A Novel Method for the Synthesis of 4(3H)‐Quinazolinones

Different metal perchlorates were screened to catalyze the three‐component reaction of anthranilic acid, triethyl orthoformate and amines to afford quinazolin‐4(3H)‐ones in solvent‐free conditions. Ni(ClO₄)₂ or Zn(ClO₄)₂ was demonstrated to be efficient to catalyze the reaction.     

2‐Amino‐5‐(2‐pyridyl)‐thiadiazole as Bidentate Ligand

The amino substituted bidentate chelating ligand 2‐amino‐5‐(2‐pyridyl)‐1,3,4‐thiadiazole (H₂ L ) was used to prepare 3:1‐type coordination compounds of iron(II), cobalt(II) and nickel(II). In the iron(II) perchlorate complex [Fe^II(H₂ L )₃](ClO₄)₂·0.6MeOH·0.9H₂O a 1:1 mixture of mer and fac isomers is present whereas [Fe^II(H₂ L )₃](BF₄)₂·MeOH·H₂O, [Co^II(H₂ L )₃](ClO₄)₂·2H₂O and [Ni^II(H₂ L )₃](ClO₄)₂·MeOH·H₂O feature merely mer derivatives. Moessbauer spectroscopy and variable temperature magnetic measurements revealed the [Fe^II(H₂ L )₃]²⁺ complex core to exist in the low‐spin state, whereas the [Co^II(H₂ L )₃]²⁺ complex core resides in its high‐spin state, even at very low temperatures.     

Copper(II) Complexes with N,N'‐Bis(picolinidene‐N‐oxide)‐2‐hydroxy‐1, 3‐diaminopropane: Designing Binuclear Entities and Helical Chains by Versatile Ligand

Three novel copper(II) complex [Cu₂(bpa)(μ‐PhCO₂)](ClO₄)₂ ( 1 ), [Cu₂(bpa) (μ‐pyz)](ClO₄)₂ ( 2 ), and [Cu(Hbpa)](ClO₄)₂·2CH₃CN ( 3 ) have been synthesized by the reaction of Hbpa with Cu(ClO₄)₂·6H₂O in the presence and absence of exogenous ligands (where Hbpa = N, N'‐bis(picolinidene‐N‐oxide)‐2‐hydroxy‐1, 3‐diamino‐propane). Molecular structures of these compounds have been elucidated by single crystal X‐ray diffraction. 1 and 2 are both binuclear complexes in which two copper atoms are linked by the endogenous alkoxide oxygen and the exogenous benzoate and pyrazolate ligands, respectively. 3 consists of a one‐dimensional polymeric structure, in which Hbpa functions as a bridging mode.     

Local Coordination Geometry and Spin State in Novel FeII Complexes with 2,6‐Bis(pyrazol‐3‐yl)pyridine‐Type Ligands as Controlled by Packing Forces: Structural Correlations

A substituted 2,6‐bis(pyrazol‐3‐yl)pyridine (3‐bpp) ligand, H₄L, created to facilitate intermolecular interactions in the solid, has been used to obtain four novel Fe^II complexes: [Fe(H₄L)₂](ClO₄)₂ ? 2 CH₃NO₂ ? 2 H₂O, [Fe(H₄L)(H₂LBF₂)](BF₄) ? 5 C₃H₆O (H₂LBF₂ is an in situ modified version of H₄L), [Fe(H₄L)₂](ClO₄)₂ ? 2 C₃H₇OH and [Fe(H₄L)₂](ClO₄)₂ ? 4 C₂H₅OH. Changing of spin‐inactive components (solvents, anions or distant ligand substituents) causes differences to the coordination geometry of the metal that are key to the magnetic proper‐ ties. Magnetic measurements show that, contrary to the previously published complex [Fe(H₄L)₂](ClO₄)₂ ? H₂O ? 2 CH₃COCH₃, the newly synthesised compounds remain in the high‐spin (HS) state at all temperatures (5–300 K). A member of the known family of Fe^II/3‐bpp complexes, [Fe(3‐bpp)₂](ClO₄)₂ ? 1.75 CH₃COCH₃ ? 1.5 Et₂O, has also been prepared and characterised structurally. In the bulk, this compound exhibits a gradual and incomplete spin transition near 205 K. The single‐crystal structure is consistent with it being HS at 250 K and partially low spin at 90 K. Structural analysis of all these compounds reveals that the exact configuration of intermolecular interactions affects dramatically the local geometry at the metal, which ultimately has a strong influence on the magnetic properties. Along this line, the geometry of Fe^II in all published 3‐bpp compounds of known structure has been examined, both by calculating various distortion indices (Σ, Θ, θ and Φ) and by continuous shape measures (CShMs). The results reveal correlations between some of these parameters and indicate that the distortions from octahedral geometry observed on HS systems are mainly due to strains arising from intermolecular interactions. As previously suggested with other related compounds, we observe here that strongly HS‐distorted systems have a larger tendency to remain in that state.     

