Synthesis and crystal structure of discrete complexes and coordination polymers containing 1,3-bis(pyrazol-1-yl)propane ligands

Potapov, Аndrei S.; Domina, Galina A.; Петренко, Т. В.; Khlebnikov, Аndrei I.

doi:10.1016/j.poly.2011.11.039

Cited by 17 publications

(11 citation statements)

References 34 publications

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“…3). Contrary to our recently reported Zn complexes with 1,3-bis(1,2,4-triazol-1-yl)propane containing a shorter alkyl bridge (Semitut et al, 2017), 1,3-bis(pyrazol-1-yl)propane (Potapov et al, 2012) and bis(imidazol-1-yl)alkanes , the title compound is a 2D polymer, because the Zn atoms are connected by btrh ligands in pairs, not in chains, thus preventing the formation of a 3D net. Each Zn atom is linked with three others via (1) the first bdc 2-ligand, (2) a second bdc 2-ligand and (3) a pair of btrh ligands.…”

Section: Structural Commentarycontrasting

confidence: 96%

Crystal structure of a Zn complex with terephthalate and 1,6-bis(1,2,4-triazol-1-yl)hexane

2018

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A new zinc coordination polymer with rigid benzene-1,4-dicarboxylate (bdc) and flexible 1,6-bis(1,2,4-triazol-1-yl)hexane (btrh), namely poly [[( 2 -benzene-1,4-dicarboxylato)[ 2 -1,6-bis(1,2,4-triazol-1-yl)hexane]zinc] dimethylformamide monosolvate], [Zn(C 8 H 4 O 4 )(C 10 H 16 N 6 )]ÁC 3 H 7 NO, was synthesized. According to the single-crystal XRD analysis, the product crystallizes in the P1 space group and has a layered structure. Analysis of the layered structure reveals {Zn(bdc)} chains which are connected by pairs of btrh ligands. The layers are packed tightly perpendicular to the [122] direction, separated by one nondisordered dimethylformamide solvent molecule per formula unit. According to thermogravimetric analysis, the product completely loses this solvent at 453 K; the desolvated compound is stable up to 503 K. As a result of the lack of hydrogen-donor groups, hydrogen bonds are not observed in the structure of the complex; however, an intermolecular C-HÁ Á Á contact of 3.07 Å occurs. Chemical contextCoordination polymers with flexible bitopic ligands have attracted great interest as prospective materials for gas separation, sensing materials, electrochemical devices or catalysis (Pettinari et al., 2016). One of the favoured classes of bitopic ligands are bis(azol-1-yl) alkanes, which have been used for the preparation of various transition metals coordination polymers with different topologies (Alkorta et al., 2017;Pellei et al., 2017;Manzano et al., 2016;Liu et al., 2012). Bitopic bis(azol-1-yl)alkanes have two separated metalbinding sites that allow them to form a wide variety of polymeric structures. Thus, coordination compounds based on these ligands could be applied in the design of various functional materials with a wide range of potential applications. Recently, we have synthesized three new Zn coordination polymers based on bis(triazol-1-yl)propane and terephtalate anions (Semitut et al., 2017). By varying the conditions, it was possible to synthesize three different polymeric compounds, which have interesting luminescent properties. As part of our studies with the aim of preparing new coordination polymers with flexible bis(triazol-1-yl)alkane ligands, we report herein the synthesis and crystal structure of [Zn(bdc)(btrh)]ÁDMF (bdc = benzene-1,4-dicarboxylate, btrh = 1,6-bis(1,2,4-triazol-1-yl)hexane, DMF = dimethylformamide).

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Section: Structural Commentarycontrasting

confidence: 96%

Crystal structure of a Zn complex with terephthalate and 1,6-bis(1,2,4-triazol-1-yl)hexane

2018

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“…For instance, we formerly observed that in 1,3-and 1,5-dialkylpyrazoles the positions of Н 4 signals in the 1 Н NMR spectra practically coincided (∆δ ≈ 0.01 ppm), and the signals of Н 3 protons appeared downfield with respect to those of Н 5 protons [16] (see the figure).…”

Section: Methodsmentioning

confidence: 89%

“…The high interest in this class of heterocyclic compounds originates as well from their large potential in modern technologies of dyes in cosmetics, photography and production of fluorescent substances and stabilizers [1][2][3][4][5]. Compounds of the pyrazole series find application both in the large-scale and fine organic synthesis [1][2][3][4][5], in the supramolecular [10] and polymer chemistry [11, 12], as liquid crystls [13], ligands for metal complex catalysis [14][15][16], in designing complexes with uncommon magnetic properties [17,18].The practical utilization of pyrazoles and the extension of their application fields requires not only development of synthetic procedures for new pyrazole derivatives, but mainly the solution of an important task of working out directional procedures for preparation of individual isomers of unsymmetrically substituted pyrazoles. The analysis of the known approaches shows the especially promising application of haloenones as initial reagents for pyrazole synthesis [19][20][21][22][23], in particular, of their individual isomers.…”

