Secondary Nitrogen Atoms Research Articles

Imino(dialkylamino)isoindolines: Structures and dynamic behavior

In 1956, Elvidge and coworkers investigated the synthesis of a series of isoindoline compounds derived from phthalonitrile. They produced a series of secondary amine-modified isoindolines known as the imino(dialkylamino)isoindolines, and in this report, we revisit this chemistry. In addition to confirming the previously observed reactivity, we structurally characterized three examples and observed a double bond character between the isoindoline carbon atom and the secondary nitrogen atom position. This results in a rotational barrier about this bond, which we observed by NMR spectroscopy and probed using computational methods. The barriers are comparable to those seen in bis-substituted amides.

Sorption Extraction of Gallium from Alumina-Alkaline Solutions

AbstractThe possibility of sorption concentration of gallium from alumina-alkaline solutions resulting by leaching of recycled soda with sludge water during alumina production—which are middlings of alumina production—has been studied. During bauxite processing, soda is accumulated in recycled alkali solutions, extracted by evaporation and used in sintering. The sludge water is formed during storage of wastes pumped in the form of slurry to the settling tank and can be used in production as wash water. Sorption processes with application of ion exchange resins with high capacity and selectivity, presented in the world market in a large assortment, seem to be a promising direction of gallium concentration from alumina-alkaline solutions. On the basis of the analysis carried out, anion exchangers AN-31 and D-403 OH form were selected for sorption concentration of gallium from alumina-alkaline solutions. A comparative analysis of the sorption properties showed that the D-403 anion exchange resin exhibited better selectivity and a higher dynamic exchange capacity for gallium. The high capacity for gallium absorption with the D-403 anion exchanger resulted from its greater basicity, since the oxyhydryl groups at the β-, γ- and δ-positions in the resin matrix exert a greater negative inductive effect on the tertiary nitrogen atom, which has a lone electron pair, compared to the oxyhydryl and hydroxy groups in the β- and γ-positions relative to the secondary nitrogen atom of the anion exchange resin AN- 31. Due to the unshared electron pair of the nitrogen atom, an additional covalent effect arose, causing stronger chemical bonding between the gallium ions and the D-403 anion exchange matrix. Studies were carried out to determine the optimal conditions for the desorption of gallium with a 2 N sodium hydroxide solution. The gallium content in the alkaline eluates was suitable for electrolytic production of metallic gallium.

Средне-щелочные алкилфенолятные присадки

The article presents the results of research on the sintesis of medium alkaline alkylphenolate additives. Additives are calcium salts of the condensation products of alkylphenols with formaldehyde and ammonia or various amines (monoethanolamine, benzylamine and allylamine) have been synthesized and studied. The physicochemical and functional properties of the synthesized products were studied by standard methods.It has been shown that all aminomethyl derivatives of alkylphenols have multifunctional properties and are superior to their analogs ИХП-101, ИХП-109 and ВНИИНП-370 in terms of their functional properties. In addition, the additives obtained on the basis of nonylphenol in terms of anticorrosion and antioxidant properties are somewhat superior to those obtained on the basis of alkylphenol (C8–C12) due to their homogeneous composition. Thus, all synthesized compounds are multifunctional, and additives containing a secondary nitrogen atom (calcium salt of dialkyldioxybenzylamine) and a benzyl radical at the nitrogen atom (calcium salt of N-benzyldialkyldioxybenzylamine) have the highest antioxidant efficiency.

