Pyridinylidenaminophosphines: Facile Access to Highly Electron-Rich Phosphines

Electron-rich tertiary phosphines are valuable species in chemical synthesis. However, their broad application as ligands in catalysis and reagents in stoichiometric reactions is often limited by their costly synthesis. Herein, we report the synthesis and properties of a series of phosphines with 1-alkylpyridin-4-ylidenamino and 1-alkylpyridin-2-ylidenamino substituents that are accessible in a very short and scalable route starting from commercially available aminopyridines and chlorophosphines. The determination of the Tolman electronic parameter (TEP) value reveals that the electron donor ability can be tuned by the substituent pattern at the aminopyridine backbone and it can exceed that of common alkylphosphines and N-heterocyclic carbenes. The potential of the new phosphines as strong nucleophiles in phosphine-mediated transformations is demonstrated by the formation of Lewis base adducts with CO₂ and CS₂. In addition, the coordination chemistry of the new phosphines towards Cu^I, Au^I, and Pd^II metal centers has been explored, and a convenient procedure to introduce the most basic phosphine into metal complexes starting from air-stable phosphonium salt is described.     

Coordination de la phosphine organo-fer [CpFeIIC6Me5CH2PPh2]+ au RhI et proprietes spectroscopiques,electrochimiques et catalytiques des complexes heterobinucleaires FeII-RhI

The reactions between the phosphine-organoiron [CpFe^II-η⁶-C₆Me₅CH₂PPh₂]⁺ PF₆^? (1) and [RhCl(η⁴-diolefin)(μ-Cl)]₂ in CH₂Cl₂ at reflux give the new heterobinuclear air-stable crystalline complexes [CpFe^II-η⁶-C₆Me₅CH₂)P(Ph)₂Rh(η⁴-diene)Cl]PF₆,(D'*-diene=cyclooctadiene (COD): 65%, 2; trimethylfluorobenzobicyclo[2.2.2]octadiene (Me₃TFB): 48%, 3). Complexes 2 and 3 have been studied by ¹H, ¹³C and ³¹P NMR spectroscopy and they are carbonylated (CO, 1 atm). Cyclic voltammetry experiments with addition of MeOH show electron transfer Fe^IRh^I → Fe^IIRh⁰, the presence of a catalytic wave Fe^I/Fe^II and the possible formation of Rh hydrides. Under normal conditions 2 is a catalyst for hydrogenation of cyclohexene, but it is less efficient than the known mononuclear Rh¹ analogues.     

Biogas Plasticization Coupled Anaerobic Digestion: Continuous Flow Anaerobic Pump Test Results

In this investigation, the Anaerobic Pump (®TAP) and a conventional continuous flow stirred tank reactor (CFSTR) were tested side by side to compare performance. TAP integrates anaerobic digestion (AD) with biogas plasticization–disruption cycle to improve mass conversion to methane. Both prototypes were fed a “real world” 50:50 mixture of waste-activated sludge (WAS) and primary sludge and operated at room temperature (20°C). The quantitative results from three steady states show TAP peaked at 97% conversion of the particulate COD in a system hydraulic residence time (HRT) of only 6 days. It achieved a methane production of 0.32 STP cubic meter CH₄ per kilogram COD fed and specific methane yield of 0.78 m³ CH₄ per cubic meter per day. This was more than three times the CFSTR specific methane yield (0.22 m³ CH₄ per cubic meter per day) and more than double the CFSTR methane production (0.15 m³ CH₄ per kilogram COD fed). A comparative kinetics analysis showed the TAP peak substrate COD removal rate (R _o) was 2.24 kg COD per cubic meter per day, more than three times the CFSTR substrate removal rate of 0.67 kg COD per cubic meter per day. The three important factors contributing to the superior TAP performance were (1) effective solids capture (96%) with (2) mass recycle and (3) stage II plasticization–disruption during active AD. The Anaerobic Pump (®TAP) is a high rate, high efficiency–low temperature microbial energy engine that could be used to improve renewable energy yields from classic AD waste substrates like refuse-derived fuels, treatment plant sludges, food wastes, livestock residues, green wastes and crop residuals.     

