the Ba atom is nine-coordinated by seven O atoms of bridging/chelating carboxylate groups from two cinnamate ligands and by two N atoms from one phenanthroline ligand, forming a distorted tricapped prismatic arrangement. Weak C-H...O hydrogen bonds and π-π stacking interactions between phenanthroline ligands are responsible to the formation of a supramolecular three-dimensional network. The thermal decompositions of (1) and (2) in the temperature range 297-1173 K revealed that they both decompose in three steps and transform to the corresponding metal oxide.

Two zinc(II) coordination complexes based on an asymmetric multidentate ligand: syntheses, structures, selective fluorescence sensing of iron(III) ions and thermal analyses.

The rational selection of ligands is vitally important in the construction of coordination complexes. Two novel ZnII complexes, namely bis(acetato-κO)bis[1-(1H-benzotriazol-1-ylmethyl)-2-propyl-1H-imidazole-κN3]zinc(II) monohydrate, [Zn(C13H15N5)2(C2H3O2)2]·H2O, (1), and bis(azido-κN1)bis[1-(1H-benzotriazol-1-ylmethyl)-2-propyl-1H-imidazole-κN3]zinc(II), [Zn(C13H15N5)2(N3)2], (2), constructed from the asymmetric multidentate imidazole ligand, have been synthesized under mild conditions and characterized by elemental analyses, IR spectroscopy and single-crystal X-ray diffraction analysis. Both complexes exhibit a three-dimensional supramolecular network directed by different intermolecular interactions between discrete mononuclear units. The complexes were also investigated by fluorescence and thermal analyses. The experimental results show that (1) is a promising fluorescence sensor for detecting Fe3+ ions and (2) is effective as an accelerator of the thermal decomposition of ammonium perchlorate.

Synthesis, Structure, and Fluorescence of a Novel Cadmium Compound

A novel cadmium compound, [(CdI3)2(μ2-I)]2(Me2-4,4'-H2bipy)3 (1) (Me = methyl; 4,4'-bipy = 4,4'-bipyridine) with the Me2-4,4'-H2bipy moiety generated in situ, has been prepared through a solvothermal reaction and structurally characterized by X-ray single crystal diffraction analysis. Compound 1 is characterized by an isolated structural motif, consisting of [(CdI3)2(μ2-I)]3– anions and Me2-4,4'-H2bipy2+ cations. The [(CdI3)2(μ2-I)]3– anions and Me2-4,4'-H2bipy2+ cations interconnect together via C–H···I hydrogen-bonding interactions to complete a three-dimensional (3D) supramolecular network. Solid state fluorescent spectrum reveals an emission band in the violet region.

Crystal structure of catena-poly[[[tetra-aqua-iron(II)]-trans-μ-1,2-bis-(pyridin-4-yl)ethene-κ2N:N'] bis-(p-toluene-sulfonate) methanol disolvate

In the title polymeric complex, {[Fe(C12H10N2)2(H2O)4](CH3C6H4SO3)2·2CH3OH} n , the FeII cation, located on an inversion centre, is coordinated by four water mol-ecules in the equatorial positions and two 1,2-bis-(pyridin-4-yl)ethene mol-ecules in the axial positions. This results in a distorted octa-hedral geometry for the [N2O4] coordination polyhedron. The 1,2-bis-(pyridin-4-yl)ethene mol-ecules bridge the FeII cations, forming polymeric chains running along the a-axis direction. Stabilization of the crystal structure is provided by O-H⋯O hydrogen bonds; these are formed by coordinated water mol-ecules as donors towards the O atoms of the methanol mol-ecules and tosyl-ate anions as acceptors of protons, leading to the formation of a three-dimensional supra-molecular network. Weak C-H⋯O hydrogen bonds are also observed in the crystal.

Crystal structure of poly[[di-μ3-acetato-tetra-aqua-bis-(μ2-cyclo-hexane-1,4-di-carboxyl-ato)dilanth-an-um(III)] dihydrate