Synthesis, characterization, DFT and biological studies of Fe(II), Cu(II), and Zn(II) complexes of keto-imine chelators

Three naphthoquinone-based chelators, 2-(pyrimidin-2-ylamino)-2,3-dihydronaphthalene-1,4-dione (HLa) 2-((4,6-dihydroxypyrimidin-2-yl)amino-2,3-dihydronaphthalene-1,4-dione (HLb), and 2-((4,6-dimethylpyrimidin-2-yl)amino-2,3-dihydronaphthalene-1,4-dione (HLc), have been synthesized by the reaction of 2-hydroxy-1,4-napthoquinone with 2-aminopyrimidine, 2-amino-4,6-dihydroxypyrimidine, and 2-amino-4,6-dimethypyrimidine respectively. Reaction of the chelators with Fe2+; Cu2+ and Zn2+ sulphate; and acetate salts; plus 2,2′-bipyridine(B) gave the resultant heteroleptic M2+ complexes, which were characterized by analytical, 1H-and 13C NMR, FT-IR, UV–vis, ESI-MS, and TG-DSC analyses. The FT-IR and NMR results showed that the chelators are bidentate and chelated with the M2+ ions via their ketonic oxygen (>CO) and secondary amine nitrogen (HN) atoms. The μeff data and UV–vis spectral evaluations of the complexes provided credence to the 6-coordinate octahedral geometries of the complexes. DFT calculations were performed to understand the mode of complex formation as well as their geometry around the metal centers. Compared to the chelators, the heteroleptic complexes have improved antimicrobial actions attributed to the extra 2-nitrogenous atoms in the 2,2′-bipyridine moiety and the presence of active metal ions. The CuLc complexes displayed the best antibacterial performance with inhibitory effects of 34.0 mm. However, the ZnLb complexes recorded the best antifungal activity (33.0 mm), due to the absorption of Zn2+ ions on the surface of the fungiform cell walls. The antioxidant assays with ferrous ions show that all the keto-imine chelators showed good chelating abilities. HLc showed values of 78.76 plus 74.5 % separately at concentrations of 200 and 100 mg/mL, which are higher than that of the standard ascorbic acid. The DPPH radical scavenging activities of the heteroleptic complexes indicate that they can be used for the synthesis of drugs for the treatment of pathological diseases arising from oxidative stress.

Engineering strong electronegative nitrogen-rich porous organic polymer for practical durable lithium-sulfur battery

The practical application of porous organic polymers (POPs) in Li–S batteries (LiSBs) is severely hampered by low sulfur loading and weak chemisorption. Here, a novel organosulfur copolymer host (POP@F/S) with polar nitrogen-rich heteroatoms is prepared by in situ anchoring of sulfur in 3D perfluorinated hierarchical porous polymers via nucleophilic aromatic substitution reaction (SNAr) reaction. The design of hierarchical pore structure with high porosity not only offers strong physical confinement to polysulfide species but also increase the sulfur loading and buffer the volume change during lithiation. Notably, calculations and experimental results indicate that the triazine and secondary amine nitrogen atoms containing lone electron pairs can act as Lewis base sites to strongly interact with the terminal lithium ions in lithium polysulfide, thereby suppressing the shuttle effect. Attributed to these merits, LiSBs with POP@F/S composite cathode exhibit excellent rate capability and ultra-low capacity decay of only 0.019% per cycle after 500 cycles at 1C. Even more excitingly, a desirable areal capacity of 8.65 mAh cm−2 is delivered when with 7.9 mg cm−2 sulfur loading, and a satisfactory lifetime of over 150 cycles is maintained even under lean electrolyte (E/S = 5 μL mg−1), demonstrating remarkable potential in developing high-performance LiSBs.

Crystal structure of 4-(2-meth-oxy-phen-yl)piper-azin-1-ium 3,5-dintrosalicylate.

The title salt [systematic name: 4-(2-methoxyphenyl)piperazin-1-ium 2-carboxy-4,6-dinitrophenolate], C11H17N2O+·C7H3N2O7 -, exhibits secondary nitro-gen atoms (N-H) in the 2-meth-oxy-phenyl-piperazine (2MeOPP) cation, which is protonated with a phenolic hydrogen atom of 3,5-di-nitro-salicylic acid (DNSA). One of the oxygen atoms of the nitro group in the 3,5-di-nitro-salicylate anion is disordered over two orientations with occupancy factors of 0.65 (7) and 0.35 (7) . The 2-meth--oxy-phenyl-piperazinium cation and 3,5-di-nitro-salicylate anion are linked in the asymmetric unit by a bifurcated N-H⋯O hydrogen bond, which formed is between the H atom in the protonated piperazinium unit of the cation and the carb-oxy-lic acid group in the anion. The piperazine ring adopts a chair conformation. The crystal structure features N-H⋯O and C-H⋯O hydrogen bonds inter-actions, which lead to the formation of a sandwich-like arrangement. Hirshfeld surface analysis was used to determine the relative contributions of various inter-molecular inter-actions, indicating that that H⋯O/O⋯H (38. 3%) and H⋯H (31. 8%) contacts are the major contributors.