A Next-Generation Air-Stable Palladium(I) Dimer Enables Olefin Migration and Selective C−C Coupling in Air

We report a new air-stable Pd^I dimer, [Pd(μ-I)(PCy₂^tBu)]₂, which triggers E-selective olefin migration to enamides and styrene derivatives in the presence of multiple functional groups and with complete tolerance of air. The same dimer also triggers extremely rapid C−C coupling (alkylation and arylation) at room temperature in a modular and triply selective fashion of aromatic C−Br, C−OTf/OFs, and C−Cl bonds in poly(pseudo)halogenated arenes, displaying superior activity over previous Pd^I dimer generations for substrates that bear substituents ortho to C−OTf.     

Crystal Structures and Ionic Conductivities of Ternary Derivatives of the Silver and Copper Monohalides: I. Superionic Phases of Stoichiometry MA4I5:RbAg4I5, KAg4I5, and KCu4I5

The superionic properties of the compounds RbAg₄I₅, KAg₄I₅ and KCu₄I₅ have been investigated by powder neutron diffraction and complex impedance spectroscopy. RbAg₄I₅ and KAg₄I₅ have room-temperature ionic conductivities of σ=0.21(6) and 0.08(5) Ω⁻¹ cm⁻¹, respectively, which increase gradually on increasing temperature. KCu₄I₅ is only stable in the temperature range between 515(5) K and its melting point of 605 K, and its ionic conductivity is σ=0.61(8) Ω⁻¹ cm⁻¹, at T=540 K. At lower temperatures, KCu₄I₅ disproportionates into KI+4CuI and the ionic conductivity falls by over three orders of magnitude. Least-squares refinements of the powder neutron diffraction data for RbAg₄I₅ at ambient temperature confirm the reported structure (space group P4₁32, Z=4, a=11.23934(3) Å), though with some differences in the preferred locations of the mobile Ag⁺. KAg₄I₅ and KCu₄I₅ are found to adopt the same basic structure as RbAg₄I₅, with the I− forming a β-Mn-type sublattice, with the K⁺ located in a distorted octahedral environment and the Ag⁺(Cu⁺) predominantly distributed over two sites which are tetrahedrally co-ordinated to I⁻. The implications for the conduction mechanism within these compounds are discussed, using a novel maximum entropy difference Fourier technique to map the distribution of the Ag⁺(Cu⁺) within the unit cell.     

Bulky Cations and Four different Polyiodide Anions in [Lu(Db18c6)(H2O)3(thf)6]4(I3)2(I5)6(I8)(I12)

Black single crystals of [Lu(Db18c6)(H₂O)₃(thf)₆]₄(I₃)₂(I₅)₆(I₈)(I₁₂) were obtained from lutetium, I₂ and Db18c6 (dibenzo‐18‐crown‐6) in THF solution. In the bulky cation, Lu³⁺ is surrounded by nine oxygen atoms, six of Db18c6 and three of water molecules to which two THF molecules are attached each. Meanwhile, four polyiodide anions, (I₃)^–, (I₅)^–, (I₈)^2– and (I₁₂)^2–, in a 2:6:1:1 ratio form a three‐dimensional network and leave space for the bulky cations.     

Synchronized separation,concentration and determination of trace chloramphenicol,thiamphenicol and florfenicol in food by using polyoxyethylene cetyl ether-salt aqueous two-phase system coupled with high-performance liquid chromatography

As a novel and green pretreatment technique to trace samples, polyoxyethylene cetyl ether (POELE20)–(NH₄)₂SO₄ aqueous two-phase extraction system was coupled with high-performance liquid chromatography to analyse synchronously chloramphenicol (CAP), thiamphenicol (TAP) and florfenicol (FF) in chicken and pork samples. It was found that the extraction efficiency (E%) and enrichment factor (F) of the three antibiotics were influenced by the types of salts, the concentration of salt, the concentration of POELE20, system temperature and pH. The final optimal condition was as following: the phase-forming salt is (NH₄)₂SO₄, the concentration of (NH₄)₂SO₄ is 0.141 g mL^?1, the concentration of POELE20 is 0.03 g mL^?1, the temperature is 298.15 K, and the system pH is 4.5. This POELE20–(NH₄)₂SO₄ ATPS was applied to separate and enrich three antibiotics in real sample under the optimal conditions, and it was found that the recovery was 97.20–102.00 % with a RSD of 0.61–4.85 %. The limit of detection for CAP, TAP and FF were 0.10, 0.50 and 0.50 μg kg^?1, and the limit of quantitation for CAP, TAP and FF was 0.15, 1.50 and 1.50 μg kg^?1. Seven times the experiments were used to verify the repeatability and veracity of this method, and the RSD for the intra-day and inter-day were 1.13–3.22 and 1.74–4.72 %.     

