Acylpyrazolone ligands: Synthesis, structures, metal coordination chemistry and applications

Marchetti, Fábio; Pettinari, Cláudio; Pettinari, Riccardo

doi:10.1016/j.ccr.2005.03.013

Cited by 263 publications

(172 citation statements)

References 213 publications

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“…Di-ketone acylpyrazolone are good biological, catalytic and analyticalreagents, as such they have been widely used [1]. They can chelate metal ions, aproperty that have been reported to increase their efficiency [2].…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of 4-propyl-3-methyl-1-phenyl-2-pyrazolin-5-one thiosemicarbazone, C15H19N5OS

Idemudia

Sadimenko

Hosten

2015

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialAnalyticalgrade reagents as procured were used without further purification.T oasolution of synthesized4-propyl-3-methyl-1-phenyl-2-pyrazolin-5-one (2.0 mmol, 0.52 g) in methanol (10 mL)was added slowly thiosemicarbazide (2.0 mmol, 0.18 g) in methanol (10 mL) while stirring and the golden brown mixture obtained was refluxed for 3h.The yellow precipitate was filtered, washed with methanol, dried at room temperature and stored over fused CaCl 2 .Yellow single crystals of the title keto imine Schiff base suitable for x-ray diffraction were grown at room temperature from slow evaporation of dimethylformamide solution. Experimental detailsCarbon-bound Hatomswere placed in calculated positions and were included in the refinement in the riding model approximation, with U iso (H) set to 1.2 U eq (C). The Hatoms of the methyl groups were allowed to rotate with afixed angle around the C-C bond to best fit the experimental electron density (HFIX 137 in the SHELX program suite [8]), with U iso (H) setto1.5U eq (C). The nitrogen-bound Ha tomsw ere located on ad ifference Fourier mapand refined freely. DiscussionDi-ketone acylpyrazolone are good biological, catalytic and analyticalreagents, as such they have been widely used [1]. They can chelate metal ions, aproperty that have been reported to increase their efficiency [2]. They form useful Schiffb ases with amino groups [3,4 ]. Thiosemicarbazides are an interesting group of compounds with versatile properties. They are good chelating reagents which form superior tridentate Schiff bases with ONS coordination sites with metal ions [5]. Acylpyrazolone with benzoyl derivative have been used for the synthesis of Schiff bases and have been reported by us earlier [3,4 ]. Presented herein is the crystal and molecular structure of a4-propyl-3-methyl-1-phenyl-2-pyrazolin-5-one Schiff base with thiosemicarbazide. In this crystal structure one molecule is present in the asymmetricunit. Thebackboneofthe structureisessentially planar indicatingan amidetyperesonance.The least-square planethrough thebackbone atoms N1-N3, C1-C3, C5 and O1 has ar.m.s. deviation of only 0.0049 Å. The intramolecular hydrogen bond N3-H3×××O1 of length 1.904(17) Åa lso helps to maintain planarity. The C11-C16 phenyl ring is rotated outofthe abovementioned plane with its least square plane making adihedralangle of 25.82(6)°w ith the main plane.T he phenylr ingh as an intramolecular C12-H12×××O1 hydrogen bond of length 2.44 Å. Thereare anumber of intermolecular hydrogen interactions forming infinite chains in the structure. The N4-H4×××S1 bond has al ength of 2.482(17) Åand in terms of Graph Set analyses [6,7]forms a chain along the b-axisthatcan be describedbyaC 1 1 (4) descriptor on the unary level. TheN5-H5B×××N2 interaction of 2.154(16) Å also formsachain along the b-axis and has adescriptor of C 1 1 (9) on the unary level. Thesum of the aforementioned classical hydrogen bonds lead to alayered structure (parallel to the ab plane).

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Section: Discussionmentioning

confidence: 99%

Crystal structure of 4-propyl-3-methyl-1-phenyl-2-pyrazolin-5-one thiosemicarbazone, C15H19N5OS

Idemudia

Sadimenko

Hosten

2015

Zeitschrift Für Kristallographie - New Crystal Structures

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“…Thep yrazole compounds arei mportant targets coordination chemistry [5][6][7].T he asymmetrical coordination moiety of the pyrazole compounds could play akey role in the catalytic properties of newo rganometal pyrazole,avast area of coordination chemistryt hati sw aiting to be furthere xploreda nd developed, particularly in thecaseofgroup VIIIBmetals, which are known to be potential catalysts in avariety of applications [8]. The introduction of carboxyl, in thestructure of pyrazole compounds, can improvethe catalyticability of metal complexes [9,10].…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of 4-(5-(benzoyloxy)-3-methyl-1H-pyrazol-1-yl)benzoic acid monohydrate, C18H16N2O5