A turn-on fluorescence sensor based on Cu2+ modulated DNA-templated silver nanoclusters for glyphosate detection and mechanism investigation

The abuse application of glyphosate can result in a potential hazard for environment and human, however its ultrasensitive detection remains challenging. Herein, a Cu2+ modulated DNA-templated silver nanoclusters (DNA-AgNCs) sensor was constructed to sensitively determine glyphosate based on the turn-on fluorescence strategy. The fluorescence quenching of DNA-AgNCs occurred with the existence of Cu2+. Upon the presence of glyphosate, the functional groups on the surface of glyphosate could chelate with Cu2+, following the fluorescence recovery of DNA-AgNCs. Through the stoichiometric methods, we unveil that Cu2+-trigged fluorescence quenching mode is a combination of static and dynamic quenching with the static mode being predominant. In DNA-AgNCs/Cu2+ system, the carboxylate, amine, and phosphonate groups of glyphosate interact with Cu2+ through chelation, in which the carboxylate oxygen, the phosphonate oxygen atoms, and the monoprotonated secondary amine nitrogen atom and Cu2+ form chelate rings. This fluorescence sensor showed a desired linearity of glyphosate analysis under the optimum conditions, ranging from 15 to 100 μg/L with a low detection down to 5 μg/L. Moreover, the proposed sensor was successfully utilized to measure glyphosate in real samples, indicating a promising application in pesticide residues detection.

New amine adducts with carbon dioxide as blowing agents in the production of integral polyurethane foams

Blowing agents play an important role in the production of cellular polyurethanes. The traditional chemical blowing agent H2O/CO2 did not meet all application requirements. This led to the introduction of physical foaming agents in the 1950–1960s, which were subject to four further modifications due to climatic hazards. The recently introduced new generation of hydrofluoroolefins (HFOs) hydrocarbons is currently in the application assessment and meets the utility and climate requirements for now. Without waiting for a long-term final assessment of this blowing agent group, an attempt was made to introduce carbon dioxide in the form of adducts with aliphatic amines into the foaming process. As example compounds, CO2 adducts with aliphatic hydrocarbons containing also primary, secondary and tertiary nitrogen atoms in the same molecule were used. The synthesis of adducts was carried out by the absorption of carbon dioxide gas in a solution of amines in monoethylene glycol (MEG) and triethanolamine (TELA). The resulting solutions containing 12–16 wt % CO2 were next used in the application-oriented study. Amines regulating the foaming and gelation processes were used for the production of adducts, which allowed the elimination of organometallic gelling additives. Selected adducts were checked during the production of furniture chair seats on an industrial scale, obtaining integral foams in the range of density 190–294 kg/m3 and hardness 22–38 °ShA. In the production process of these foams carried out at PLASTPUR a double-stream foaming machine from Hennecke was used.