A Sequential Method to Prepare Polymorphs and Solvatomorphs of [Fe(1,3‐bpp)2](ClO4)2⋅nH2O (n=0, 1, 2) with Varying Spin‐Crossover Behaviour

Two polymorphs of the spin crossover (SCO) compound [Fe(1,3‐bpp)₂](ClO₄)₂ ( 1 and 2 ; 1,3‐bpp=2‐(pyrazol‐1‐yl)‐6‐(pyrazol‐3‐yl)pyridine) were prepared using a novel, stepwise procedure. Crystals of 1 deposit from dry solvents, while 2 is obtained from a solid‐state procedure, by sequentially removing lattice H₂O molecules from the solvatomorph [Fe(1,3‐bpp)₂](ClO₄)₂?2 H₂O ( 2 ?2 H₂O), using single‐crystal‐to‐single‐crystal (SCSC) transformations. Hydrate 2 ?2 H₂O is obtained through the same reaction as 1 , now with 2.5 % of water added. Compounds 2 and 2 ?2 H₂O are unstable in the atmosphere and absorb or lose one equivalent of water, respectively, to both yield the stable solvatomorph [Fe(1,3‐bpp)₂](ClO₄)₂?H₂O ( 2 ?H₂O), also following SCSC processes. The four derivatives have been characterised by single‐crystal X‐ray diffraction (SCXRD). Furthermore, the homogeneity of the various compounds as well as their SCSC interconversions have been confirmed by powder X‐ray diffraction (PXRD). Polymorphs 1 and 2 exhibit abrupt SCO behaviour near room temperature with T_1/2↑=279/316 K and T_1/2↓=276/314 K (near 40 K of shift) and different cooperativity.     

Zr(HSO4)4‐catalyzed one‐pot three‐component synthesis of 7‐alkyl‐6H,7H‐naphtho[1′,2′:5,6]pyrano[3,2‐c]chromen‐6‐ones

A new, one‐pot, simple thermally efficient and solvent‐free method for the preparation of 7‐alkyl‐6H,7H‐naphtho[1′,2′:5,6]pyrano[3,2‐c]chromen‐6‐ones by condensation of β‐naphthol, aromatic aldehydes, and 4‐hydroxycoumarin using Zr(HSO₄)₄ as a safe and efficient catalyst is described. This method has the advantages of high yields, a cleaner reaction, simple methodology, short reaction times, easy workup, and greener conditions. J. Heterocyclic Chem., (2011).     

Bis(3‐amino­pyridine‐κN)(4,4′‐di­methyl‐2,2′‐bipyridine‐κ2N,N′)(per­chlorato‐κO)copper(II) per­chlorate

The title compound, [Cu(ClO₄)(C₅H₆N₂)₂(C₁₂H₁₂N₂)]ClO₄, was prepared by in situ partial ligand substitution between 3‐amino­pyridine and 4,4′‐dimethyl‐2,2′‐bipyridine at room temperature. The central copper(II) ion is five‐coordinated by one bidentate 4,4′‐dimethyl‐2,2′‐bipyridine mol­ecule, two monodentate pyridine‐coordinated 3‐amino­pyridine mol­ecules and one apical O atom from the perchlorate counter‐ion. Inter­molecular N—H⋯O and C—H⋯O hydrogen‐bonding inter­actions form a hydrogen‐bond‐sustained network.     