Zhao

Ding

et al. 2015

Zeitschrift Für Kristallographie - New Crystal Structures

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“…They arebioactive di-ketone heterocycles [3]and are capable of formingSchiffbases with aminogroups [4,5].Successful coordination of acylpyrazolone diketones with transition metals have been reported to increase their catalyticp roperties [6]. We have already reported abioactive cobalt complex of acylpyrazolone [7].…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of cis bis(4-benzoyl-3-methyl-1-phenyl pyrazol-5-one)- cis bis(methanol)-cobalt(II), C36H34CoN4O6

Idemudia

Sadimenko

Hosten

2015

Zeitschrift Für Kristallographie - New Crystal Structures

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C 36 H 34 CoN 4 O 6 ,monoclinic, P2 1 /n (no. 14), a =13.9021(5) Å, b =13.9557(5) Å, c =17.3379(6) Å, b =101.254(2)°, V =3299.1 Å 3 , Z =4,R gt (F) =0.0316, wR ref (F 2 ) =0.0869, T =200 K. Source of materialTo as olution of Bmpp-Ph (3-methyl-1-phenyl-4-[(phenyl)(2-phenylhydrazin-1-yl)methylidene]-1H-pyrazol-5(4H)-one, 2 mmol, 0.74 g) in hot ethanol (40 mL) was addedindrops aqueous solution of CoCl 2 ×4H 2 O(1mmol, 0.20 g) while stirring under reflux. After 4hofreflux, the pink precipitate was filtered, washed with ethanol/water (1:1), dried at room temperature and stored over fused CaCl 2 .Slow evaporation of asolution of the resultant pink solid in methanol afforded orange crystals of an unprecedented Co(Bmpp) 2 (MeOH) 2 suitable forx-raycrystallography. Experimental detailsCarbon-boundHatoms were placed in calculated positionsand were included in therefinement in the riding model approximation, with U iso (H) set to 1.2 U eq (C). The Hatoms of the methyl groups were allowed to rotate with afixed angle around the C-C bond to best fit the experimental electron density (HFIX 137 in the SHELX program suite [11]), with U iso (H) set to 1.5 U eq (C). The oxygen-bound Hatomswere located on adifference Fourier mapand refined freely. DiscussionAs an analytical reagent acylpyrazolones have been employed as good spectroscopicchelating ligand forthe determinationofmetalsintrace amounts[1],they have also been used as excellent catalysts [2]. They arebioactive di-ketone heterocycles [3]and are capable of formingSchiffbases with aminogroups [4,5].Successful coordination of acylpyrazolone diketones with transition metals have been reported to increase their catalyticp roperties [6]. We have already reported abioactive cobalt complex of acylpyrazolone [7]. In view of our interest in metal complexes of Schiff bases, presentedhereinisthe molecularand crystal structure of anew cobalt complex. The studies on the bioactive and catalytic activities of the title compound are presently ongoing. In thecrystal structurethe title complex has an octahedral coordination geometry consisting of two Bmpp ligands and two coordinating methanol molecules. Each 4-benzoyl-3-methyl-1-phenyl pyrazol-5-one (Bmpp)l igand is deprotonated with the negative charge delocalized. The Bmpp ligands occur cis to each other similarly to the cis complex reported by Wu et al. [8]which has one methanol and one ethanol ligand. In contrast the complex we reported earlier [7]with two coordinating ethanol ligands has two Bmpp ligands trans to each other. Theaverage Bmpp Co-O bond length here is 2.070(33) Åwhich is very similar to the mixed ethanol methanol complex [8] wheret he average bond length is 2.071(29) Å. In the complex with the two trans ethanols [7] the average Co-O bond length is only slightly shorter at 2.038(36) Å. The title complex is obviously non-centrosym-metrical therefore the two Bmpp ligands having different geometrical configurations. In the first ligand the dihedral angle between the least square planes through the phenyl rings is 20.76(...

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Acylpyrazolone ligands: Synthesis, structures, metal coordination chemistry and applications

Cited by 263 publications

References 213 publications

Crystal structure of 4-propyl-3-methyl-1-phenyl-2-pyrazolin-5-one thiosemicarbazone, C15H19N5OS

Crystal structure of 4-propyl-3-methyl-1-phenyl-2-pyrazolin-5-one thiosemicarbazone, C15H19N5OS

Crystal structure of 4-(5-(benzoyloxy)-3-methyl-1H-pyrazol-1-yl)benzoic acid monohydrate, C18H16N2O5

Crystal structure of cis bis(4-benzoyl-3-methyl-1-phenyl pyrazol-5-one)- cis bis(methanol)-cobalt(II), C36H34CoN4O6

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