Symbiotic prodrugs (SymProDs) dual targeting of NFkappaB and CDK

The release of an active drug from the prodrug generates a pro-fragment that typically has no biological activity and could result in adverse effects. By combining two drugs, wherein each drug acts as a pro-fragment of the other drug will eliminate the pro-fragment in the prodrug. As they are prodrugs of each other and are symbiotic, we termed these as symbiotic prodrugs (SymProDs). To test this idea, we generated SymProDs using NFκB inhibitors that contain the reactive α-methylene-γ-butyrolactone moiety and CDK inhibitors with solvent exposed secondary nitrogen atoms. We show that secondary amine prodrugs of α-methylene-γ-butyrolactone containing NFκB inhibitors undergo slow release over a 72hr period. Using an alkyne-tagged secondary amine prodrug of α-methylene-γ-butyrolactone containing NFκB inhibitor, we demonstrate target engagement. The NFκB-CDK SymProDs were ~20- to 200-fold less active against the corresponding CDK inhibitors in in vitro CDK kinase assays. Growth inhibition studies in a panel of ovarian cancer cell lines revealed potency trends of the SymProDs mirrored those of the single treatments suggesting their dissociation in cells. In conclusion, our results suggest that SymProDs offer a productive path forward for advancing compounds with reactive functionality and can be used as dual targeting agents.

Synthesis, crystal structure, and photoluminescent properties of mononuclear Er(III) and Yb(III) complexes showing near-infrared emission

Lanthanide coordination complexes [Er(H3thaea)2](NO3)3·2H2O·2CH3OH (1) and [Yb(H3thaea)2](NO3)3·2H2O·2CH3OH (2) were prepared by the reaction of Er(NO3)3·5H2O or Yb(NO3)3·5H2O with tris(((2-hydroxy-3-methoxybenzyl)amino)ethyl)amine (H3thaea) in methanol. The complexes were characterized by elemental analysis, spectroscopy, photoluminescence, and single crystal X-ray diffraction. The erbium(III) ion of 1 is coordinated by six oxygen atoms of two H3thaea ligands and shows a nearly octahedral geometry structure. The coordinated oxygen atoms are deprotonated (O−) and three secondary nitrogen atoms of H3thaea are protonated ((-CH2)2NH2+). Complex 2 shows almost the same structure to that of 1. Complex 1 exhibits three emission peaks in near IR region due to Er(III) ion at 973, 1013, and 1233 nm, while complex 2 displays one sharp emission at 977 nm with broad band from 920 to 1100 nm due to Yb(III) ion.

Adsorption behavior of PAMAM dendrimers functionalized silica for Cd(II) from aqueous solution: Experimental and theoretical calculation

Abstract The adsorption behavior of polyamidoamine (PAMAM) dendrimers functionalized silica (SG-G0∼SG-G4.0) for Cd(II) from aqueous solution was investigated by combining experimental and theoretical method. The influences of dendrimer generation, terminal functional group, solution pH, contact time, temperature, as well as the initial concentration of Cd(II) on the adsorption behavior were explored. Static adsorption indicates that the adsorption capacity increases first and then decreases with the increase of dendrimer generation, SG-G2.0 and SG-G2.5 possess the highest adsorption capacity for amino- and ester-terminated PAMAM functionalized silica, respectively. The optimal adsorption pH value is 6 for all the adsorbents. Kinetic adsorption implicates that the adsorption can approach equilibrium at about 200 min. The kinetic adsorption follows pseudo-second-order kinetic model and is dominated by film diffusion. The isotherm adsorption demonstrates that the adsorption favors high concentration and the adsorption capacity first increases and then decreases with the increase of temperature. Adsorption isotherm process can be well described by Langmuir model. FTIR technique and DFT calculation reveal that the involvement primary and secondary nitrogen atoms, as well as carbonyl oxygen atoms dominate the adsorption. As SG-G0∼SG-G4.0 displays excellent adsorption performance for Cd(II), they could be potentially used as effective adsorbents for the decontamination of aqueous Cd(II).

Removal of Cr(III) from aqueous solution by silica-gel/PAMAM dendrimer hybrid materials.