1‐(2‐Hydroxyethyl)‐3‐nitro‐1, 2, 4‐triazole and its Complexes with Copper(II) Chloride and Copper(II) Perchlorate

1‐(2‐Hydroxyethyl)‐3‐nitro‐1, 2, 4‐triazole (hnt), prepared by alkylation of 3‐nitro‐1, 2, 4‐triazole with 2‐chloroethanol, was found to react with copper(II) chloride and copper(II) perchlorate in acetonitrile/ethanol solutions giving complexes [Cu₂(hnt)₂Cl₄(H₂O)₂] and[Cu(hnt)₂(H₂O)₃](ClO₄)₂, respectively. They are the first examples of coordination compounds with a neutral N‐substituted 3‐nitro‐1, 2, 4‐triazole ligand. 1‐(2‐Hydroxyethyl)‐3‐nitro‐1, 2, 4‐triazole and the obtained complexes were characterized by NMR and IR spectroscopy, X‐ray, and thermal analyses. [Cu₂(hnt)₂Cl₄(H₂O)₂] presents a dinuclear chlorido‐bridged complex in which hnt acts as a chelating bidentate ligand, coordinated to the metal by a nitrogen atom of the triazole ring and an oxygen atom of the nitro group, and the copper atoms are inconsiderably distorted octahedral coordination. [Cu(hnt)₂(H₂O)₃](ClO₄)₂comprises a mononuclear complex cation, in which two nitrogen atoms of two hnt ligands in trans configuration and three water oxygen atoms form a square pyramidal environment around the copper atom, which is completed to an distorted octahedron with a bifurcated vertex due to two additional elongated Cu–O bonds with two nitro groups. In both complexes, Cu–O bonds with the nitro groups may be considered as semi‐coordinated.     

Desulfuration and Cyclization of (Z)‐2‐[Amino(pyridine‐2‐yl)methylene]‐ hydrazonecarbothioamide in the Presence of Manganese(II)

The reaction of (Z)‐2‐[amino(pyridine‐2‐yl)methylene]hydrazonecarbothioamide (HAm4DH) with Mn(ClO₄)₂·6H₂O afforded different mononuclear or polynuclear manganese(II) complexes, the nature of which apparently depended on the solvent used. For example, in ethanol a compound of formula [Mn(HAm4DH)₂](ClO₄)₂ ( 1 ) was obtained, where HAm4DH coordinates as a common tridentate NNS donor, but the [Mn(bpy)₂(NCS)₂] complex ( 2 ) (bpy = 2,2'‐bipyridine) has also been obtained – probably due to C–N bond cleavage of the thiosemicarbazone. Nevertheless, in a basic aqueous medium [Mn(bpy)₃](ClO₄)₂·0.5bpy ( 3 ) is formed and there is structural evidence for chemical transformations of the thiosemicarbazone promoted by Mn^II. Thus, the sulfate in {[Mn(py)₄Mn(py)₂(H₂O)₂(μ‐SO₄)₂]·4H₂O}_n ( 4 ) or sulfate and cyclooctasulfur in [Mn(pta)₂(pdo)]₄(SO₄)₂·4H₂O·S₈] ( 5 ), where pta is 3‐(pyridin‐2‐yl)‐1,2,4‐triazol‐5‐amine and pdo is (2R,4R/2S,4S)‐pentane‐2,4‐diolato, arise from the desulfuration and oxidation of the thiosemicarbazone ligand. The structures of complexes 2 to 5 were established by single‐crystal X‐ray diffraction. The formation of pta is the result of the oxidative cyclization of HAm4DH. In the polynuclear complex 4 , the sulfate acts as an (O,O') bridge between alternating Mn(py)₂(H₂O)₂ and Mn(py)₄ centers. In the tetranuclear complex 5 , pta acts as a bischelating ligand through the N‐pyridine and N‐triazole, and pdo act as a bridge between two manganese atoms. It is also noteworthy that in complexes 4 and 5 hydrogen bonds give rise to different self‐assembly behaviour that leads to complicated supramolecular structures.     