The title compound, {[La2(CH3COO)2(C8H10O4)2(H2O)4]·2H2O} n or [La2(ac)2(e,a-cis-1,4-chdc)2(H2O)4]·2H2O, where ac is acetate and 1,4-chdc is cyclo-hexane-1,4-di-carboxyl-ate anion, is a binuclear lanthanum(III) complex. Each metal atom is deca-coordinated by four O atoms from two distinct 1,4-chdc2- ligands, four O atoms from three acetate groups and two O atoms from coordinated water mol-ecules to form a distorted bicapped square-anti-prismatic geometry. Two non-coordinated water mol-ecules are also present in the formula unit. The most remarkable feature of this compound is that it possesses a only cis conformation for cyclo-hexane-1,4-di-carb-oxy-lic acid, although the raw material consists of a mixture of cis and trans isomers. The μ3-η2:η2 coordination mode of the bridging acetate group and the flexible di-carboxyl-ate fragments of 1,4-chdc2- results in the formation of infinite two-dimensional lanthanide-carboxyl-ate layers within the crystal structure. The directionality of strong inter-molecular O-H⋯O and weak C-H⋯O inter-actions provides robustness to the layers, which leads to the construction of a three-dimensional supra-molecular network. The crystal studied was refined as a two-component twin.

A one-dimensional HgII coordination polymer based on bis-(pyridin-3-ylmeth-yl)sulfane.

The reaction of mercury(II) chloride with bis-(pyridin-3-ylmeth-yl)sulfane (L, C12H12N2S) in methanol afforded the title crystalline coordination polymer catena-poly[[di-chlorido-mercury(II)]-μ-bis-(pyridin-3-ylmeth-yl)sulfane-κ2N:N'], [HgCl2L] n . The asymmetric unit consists of one HgII cation, one L ligand and two chloride anions. Each HgII ion is coordinated by two pyridine N atoms from separate L ligands and two chloride anions. The metal adopts a highly distorted tetra-hedral geometry, with bond angles about the central atom in the range 97.69 (12)-153.86 (7)°. Each L ligand bridges two HgII ions, forming an infinite -(Hg-L) n - zigzag chain along the b axis, with an Hg⋯Hg separation of 10.3997 (8) Å. In the crystal, adjacent chains are connected by inter-molecular C-H⋯Cl hydrogen bonds, together with Hg-Cl⋯π inter-actions [chloride-to-centroid distance = 3.902 (3) Å], that form between a chloride anion and the one of the pyridine rings of L, generating a two-dimensional layer extending parallel to (101). These layers are further linked by inter-molecular C-H⋯π hydrogen bonds, forming a three-dimensional supra-molecular network.

Preparation and characterization of two new CuII supramolecular coordination polymers incorporating sulfobenzoate and flexible heterocyclic ligands.

The assembly of CuII with the multifunctional ligand 2-amino-4-sulfobenzoic acid (H2asba) in the presence of the auxiliary flexible ligands 1,4-bis(triazol-1-ylmethyl)benzene (bbtz) and 1,4-bis(imidazol-1-ylmethyl)benzene (bix) under ambient conditions resulted in two new supramolecular coordination polymers, namely poly[[(3-amino-4-carboxybenzenesulfonato-κO)aquabis[μ2-1,4-bis(triazol-1-ylmethyl)benzene-κ2N4:N4']copper(II)] 3-amino-4-carboxybenzenesulfonate tetrahydrate], {[Cu(C7H6NO5S)(C12H12N6)2(H2O)](C7H6NO5S)·4H2O}n, (1), and poly[[bis(μ2-2-amino-4-sulfonatobenzoato-κ3O1:N,O1')tetraaqua[μ2-1,4-bis(triazol-1-ylmethyl)benzene-κ2N4:N4']dicopper(II)] tetrahydrate], {[Cu2(C7H5NO5S)2(C14H14N4)(H2O)4]·4H2O}n, (2). Single-crystal X-ray structure diffraction analysis of (1) reveals that the bbtz ligand acts as a bridge, linking adjacent CuII ions into a two-dimensional cationic (4,4) topological network, in which the coordinated 3-amino-4-carboxybenzenesulfonate (Hasba-) anion uses its sulfonate group to bind with the CuII ion in a monodentate fashion and the carboxylate group remains protonated. The lattice Hasba- anion resides in the two-dimensional layer and balances the charge. The carboxylate group of the 2-amino-4-sulfonatobenzoate (asba2-) ligand in (2) is involved in bidentate coordination, connecting adjacent CuII ions into carboxylate-bridged chains which are further bridged by the auxiliary flexible bix ligand in a trans-gauche (TG) mode, resulting in the formation of a two-dimensional network architecture. The amino group of the asba2- ligand in (2) also takes part in the coordination with the central CuII ion. The six-coordinated CuII centres in (1) and (2) exhibit distorted octahedral coordination geometries. Extensive hydrogen bonding exists in both (1) and (2). The interlayer hydrogen bonds in both compounds further extend adjacent two-dimensional layers into three-dimensional supramolecular network architectures. Furthermore, a detailed analysis of the solid-state UV-Vis-NIR (NIR is near IR) diffuse reflectance data indicates that (1) and (2) may have potential as wide band gap indirect semiconductor materials. Compounds (1) and (2) show reversible and irreversible dehydration-rehydration behaviours, respectively.