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confidence: 99%

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Synthesis and structure of 1-tert-butyl-substituted 3(5)-alkylpyrazoles from 2-chlorovinyl ketones

et al. 2015

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Reactions of alkyl, halomethyl 2-chlorovinyl ketones with tert-butylhydrazine in the presence of triethylamine afford unsymmetrical 1-(tert-butyl)-3-and -5-disubstituted pyrazoles. The reaction direction is governed by the ketone ability of the nucleophilic substitution of chlorine and of the dehydrochlorination leading to acetylene ketones. 2-Chlorovinyl ketones react with tert-butylhydrazine along two routes giving mixtures of 1-(tert-butyl)-3-and -5-alkylpyrazoles. The content of 3-alkyl-1-(tert-butyl)pyrazole in the formed isomers mixture grows up to 73% with growing length of the alkyl chain of the ketone and up to 87 and 94% at introducing halogen atom in the alkyl fragment of the chloroenone.Pyrazole and its derivatives attract attention due to the widest range of their pharmacologic activity [1][2][3][4][5], versatile specific agrochemical properties [6][7][8][9]. The high interest in this class of heterocyclic compounds originates as well from their large potential in modern technologies of dyes in cosmetics, photography and production of fluorescent substances and stabilizers [1][2][3][4][5]. Compounds of the pyrazole series find application both in the large-scale and fine organic synthesis [1][2][3][4][5], in the supramolecular [10] and polymer chemistry [11, 12], as liquid crystls [13], ligands for metal complex catalysis [14][15][16], in designing complexes with uncommon magnetic properties [17,18].The practical utilization of pyrazoles and the extension of their application fields requires not only development of synthetic procedures for new pyrazole derivatives, but mainly the solution of an important task of working out directional procedures for preparation of individual isomers of unsymmetrically substituted pyrazoles. The analysis of the known approaches shows the especially promising application of haloenones as initial reagents for pyrazole synthesis [19][20][21][22][23], in particular, of their individual isomers. The systematic investigation of the reactivity of versatile haloenones [24][25][26][27][28][29] demonstrated that the reactions of 2,2-dihalovinyl ketones with unsymmetrical dialkylhydrazines, alkyl-, arylhydrazines under various condition resulted in the chemo-and regiospecific formation of 1-alkyl(aryl)-5-halo-3-alkyl(aryl)(haloalkyl)pyrazoles. Therewith the hydrazine character does not considerably affect the process direction.The preparation of 1,3-disubstituted pyrazoles with no halogen atoms in the ring from 2-chlorovinyl ketones is governed by the hydrazine structure. The regioselective synthesis of 1,3-disubstituted pyrazoles from 2-chlorovinyl ketones occurs at the use of 1,1-dialkyl-and arylhydrazines [29][30][31]. At the same time no formation of two isomers was observed in the reactions of 2-chlorovinyl ketones with hydrazines containing a long alkyl chain [32].In extension of the research on the development of syntheses of dialkyl-substituted pyrazoles we studied the reactions of a number of 2-chlorovinyl ketones with tert-butylhydrazine. The goal of the work consiste...

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“…[15][16][17] In recent years, increasing interest has been focused on polypyrazole constructs which are promising ligands. 18 Some pyrazole ligands can be used in transition metal-catalyzed reactions. 19 Pyrazoles are used in supramolecular 20 and polymer chemistry, 21 in the food industry, as cosmetic colorings 22 and UV stabilizers 23 and some possess liquid crystal properties.…”

Section: Introductionmentioning

confidence: 99%

Novel directed synthesis of functionalized pyrazole derivatives via regioselective solvent-free thiylation of 3-alkenylpyrazoles with arenethiols

Levkovskaya¹,

Rudyakova²,

Kobelevskaya³

et al. 2016

Arkivoc

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Unprecedented easy (3 min., room temperature) regioselective addition of thiols to the endocyclic double bond of 3-vinyl-, prop-1-enyl-and isopropenyl, including those with bulky substituents in the position 1 of the pyrazole ring, has been found for the reaction of arenethioles with 3-alkenyl-5-chloropyrazoles. The reaction proceeds under solvent-free and catalyst-free conditions to afford 3-[(2-arylsulfanyl)alkyl]-5-chloropyrazoles in excellent yields. High rate of the process is likely due to protonation of the "pyridine" nitrogen atom of the pyrazole ring to give a pyrazolium ion which activates the vinyl group towards nucleophilic attack by the simultaneously formed arylthiolate anions.

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Synthesis and crystal structure of discrete complexes and coordination polymers containing 1,3-bis(pyrazol-1-yl)propane ligands

Cited by 17 publications

References 34 publications

Crystal structure of a Zn complex with terephthalate and 1,6-bis(1,2,4-triazol-1-yl)hexane

Crystal structure of a Zn complex with terephthalate and 1,6-bis(1,2,4-triazol-1-yl)hexane

Synthesis and structure of 1-tert-butyl-substituted 3(5)-alkylpyrazoles from 2-chlorovinyl ketones

Novel directed synthesis of functionalized pyrazole derivatives via regioselective solvent-free thiylation of 3-alkenylpyrazoles with arenethiols

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