Supramolecular structures of 5‐[3‐(4‐methyl­phenyl)‐ and 5‐[3‐(4‐chloro­phenyl)‐2‐propenyl­idene]‐2,2‐di­methyl‐1,3‐dioxane‐4,6‐dione

2,2‐Di­methyl‐5‐[3‐(4‐methyl­phenyl)‐2‐propenyl­idene]‐1,3‐di­ox­ane‐4,6‐dione, C₁₆H₁₆O₄, crystallizes in the triclinic space group , with two mol­ecules in the asymmetric unit. These mol­ecules and a centrosymmetrically related pair, linked together by weak C—H?O hydrogen bonds, form a tetramer. 5‐[3‐(4‐Chloro­phenyl)‐2‐propenyl­idene]‐2,2‐di­methyl‐1,3‐dioxane‐4,6‐dione, C₁₅H₁₃ClO₄, also crystallizes in the triclinic space group , with one mol­ecule in the asymmetric unit. Centrosymmetrically related mol­ecules are linked together by weak C—H?O hydrogen bonds to form dimers which are further linked by yet another pair of centrosymmetrically related C—H?O hydrogen bonds to form a tube which runs parallel to the a axis.     

Two 2,5‐bis(2‐pyridinyl)‐1,3,4‐oxa­diazo­le–metal complexes (M = Cu and Ni)

The reaction of the diazine ligand 3,5‐bis(2‐pyridinyl)‐1,3,4‐oxa­diazole (pod, C₁₂H₈N₄O), with Cu(CF₃SO₃)₂ or Ni(ClO₄)₂ afforded the title complexes di­aqua­bis­[3,5‐bis(2‐pyridinyl)‐1,3,4‐oxa­diazole‐N²,N³]copper(II) bis­(tri­fluoro­methane­sul­fon­ate), [Cu(pod)₂(H₂O)₂](CF₃SO₃)₂, and di­aqua­bis­[3,5‐bis(2‐pyridinyl)‐1,3,4‐oxa­diazo­le‐N²,N³]­nickel(II) diperchlorate, [Ni(pod)₂(H₂O)₂](ClO₄)₂. Both complexes present a crystallographically centrosymmetric mononuclear cation structure which consists of a six‐coordinated Cu^II or Ni^II ion with two pod mol­ecules acting as bidentate ligands and two axially coordinated water mol­ecules.     

{Δ‐1,4,7,10‐Tetrakis[(S)‐2‐hydroxy­propyl‐κO]‐1,4,7,10‐tetra­aza­cyclo­do­dec­ane‐κ4N}cad­mium(II) 4‐nitrophenolate per­chlor­ate hydrate

Crystallization of [Cd(S‐thpc12)](ClO₄)₂·H₂O {S‐thpc12 is 1,4,7,10‐tetra­kis[(S)‐2‐hy­drox­y­propyl]‐1,4,7,10‐tetra­aza­cy­clo‐do­dec­ane} in the presence of sodium p‐nitrophenolate forms the title complex, [Cd(C₂₀H₄₄N₄O₄)](C₆H₄NO₃)(ClO₄)·H₂O, in which p‐nitrophenolate and water separately hydrogen bond to a different pair of cis‐related pendant hydroxyl groups which, together with the four N atoms, are themselves bound to Cd^II in an approximately square antiprismatic arrangement. The diastereoselectivity of the complex‐forming process is apparent from the fact that both different disymmetric cations in the asymmetric unit have the same Δ helicity.     