Water pollution caused by Cr(III) is a serious environmental problem which bring adverse effect to environmental protection and public safety. Efficient removal of Cr(III) from aqueous solution is important for the remediation of Cr(III) pollution. Herein, a series of silica-gel/polyamidoamine (PAMAM) dendrimer hybrid materials (SG-G0~SG-G4.0) were used for the removal of Cr(III) from aqueous solution. The factors that affect the adsorption were extensively studied and the adsorption mechanism was demonstrated based on the experimental results and density functional theory (DFT) calculation. Result demonstrates the adsorption capacity of ester-terminated silica-gel/PAMAM dendrimers follow the order of SG-G2.5 > SG-G3.5 > SG-G1.5 > SG-G0.5, while that of amino-terminated ones decrease in the order of SG-G2.0 > SG-G4.0 > SG-G3.0 > SG-G1.0 > SG-G0. The highest adsorption is achieved at pH 4.0 for both ester- and amino-terminated materials. Adsorption kinetic indicates the adsorption equilibrium can be reached at about 240 and 180 min for amino- and ester-terminated hybrids, respectively. Adsorption kinetic can be well fitted by pseudo-second-order kinetic model with film diffusion process as the rate-limiting step. Adsorption isotherm follows Langmuir model with monolayer adsorption behavior. Fourier transform infrared spectra (FTIR) indicate the adsorption of Cr(III) by PAMAM dendrimer mainly involve the participation of N-H and C=O groups. DFT calculation demonstrates the uptake of Cr(III) by ester-terminated adsorbents mainly involves carbonyl oxygen and secondary amine nitrogen atoms to form tetra-coordinated chelate, while that of amino-terminated one tends to form hexa-coordinated chelates by carbonyl oxygen, primary and secondary amine nitrogen atoms.

Outer Coordination Sphere Proton Relay Base and Proximity Effects on Hydrogen Oxidation with Iron Electrocatalysts

The intra- and intermolecular deprotonation reactions of [(CpC5F4N)Fe(PEtNR′PEt)H]+ (PEtNR′PEt = (Et2PCH2)2NR′) complexes are rate-limiting processes in the electrocatalytic oxidation of hydrogen and can be mediated by an amine base in the outer coordination sphere (OCS) by facilitating the matching of energy of deprotonation intermediates. A series of complexes with different N-substituents (R′ = Me, Et, CH2OMe, CH2N(Ph)Me, and (CH2)nNMe2; n = 1–4) was examined computationally using density functional theory to determine the influence of the identity and proximity of the OCS base on the intramolecular deprotonation. Complexes with an OCS dimethylamino substituent were the most suitably energy matched. The number of carbon atoms between the secondary and OCS nitrogen atoms dictated the strength of the hydrogen-bonding interaction and ring strain following deprotonation of the iron hydride. The previously reported [(CpC5F4N)Fe(PEtNR′PEt)H]+ (R′ = (CH2)3NMe2) electrocatalyst was predicted to have the most f...

Influence of the Number of Metallophilic Interactions and Structures on the Optical Properties of Heterometallic Au/Ag Complexes with Mixed-Donor Macrocyclic Ligands.

The reactivity of the polymeric gold(I)/silver(I) compound [Au2Ag2(C6F5)4(OEt2)2] n toward the 12-membered mixed-donor macrocyclic ligands 1,7-diaza-4,10-dithiacyclododecane (L1), 1-aza-4,7,10-trithiacyclododecane (L2), N-quinolinylmethyl-1-aza-4,7,10-trithiacyclododecane (L3), and N, N'-bis(quinolinylmethyl)-1,7-diaza-4,10-dithiacyclododecane (L4) was studied. The reactions were carried out using different molar ratios depending on the coordination properties of the ligands, which were modified by changing the donor atoms present in the macrocyclic framework (sulfur or nitrogen) or by linking one or two methylquinoline pendant-arms at the secondary nitrogen atom(s). X-ray diffraction analysis of the new complexes obtained show a nuclearity that increases on increasing the number of donor atoms in the ligands. The rich structural diversity observed determines different optical responses when the complexes are irradiated with UV-vis light in the solid state and in THF solution. The study of the optical properties reveals that in complexes for which the luminescence is due to metal-metal interactions, higher emission wavelengths are observed as the number of these metallophilic contacts increases, while the luminescence of ionic complexes has its origin in the macrocyclic ligands. TD-DFT calculations were carried out to verify the origin of these interesting structural-optical property relationships.