Sterically Demanding AgI and CuI N-Heterocyclic Carbene Complexes: Synthesis,Structures, Steric Parameters,and Catalytic Activity

The synthesis and full characterization of new air-stable Ag^I and Cu^I complexes bearing structurally bulky expanded-ring N-heterocyclic carbene (erNHC) ligands is presented. The condensation of protonated NHC salts with Ag₂O afforded a collection of Ag^I complexes, and their first use as ligand transfer reagents led to novel isostructural Cu^I or Au^I complexes. In situ deprotonation of the NHC salts in the presence of a copper(I) source, provides a library of new Cu^I complexes. The solid-state structures feature large N-C_NHC-N angles (118–128°) and almost identical angles between the aryl groups on the nitrogen atoms and the plane of the N-C-N unit of the carbene (i.e. torsion angles close to 0°). Among the steric parameters, the percent buried volume (%V_bur) values span easily in the 50–57 % range, and that one of (9-Dipp)CuBr complex (%V_bur=57.5) overcomes to other known erNHC–metal complexes reported to date. Preliminary catalytic experiments in the copper-catalyzed coupling between N-tosylhydrazone and phenylacetylene, afforded 76–93 % product at the 0.5–2.5 mol % catalyst loading, proving the stability of Cu^I erNHC complexes at elevated temperatures (100 °C).     

Electrocatalytic H2 Generation from Water Relying on Cooperative Ligand Electron Transfer in “PN3P” Pincer-Supported NiII Complexes

Water is the most sustainable source for H₂ production, and the efficient electrocatalytic production of H₂ from mixed water/acetonitrile solutions by using two new air-stable nickel(II) pincer complexes, [Ni(κ³-2,6-{Ph₂PNR}₂(NC₅H₃)Br₂] (R=H I , Me II ) is reported. Hydrogen generation from H₂O/CH₃CN solutions is initiated at −2 V against Fc^+/0, and bulk electrocatalysis studies showed that the catalyst functions with an excellent Faradaic efficiency and a turnover frequency of 160 s⁻¹. A DFT computational investigation of the reduction behavior of I and II revealed a correlation of H₂ formation with charge donation from electrons originating in a reduced ligand-localized orbital. As a result, these catalysts are proposed to proceed by a novel mechanism involving electron/proton transfer between a Ni^0I species bonded to an anionic PN³P ligand (“L⁻/Ni^0I”) and a Ni^I-hydride (“Ni−H”). Furthermore, these catalysts are able to reduce phenol and acetic acid, more active proton sources, at lower potentials that correlate with the substrate pK_a.     

A new three‐dimensional silver(I) coordination framework with a diamondoid topology constructed from 2‐(pyridin‐4‐yl)‐1H‐imidazole‐4,5‐dicarboxylic acid

The title compound, poly[[μ₄‐5‐carboxy‐4‐carboxylato‐2‐(pyridin‐4‐yl)‐1H‐imidazol‐1‐ido]disilver(I)], [Ag₂(C₁₀H₅N₃O₄)]_n, was synthesized by reacting silver nitrate with 2‐(pyridin‐4‐yl)‐1H‐imidazole‐4,5‐dicarboxylic acid (H₃PyIDC) under hydrothermal conditions. The asymmetric unit contains two crystallographically independent Ag^I cations and one unique HPyIDC²⁻ anion. Both Ag^I cations are three‐coordinated in distorted T‐shaped coordination geometries. One Ag^I cation is coordinated by one N and two O atoms from two HPyIDC²⁻ anions, while the other is bonded to one O and two N atoms from two HPyIDC²⁻ anions. It is interesting to note that the HPyIDC²⁻ group acts as a μ₄‐bridging ligand to link the Ag^I cations into a three‐dimensional framework, which can be simplified as a diamondoid topology. The thermal stability and photoluminescent properties of the title compound have also been studied.     