{μ‐N,N′‐Bis[3‐(dimethyl­amino)prop­yl]­oxamidato(2–)‐κ6N,N′,O′:N′′,N′′′,O}­bis­[(1H‐imidazole‐κN3)(methanol‐κO)copper(II)] bis­(perchlorate)

The structure of the title compound, [Cu₂(C₁₂H₂₄N₄O₂)(C₃H₄N₂)₂(CH₄O)₂](ClO₄)₂ or [Cu₂(dmoxpn)(HIm)₂(CH₃OH)₂](ClO₄)₂, where dmoxpn is the dianion of N,N′‐bis­[3‐(dimethyl­amino)prop­yl]oxamide and HIm is imidazole, consists of a centrosymmetric trans‐oxamidate‐bridged copper(II) binuclear cation, having an inversion centre at the mid‐point of the central C—C bond, and two perchlorate anions. The Cu^II atom has square‐pyramidal coordination geometry involving two N atoms and an O atom from the dmoxpn ligand, an N atom from an imidazole ring, and an O atom from a methanol mol­ecule. The crystal structure is stabilized by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds and imidazole π–π stacking inter­actions to form a three‐dimensional supra­molecular array.     

Preparation of new 2‐amino‐ and 2,3‐diamino‐pyridine trifluoroacetyl enamine derivatives and their application to the synthesis of trifluoromethyl‐containing 3H‐pyrido[2,3‐b][1,4] diazepinols

The synthesis of a novel series of the intermediates N²(N³)‐[1‐alkyl(aryl/heteroaryl)‐3‐oxo‐4,4,4‐trifluoroalk‐1‐en‐1‐yl]‐2‐aminopyridines [F₃CC(O)CH?CR¹(2? NH?C₅H₃N)] and 2,3‐diaminopyridines [F₃CC(O)CH?CR¹(2‐NH₂‐3‐NH? C₅H₃N)], where R¹ = H, Me, C₆H₅, 4‐FC₆H₄, 4‐CIC₆H₄, 4‐BrC₆H₄, 4‐CH₃C₆H₄, 4‐OCH₃C₆H₄, 4,4′‐biphenyl, 1‐naphthyl, 2‐thienyl, 2‐furyl, is reported. The corresponding series of 2‐aryl(heteroaryl)‐4‐trifluoromethyl‐3H‐pyrido[2,3‐b][1,4]diazepin‐4‐ols obtained from intramolecular cyclization reaction of the respective trifluoroacetyl enamines or from the direct cyclocondensation reaction of 4‐methoxy‐1,1,1‐trifluoroalk‐3‐en‐2‐ones with 2,3‐diaminopyridine, under mild conditions, is also reported.     

Methyl 2‐benzamido‐4‐(3,4‐dimethoxyphenyl)‐5‐methylbenzoate and N‐{5‐benzoyl‐2‐[(Z)‐2‐methoxyethenyl]‐4‐methylphenyl}benzamide

Methyl 2‐benzamido‐4‐(3,4‐dimethoxyphenyl)‐5‐methylbenzoate, C₂₄H₂₃NO₅, (Ia), and N‐{5‐benzoyl‐2‐[(Z)‐2‐methoxyethenyl]‐4‐methylphenyl}benzamide, C₂₄H₂₁NO₃, (IIa), were formed via a Diels–Alder reaction of appropriately substituted 2H‐pyran‐2‐ones and methyl propiolate or (Z)‐1‐methoxybut‐1‐en‐3‐yne, respectively. Each of these cycloadditions might yield two different regioisomers, but just one was obtained in each case. In (Ia), an intramolecular N—H...O hydrogen bond closes a six‐membered ring. A chain is formed due to aromatic π–π interactions, and a three‐dimensional framework structure is formed by a combination of C—H...O and C—H...π(arene) hydrogen bonds. Compound (IIa) was formed not only regioselectively but also chemoselectively, with just the triple bond reacting and the double bond remaining unchanged. Compound (IIa) crystallizes as N—H...O hydrogen‐bonded dimers stabilized by aromatic π–π interactions. Dimers of (IIa) are connected into a chain by weak C—H...π(arene) interactions.     