Removal of Co(II) from fuel ethanol by silica-gel supported PAMAM dendrimers: Combined experimental and theoretical study

Silica-gel supported PAMAM dendrimers (SiO2-G0.5∼SiO2-G3.0) were used for the removal of Co(II) from fuel ethanol by batch method. The adsorption mechanism was revealed by combining the results of experiment and density functional theory (DFT) calculation. Results indicated the adsorption capacity was closely related with the generation number of PAMAM dendrimer, contact time, Co(II) concentration, and temperature. Amino-terminated PAMAM dendrimers exhibited better adsorption performance than the corresponding ester-terminated ones. Kinetic adsorption followed pseudo-second-order model and dominated by film diffusion. Isotherm adsorption can be well depicted by Langmuir isotherm model and proceeded by chemical mechanism. Thermodynamic parameters implied the adsorption was spontaneous, endothermic, and randomness incremental process. DFT calculation demonstrated that ester-terminated PAMAM tended to chelate with Co(II) by secondary amine nitrogen atoms and carbonyl oxygen atoms in a quadri-coordinated manner, while amino-terminated PAMAM preferred to act as tetradentate and pentadentate ligand to bind Co(II) with secondary amine nitrogen atom, carbonyl oxygen atom, and primary amine nitrogen atom. Charge transfer of the adsorption process mainly occurred from PAMAM dendrimer to Co(II).

Acid-Base Interactions of Polystyrene Sulfonic Acid in Amorphous Solid Dispersions Using a Combined UV/FTIR/XPS/ssNMR Study.

This study investigates the potential drug-excipient interactions of polystyrene sulfonic acid (PSSA) and two weakly basic anticancer drugs, lapatinib (LB) and gefitinib (GB), in amorphous solid dispersions. Based on the strong acidity of the sulfonic acid functional group, PSSA was hypothesized to exhibit specific intermolecular acid-base interactions with both model basic drugs. Ultraviolet (UV) spectroscopy identified red shifts, which correlated well with the color change observed in lapatinib-PSSA solutions. Fourier transform infrared (FTIR) spectra suggest the protonation of the quinazoline nitrogen atom in both model compounds, which agrees well with data from the crystalline ditosylate salt of lapatinib. X-ray photoelectron spectroscopy (XPS) detected increases in binding energy of the basic nitrogen atoms in both lapatinib and gefitinib, strongly indicating protonation of these nitrogen atoms. (15)N solid-state NMR spectroscopy provided direct spectroscopic evidence for protonation of the quinazoline nitrogen atoms in both LB and GB, as well as the secondary amine nitrogen atom in LB and the tertiary amine nitrogen atom in GB. The observed chemical shifts in the LB-PSSA (15)N spectrum also agree very well with the lapatinib ditosylate salt where proton transfer is known. Additionally, the dissolution and physical stability behaviors of both amorphous solid dispersions were examined. PSSA was found to significantly improve the dissolution of LB and GB and effectively inhibit the crystallization of LB and GB under accelerated storage conditions due to the beneficial strong intermolecular acid-base interaction between the sulfonic acid groups and basic nitrogen centers.

Visible-Light/Photoredox-Mediated sp(3) C-H Functionalization and Coupling of Secondary Amines with Vinyl Azides in Flow Microreactors.

Structurally diverse imidazole derivatives were synthesized by a visible-light/[Ru(bpy)3 ][(PF6 )2 ]-mediated coupling of vinyl azides and secondary amines in flow microreactors. This operationally simple and atom-economical protocol allows the formation of three new C-N bonds through the functionalization of sp(3) C-H bonds adjacent to the secondary nitrogen atom. In order to get mechanistic insight of the coupling reaction, several control experiments were carried out and discussed.