Distorted Porphyrins with High Stability: Synthesis and Characteristic Electronic Properties of Mono- and Di-Nuclear Tricarbonyl Rhenium Tetraazaporphyrin Complexes

Mono- and di-nuclear tricarbonyl Re(I) tetraazaporphyrin complexes ( Re₁TAP and Re₂TAP ) are investigated and compared with Re(I) phthalocyanine complexes ( Re₁Pc and Re₂Pc ). Although Re₂Pc is unstable in polar solvents, and easily undergoes demetallation reaction, the coordination of the TAP ligand significantly improves the tolerance toward polar solvents, affording more stability to Re₂TAP . Additionally, the incorporation of [Re(CO)₃]⁺ unit(s) and the TAP ligand results in remarkable positive shifts in both oxidation and reduction potentials. Consequently, the more positive oxidation potentials of the ReTAP complexes significantly increase the tolerance toward oxidation, while the reduction potential indicates that Re₂TAP is suitable for a soluble electron acceptor. In contrast to Re₁Pc and Re₂Pc , Re₁TAP and Re₂TAP show unique broad Q bands, which can be attributed to the admixture of the π-π* and metal-to-ligand charge transfer characters, owing to the lowered π orbital energy in the TAP complexes. This study is useful for controlling electronic properties and realizing high stability in Pc analogues.     

Air-Stable PdI Dimer Enabled Remote Functionalization: Access to Fluorinated 1,1-Diaryl Alkanes with Unprecedented Speed

While remote functionalization via chain walking has the potential to enable access to molecules via novel disconnections, such processes require relatively long reaction times and can be in need of elevated temperatures. This work features a remote arylation in less than 10 min reaction time at room temperature over a distance of up to 11 carbons. The unprecedented speed is enabled by the air-stable Pd^I dimer [Pd(μ-I)(PCy₂^tBu)]₂, which in contrast to its P^tBu₃ counterpart does not trigger direct coupling at the initiation site, but regioconvergent and chemoselective remote functionalization to yield valuable fluorinated 1,1-diaryl alkanes. Our combined experimental and computational studies rationalize the origins of switchability, which are primarily due to differences in dispersion interactions.     

Encapsulation of tricopper cluster in a synthetic cryptand enables facile redox processes from CuICuICuI to CuIICuIICuII states

One-pot reaction of tris(2-aminoethyl)amine (TREN), [Cu^I(MeCN)₄]PF₆, and paraformaldehyde affords a mixed-valent [TREN₄Cu^IICu^ICu^I(μ₃-OH)](PF₆)₃ complex. The macrocyclic azacryptand TREN₄ contains four TREN motifs, three of which provide a bowl-shape binding pocket for the [Cu₃(μ₃-OH)]³⁺ core. The fourth TREN caps on top of the tricopper cluster to form a cryptand, imposing conformational constraints and preventing solvent interaction. Contrasting the limited redox capability of synthetic tricopper complexes reported so far, [TREN₄Cu^IICu^ICu^I(μ₃-OH)](PF₆)₃ exhibits several reversible single-electron redox events. The distinct electrochemical behaviors of [TREN₄Cu^IICu^ICu^I(μ₃-OH)](PF₆)₃ and its solvent-exposed analog [TREN₃Cu^IICu^IICu^II(μ₃-O)](PF₆)₄ suggest that isolation of tricopper core in a cryptand enables facile electron transfer, allowing potential application of synthetic tricopper complexes as redox catalysts. Indeed, the fully reduced [TREN₄Cu^ICu^ICu^I(μ₃-OH)](PF₆)₂ can reduce O₂ under acidic conditions. The geometric constraints provided by the cryptand are reminiscent of Nature''s multicopper oxidases (MCOs). For the first time, a synthetic tricopper cluster was isolated and fully characterized at Cu^ICu^ICu^I (4a), Cu^IICu^ICu^I (4b), and Cu^IICu^IICu^I (4c) states, providing structural and spectroscopic models for many intermediates in MCOs. Fast electron transfer rates (10⁵ to 10⁶ M⁻¹ s⁻¹) were observed for both Cu^ICu^ICu^I/Cu^IICu^ICu^I and Cu^IICu^ICu^I/Cu^IICu^IICu^I redox couples, approaching the rapid electron transfer rates of copper sites in MCO.

Geometric constraints and site isolation provided by the cryptand enable reversible redox of tricopper μ-oxo cluster.     