Crystal structure of bis[bis(4-azaniumylphenyl) sulfone] tetranitrate monohydrate.

In the title compound, the hydrated tetra-(nitrate) salt of dapsone (4,4'-di-amino-diphenyl-sulfone), 2C12H14N2O2S2+·4NO3-·H2O {alternative name: bis[bis-(4,4'-di-aza-niumylphen-yl) sulfone] tetra-nitrate monohydrate}, the cations are conformationally similar, with comparable dihedral angles between the two benzene rings in each of 70.03 (18) and 69.69 (19)°. In the crystal, mixed cation-anion-water mol-ecule layers lying parallel to the (001) plane are formed through N-H⋯O, O-H⋯O and C-H⋯O hydrogen-bonding inter-actions and these layers are further extended into an overall three-dimensional supra-molecular network structure. Inter-ring π-π inter-actions are also present [minimum ring centroid separation = 3.693 (3) Å].

Syntheses, structures, fluorescence sensing and magnetic properties of two coordination polymers based on 5-(benzimidazol-2-yl) isophthalic acid ligand

Two coordination complexes, constructed by 5-(benzimidazol-2-yl) isophthalic acid ligand, namely, [Eu(HL)2(NO3)]n (1) and [Tb(HL)2(NO3)]n (2) (H2L = 5-(benzimidazol-2-yl) isophthalic acid), were obtained under the same reaction conditions and characterized. Complexes 1 and 2 were isostructral, the Ln3+ cations were linked by the carboxylate groups of L ligand to form 1-D coordination chain. And these chains were connected with four adjacent ones through hydrogen bonds to form a three-dimensional supramolecular network structure. The fluorescence properties of complexes 1 and 2 have been studied. The emission bands are located at violent region 418 nm. The fluorescence intensity is apparently affected by different solvents and metal ions. Among which, the nitrobenzene and Cu2+ can quench the fluorescence emission efficiently; however, the addition of Cd2+ enhances the fluorescence intensity. The variable temperature susceptibility of complexes 1 and 2 were also studied.

Crystal structure of an AgI inter-calation compound: catena-poly[[silver(I)-μ-N-(pyridin-3-ylmeth-yl)pyridin-3-amine-κ2N:N'] hexa-fluorido-phosphate aceto-nitrile disolvate

The asymmetric unit in the title compound, [Ag(C11H11N3)]PF6·2CH3CN or {[AgL]·PF6·2CH3CN} n , L = N-(pyridin-3-ylmeth-yl)pyridin-3-amine, comprises one AgI atom, one L ligand, two aceto-nitrile solvent mol-ecules and one PF6- anion disordered over two orientations in a 0.567 (11):0.433 (11) ratio. Each AgI atom is coordinated by two pyridine N atoms from two L ligands in a slightly distorted linear coordination geometry [N-Ag-N = 170.55 (8)°]. Each L ligand bridges two AgI ions, resulting in the formation of a zigzag chain propagating along the [101] direction. In the crystal, Ag⋯Ag contacts [3.3023 (5) Å] and inter-molecular π-π stacking inter-actions [centroid-to-centroid distance = 3.5922 (15) Å] between the pyridine rings link these chains into a corrugated layer parallel to the ([Formula: see text]01) plane. The layers are stacked with a separation of 10.4532 (5) Å, and aceto-nitrile solvent mol-ecules and PF6- anions as guests are inter-calated between the layers. The layers are connected through several N/C-H⋯F hydrogen bonds and P-F⋯π inter-actions [F⋯ring centroid = 3.241 (8) Å] between the layer and the inter-calated guests and between the inter-calated guests, forming a three-dimensional supra-molecular network.

N′-[(E)-4-Chlorobenzylidene]-2-(2,3-dimethylanilino)benzohydrazide

In the title compound, C22H20ClN3O, the dihedral angle between the planes of the chlorophenyl and dimethylphenyl rings is 66.50 (9)°. These rings make dihedral angles 47.79 (8) and 69.24 (9)°, respectively, with the central benzene ring. In the crystal, molecules are linked into a three-dimensional supramolecular network by N—H...O, C—H...O hydrogen bonds and weak C—H...π interactions.