Synthesis and inhibitory activity of substrate-analog fructosyl peptide oxidase inhibitors

Fructosyl peptide oxidases (FPOXs) play a crucial role in the diagnosis of diabetes. Their main function is to cleave fructosyl amino acids or fructosyl peptides into glucosone and the corresponding amino acids/dipeptides. In this study, the substrate-analog FPOX inhibitors 1a-c were successfully designed and synthesized. These inhibitors mimic N(α)-fructosyl-L-valine (Fru-Val), [N(α)-fructosyl-L-valyl]-L-histidine (Fru-ValHis), and N(ε)-fructosyl-L-lysine (εFru-Lys), respectively. The secondary nitrogen atom in the natural substrates, linking fructose and amino acid or dipeptide moieties, was substituted in 1a-c with a sulfur atom to avoid enzymatic cleavage. Kinetic studies revealed that 1a-c act as competitive inhibitors against an FPOX obtained from Coniochaeta sp., and Ki values of 11.1, 66.8, and 782 μM were obtained for 1a-c, respectively.

Regioselective long-range proton transfer in new rifamycin antibiotics: a process in which crown ethers act as stronger Brønsted bases than amines.

Water-mediated proton transfer in six new derivatives of 3-formylrifamycin SV that contain crown, aza-crown, and benzo-crown ether rings were investigated by FTIR and NMR spectroscopy. (1)H-(1)H COSY couplings provide evidence for the formation of zwitterionic structures of the aza-crown and crown ether derivatives of rifamycin, in which a proton from one of the phenolic groups is transferred to tertiary and secondary nitrogen atoms. The increased intensity of the continuous absorption in the mid-infrared region together with the NMR data indicate proton transfer from the phenol group of the rifamycin core to the cavity of the benzo-crown ether ring. This proton transfer is achieved by formation of hydronium (H3O(+)) or Zundel ions (H5O2(+)), which form intermolecular hydrogen bonds with the oxygen atoms of the crown ether. DFT calculations are in agreement with the spectroscopic data and allow visualization of the structures of all new rifamycin derivatives, characterized by different intramolecular protonation sites.

An asymmetrical dinuclear copper(II) β-amino-oxime/oximato-diamine compound with Cu–(OH)–Cu and Cu–(N–O)–Cu bridging; [Cu2(detenoxH)(detenox)(OH)](ClO4)2 (detenoxH = 4,4-dimethyl-7-(N,N-diethylamine)-5-azaheptan-2-one oxime)

The dark blue compound [Cu2(detenoxH)(detenox)(OH)](ClO4)2 (detenoxH=4,4-dimethyl-7-(N,N-diethylamine)-5-azaheptan-2-one oxime), [Cu2(C12H27N3O)(C12H26N3O)(OH)](ClO4)2, is formed by reaction of (N,N-diethyl-ethane-1,2-diamine)copper(II) perchlorate, 4-methylpent-3-ene-2-one oxime and base. The asymmetrical dinuclear cation has ion Cu1 in asymmetrical square pyramidal coordination by the oxime nitrogen atom (Cu1–Noxime=2.041(3)Å) and the secondary amine nitrogen atom (Cu1–Nsecondary=1.995(3) Å) of a detenoxH ligand, the bridging oximato oxygen atom of the detenox− ligand bonded to Cu2 (Cu1–Ooximato=1.928(2)Å) and the bridging OH− ion (Cu1–OOH=1.928(3)Å) with rms displacements from the N2O2 plane±0.246(1) with Cu1 in the plane). The tertiary amine nitrogen atom of the detenoxH ligand is weakly coordinated axially (Cu1–Ntertiary=2.328(3)Å). Ion Cu2 is in tetrahedrally twisted square-planar coordination by a detenox− ligand, with Cu2–Noxime=1.992(3), Cu2–Nsecondary=1.979(3), Cu2–Ntertiary=2.053(3), and by the bridging hydroxide ion (Cu2–O=1.878(3)Å), with rms displacements from the N3O best plane ±0.178(2)Å, with Cu2 in the plane). The dinuclear cation has Cu1–O=N–Cu2 bridging by the oximato group of detenox− and Cu1–(OH)–Cu2 bridging by a hydroxide ion, with Cu⋯Cu=3.3136(6)Å. The components of the dinuclear cation are further linked by a hydrogen bond between the oxime OH and oximato O− groups. The effective magnetic moment of 2.21 B.M. indicates that there is no significant spin coupling.