A novel three‐dimensional copper(II) network via hydrogen bonds: diaquabis[bis(pyrazol‐1‐yl‐κN2)methane]copper(II) diperchlorate

The crystal structure of the title complex, [Cu(C₇H₈N₄)₂(H₂O)₂](ClO₄)₂, consists of a discrete centrosymmetric [Cu(C₇H₈N₄)₂(H₂O)₂]²⁺ cation and two perchlorate anions. The Cu^II centre is six‐coordinated by four N donors from the two pyrazole rings [Cu—N 1.998 (2) and 2.032 (3) Å] and two O atoms from the water mol­ecules occupying the apical sites [Cu—O 2.459 (3) Å]. The coordination geometry of the complex can be described as octahedral. There is a unique three‐dimensional network in which the perchlorate units are linked by a combination of strong O—H?O and weak C—H?O hydrogen bonds.     

Simple Synthesis of 3‐Oxopropanenitriles via Electrophilic Cyanoacetylation of Heterocycles with Mixed Anhydrides

A simple and efficient method for the synthesis of 3‐oxopropanenitriles from variously substituted heterocyclic compounds via direct electrophilic cyanoacetylation is described. A series of heterocyclic 3‐oxopropanenitriles ( 2a , 2b , 2c , 2d , 2e , 2f , 2g , 2h , 2i , 2j , 2k ) have been synthesized using mixed anhydride (acetic or trifluoroacetic anhydride:cyanoacetic acid) in the presence of Mg(ClO₄)₂·2H₂O as catalyst. This method can be extended also for the cyanoacetylation of electron poor aromatic compounds.     

Bis(μ‐4‐chloro­benzoato‐κ2O:O)bis[(2‐aminopyridine‐κN)silver(I)]

The title compound, [Ag₂(C₇H₄ClO₂)₂(C₅H₆N₂)₂], lies about an inversion centre and the Ag atom is three‐coordinated by two O atoms and one N atom from three different ligands. The 4‐chloro­benzoate anion acts as a monodonor ligand, bridging two inversion‐related Ag atoms of the compound into a dimer. There are weak intermolecular N—H⋯O hydrogen bonds in the structure.     

One‐dimensional Europium(III) Coordination Polymer Based on 3‐Pyridylacrylic Acid

Under hydrothermal conditions, the reaction of racemic 3‐pyridyl‐3‐aminopropionic acid (rac‐HPAPA) with Eu(ClO₄)₃· 6H₂O affords a 1‐D chain complex, [Eu(3‐PYA)₃(H₂O)]_n ( 1 ) (3‐PYA=3‐pyridylacrylate), which represents an example of neutral 1‐D coordination polymeric material based on 3‐HPYA (HPYA= pyridylacrylic acid) ligand with strong red fluorescent emission in the solid state.     

μ‐{N,N′‐Bis[2‐(dimethyl­amino)ethyl]oxamidato(2–)}‐1κ2O,O′:2κ4N,N′,N′′,N′′′‐bis­(4,4′‐dimethyl‐2,2′‐bipyridine‐1κ2N,N′)dinickel(II) bis­(perchlorate)

In the crystal structure of the title complex, [Ni₂(C₁₀H₂₀N₄O₂)(C₁₂H₁₂N₂)₂](ClO₄)₂ or [Ni(dmaeoxd)Ni(dmbp)₂](ClO₄)₂ {H₂dmaeoxd is N,N′‐bis­[2‐(dimethyl­amino)ethyl]oxamide and dmbp is 4,4′‐dimethyl‐2,2′‐bipyridine}, the deprotonated dmaeoxd²⁻ ligand is in a cis conformation and bridges two Ni^II atoms, one of which is located in a slightly distorted square‐planar environment, while the other is in an irregular octa­hedral environment. The cation is located on a twofold symmetry axis running through both Ni atoms. The dmaeoxd²⁻ ligands inter­act with each other via C—H⋯O hydrogen bonds and π–π inter­actions, which results in an extended chain along the c axis.