A copper(I) coordination polymer incorporation the corrosion inhibitor 1H‐benzotriazole: poly[μ3‐benzotriazolato‐κ3N1:N2:N3‐copper(I)]

The title complex, [Cu(C₆H₄N₃)]_n, was synthesized by the reaction of cupric nitrate, 1H‐benzotriazole (BTAH) and aqueous ammonia under hydrothermal conditions. The asymmetric unit contains three crystallographically independent Cu^I cations and two 1H‐benzotriazolate ligands. Two of the Cu^I cations, one with a linear two‐coordinated geometry and one with a four‐coordinated tetrahedral geometry, are located on sites with crystallographically imposed twofold symmetry. The third Cu^I cation, with a planar three‐coordinated geometry, is on a general position. Two Cu^I cations are doubly bridged by two BTA⁻ ligands to afford a noncentrosymmetric planar [Cu₂(BTA)₂] subunit, and two [Cu₂(BTA)₂] subunits are arranged in an antiparallel manner to form a centrosymmetric [Cu₂(BTA)₂]₂ secondary building unit (SBU). The SBUs are connected in a crosswise manner via the sharing of four‐coordinated Cu^I cations, Cu—N bonding and bridging by two‐coordinate Cu^I cations, resulting in a one‐dimensional chain along the c axis. These one‐dimensional chains are further linked by C—H...π and weak van der Waals interactions to form a three‐dimensional supramolecular architecture.     

Organic–Inorganic Hybrid Gold Halide Perovskites: Structural Diversity through Cation Size

Crystal structures of a series of organic–inorganic hybrid gold iodide perovskites, formulated as A₂[Au^II₂][Au^IIII₄] [A=methylammonium (MA) ( 1 ) and formamidinium (FA) ( 2 )], A′₂[I₃]_1−x[Au^II₂]_x[Au^IIII₄] [A′=imidazolium (IMD) ( 3 ), guanidinium (GUA) ( 4 ), dimethylammonium (DMA) ( 5 ), pyridinium (PY) ( 6 ), and piperizinium (PIP) ( 7 )], systematically changed depending on the cation size. In addition, triiodide (I₃⁻) ions were partly incorporated into the AuI₂⁻ sites of 3 – 7 , whereas they were not incorporated into those of 1 and 2 . Such a difference comes from the size of the organic cation. Optical absorption spectra showed characteristic intervalence charge-transfer bands from Au^I to Au^III species, and the optical band gap increased as the size of the cation became larger.     

Polyethyleneoxide (PEO)-based, anion conducting solid polymer electrolyte for PEC solar cells

Solid polymer electrolyte membranes were prepared by complexing tetrapropylammoniumiodide (Pr₄N⁺I^?) salt with polyethylene oxide (PEO) plasticized with ethylene carbonate (EC), and these were used in photoelectrochemical (PEC) solar cells fabricated with the configuration glass/FTO/TiO₂/dye/electrolyte/Pt/FTO/glass. The PEO/Pr₄N⁺I^?+I₂?=?9:1 ratio gave the best room temperature conductivity for the electrolyte. For this composition, the plasticizer EC was added to increase the conductivity, and a further conductivity enhancement of four orders of magnitude was observed. An abrupt increase in conductivity occurs around 60–70 wt% EC; the room temperature conductivity was 5.4?×?10^?7 S cm^?1 for 60 wt% EC and 4.9?×?10^?5 S cm^?1 for the 70 wt% EC. For solar cells with electrolytes containing PEO/Pr₄N⁺I^?+I₂?=?9:1 and EC, IV curves and photocurrent action spectra were obtained. The photocurrent also increased with increasing amounts of EC, up to three orders of magnitude. However, the energy conversion efficiency of this cell was rather low.     

Untersuchungen an Polyhalogeniden III. Tetrammin-kupfer(II)-tetraiodid, [Cu(NH3)4I2 · I2], und Tetrammin-kupfer(II)-hexaiodid, [Cu(NH3)4I3]I3

Studies on Polyhalides. III. Crystal Structures of [Cu(NH₃)₄I₂ · I₂] and [Cu(NH₃)₄I₃]I₃ Tetramminecopper(II)tetraiodide [Cu(NH₃)₄I₂ · I₂] (I) crystallizes monoclinically in the space group C2/m with a = 1 185.9 pm, b = 892.8 pm, c = 656.8 pm, β = 111.10° and Z = 2 formula units. Tetramminecopper(II)hexaiodide [Cu(NH₃)₄I₃]I₃ (II) crystallizes orthorhombically in the space group Pnnm with a = 874.9 pm, b = 1 089.8 pm, c = 885.3 pm, and Z = 2 formula units. A special feature of these structures are coordinated polyiodide ions I₄^2? (I) or I₃^? (II). In both compounds four coplanar nitrogen atoms and two axial iodine atoms form a quasi-octahedral coordination around copper with the usual (4+2)-tetragonal distortion. The copper ions are connected by linear, centrosymmetric polyiodide ions I₄^2? (I) or I₃^? (II). Therefore infinite planar zigzag chains of units [Cu(NH₃)₄I₄] (I) or [Cu(NH₃)₄I₃]⁺(II) are resulting. The counterion I₃^? (II) is intercalated between these chains.     

Reversible Transformation between Cubane and Stairstep Cu4I4 Clusters Using Heat or Solvent Vapor

The controlled self‐assembly of CuI and an asymmetric ligand with mixed N/S donors, 2‐(tert‐butylthio)‐N‐(pyridin‐3‐yl)acetamide ( L ), afforded three Cu^I coordination polymers (CPs), [Cu₄I₄ L ₂(MeCN)₂]_n ( 1 ), [Cu₄I₄ L ₂]_n ( 2 ), and {[Cu₄I₄ L ₂] ? MeOH}_n ( 3 ). X‐ray analyses showed that CPs 1 – 3 are supramolecular isomers with 1, 2, and 3D structures, respectively. CP 1 adopts a stairstep Cu₄I₄ cluster, whereas CPs 2 and 3 are composed of cubane‐like Cu₄I₄ clusters. Crystal‐to‐crystal transformations of 1 to 2 and 3 showed reversible transformations between different Cu₄I₄ clusters using heat or solvent (acetonitrile or methanol) vapor. CP 2 was reversibly transformed to 3 by the addition of methanol and heat. Therefore, the transformations between supramolecular isomers 1 , 2 , and 3 are completely reversible.     

Interaction of Iodine with Hexaaza-18-crown-6 and Tetraaza-14-crown-4 in Chloroform Solution

Interactions of hexaaza-18-crown-6 (HA18C6) and tetraaza-14-crown-4 (TA14C4) with iodine have been investigated spectrophotometrically in chloroform solution. The observed time dependence of the charge-transfer band and subsequent formation of I₃ ^- in solution were related to the slow transformation of the initially formed 1:1 macrocycle. I₂ outer complex to an inner electron donor-acceptor (EDA) complex, followed by fast reaction of the inner complex with iodine to form a triiodide ion, as follows: macrocycle + I₂→_fast ^K _f macrocycle.I₂ (outer complex) macrocycle.I₂ (outer complex) →^slow (macrocycle.I⁺)I^- (inner complex) macrocycle.I⁺)I^- (inner complex) + I²→^slow (macrocycle.I⁺)I₃ ^-. The pseudo-first-order rate constants at various temperatures for thetransformation process were evaluated from the absorbance-time data. The activation parameters (E_a, Δ H^?, and Δ S^?) for thetransformation were obtained from the temperature dependence of the rate constants. The stoichiometry and formation constants of the resulting EDA complexes have also been determined. It was found that the (TA14C4.I⁺)I₃ ^- is more stable the (HA18C6.I⁺)I₃ ^- complex in chloroform solution.     

A three‐dimensional framework of bis­[tris­(ethyl­enediamine)zinc] tetra­iodo­cadmate diiodide assisted by N—H⋯I hydrogen bonds

The title salt, [Zn(C₂N₂H₈)₃]₂[CdI₄]I₂, conventionally abbreviated [Zn(en)₃]₂[CdI₄]I₂, where en is ethyl­enediamine, contains discrete [Zn(en)₃]²⁺ cations and [CdI₄]²⁻ anions with distorted octa­hedral and nearly tetra­hedral geometries, respectively, as well as uncoordinated I⁻ ions. The cation and the free I⁻ anion lie on twofold rotation axes and the [CdI₄]²⁻ anion lies on a axis in the space group I2d. The structure exhibits numerous weak inter‐ionic hydrogen bonds of two types, viz. N—H⋯I⁻(free ion) and N—H⋯I([CdI₄]²⁻), which support the resulting three‐dimensional framework.