Transition metal complexes with pyrazole based ligands, part 18: new binuclear Cu(I), Cu(II) and Co(II) complexes with 3,5-dimethyl-1-thiocarboxamide pyrazole: synthesis, structural and magnetic studies

Evans, Ivana Radosavljević; Howard, Judith A. K.; Howard, Luciano E. M.; Evans, John S. O.; Jaćimović, Željko K.; Jevtović, Violeta; Leovac, Vukadin M.

doi:10.1016/j.ica.2004.06.058

Cited by 32 publications

(16 citation statements)

References 19 publications

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“…[12], that of the Co 2 L 2 Cl 4 , Cu 2 L 2 Cl 4 and Cu 2 L 2 Br 2 complexes as in Ref. [17]. The infrared spectra were recorded between 4000 and 150 cm À1 on a Perkin-Elmer System 2000 FT-IR spectrometer equipped with an MCT detector for the mid-IR range and with a DTGS detector for the far-IR range.…”

Section: Methodsmentioning

confidence: 99%

Vibrational spectroscopic and theoretical study of 3,5-dimethyl-1-thiocarboxamide pyrazole (L) and the complexes Co2L2Cl4, Cu2L2Cl4 and Cu2L2Br2

et al. 2006

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Section: Methodsmentioning

confidence: 99%

Vibrational spectroscopic and theoretical study of 3,5-dimethyl-1-thiocarboxamide pyrazole (L) and the complexes Co2L2Cl4, Cu2L2Cl4 and Cu2L2Br2

et al. 2006

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“…The structure of Cu 2 L 2 Cl 4 , Cu 2 L 2 Br 2 and Co 2 L 2 Cl 4 has been determined by single crystal X-ray diffraction [23]. Cu 2 L 2 Cl 4 and Co 2 L 2 Cl 4 are isostructural.…”

Section: Resultsmentioning

confidence: 99%

Transition metal complexes with pyrazole-based ligands

Szécsényi

Leovac

Kovács

et al. 2005

J Therm Anal Calorim

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“…As a part of systematic study on complexing properties of pyrazolyl molecules [1][2][3], the present paper reports on a new Ni(II) complex.…”

Section: Discussionmentioning

confidence: 99%

“…As a part of systematic study on complexing properties of pyrazolyl molecules [1][2][3], the present paper reports on a new Ni(II) complex. The crystal structure of the ligand 3,5-dimethyl-1-thiocarboxamide pyrazole (L1) was recently reported [4] and a DFT computation has been used to obtain in-vacuo theoretical geometry [5].…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of bis(μ2-thiocyanato)tetrakis(3,5-dimethyl-1- (thiocarbamoyl)pyrazole)dinickel(II) dichloride ethanol disolvate, [Ni(NCS)2(C6H6N3S)4][Cl]2 · 2C2H5OH

Jaćimović¹,

Radović²,

Leovac³

et al. 2007

Zeitschrift Für Kristallographie - New Crystal Structures

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C 30 H 48 Cl 2 N 14 Ni 2 O 2 S 6 , monoclinic, P12 1 /c1 (no. 14), a = 12.0407(7) Å, b = 11.8861(6) Å, c = 15.7389(9) Å, b = 93.904(1)°, V = 2247.3 Å 3 , Z = 2, Rgt(F) = 0.032, wR ref (F 2 ) = 0.069, T = 120 K. Source of materialThe complex was synthesized by mixing hot ethanolic solution of the ligand 3,5-dimethyl-1-thiocarboxamide pyrazole (Pz-CS, 1 mmol) and NiCl 2 · 6H 2 O (0.5 mmol). DiscussionAs a part of systematic study on complexing properties of pyrazolyl molecules [1][2][3], the present paper reports on a new Ni(II) complex.The crystal structure of the ligand 3,5-dimethyl-1-thiocarboxamide pyrazole (L1) was recently reported [4] and a DFT computation has been used to obtain in-vacuo theoretical geometry [5].The interesting aspect of this ligand and its derivative is its ambidentate nature. It can coordinate bidentately to metal through the pyrazole ring nitrogen and thiolato sulfur or by using ring nitrogen and iminyl nitrogen (of thiocarbamyl group). Explanation of the ambidentate nature of this ligand in terms of the HSAB model [6] implies its capability to stabilize different oxidation state of the same metal. It could be also expected that oxidation state of the ligand would influence the mode of coordination. It was found that in the case of Co(III)(L) 3 complex [7], monodeprotonated L1 is bound to metal through the pyrazole ring nitrogen and the thiocarboxamide nitrogen. However, in the Co2L2Cl4 fivecoordinated Co (II) is bound to neutral L1, through the pyrazole nitrogen and thiol sulfur. In accordance with the HSAB model [8], it is expected that ligand L1 will bind to Ni(II) through the pyrazole nitrogen and sulfur from the thiocarboxamide fragment. This mode of coordination was observed in the Ni(II) complex with the closely related monodeprotonated ligand 3,5-dimethyl-1-(N-ethyl)-thiocarbamylpyrazole (L2) [9]. In contrast to this, recent X-ray powder diffraction study [10] revealed that monodeprotonated ligand L1 is bound to Ni(II) through the nitrogen atoms of the pyrazole ring and the thiocarboxamide group. This observation is not in accordance with the expectations based on HSAB model, which stress the importance of obtaining more information on the factors important for complexing properties of this ligand. The crystal structure of the title compound is built up of discrete centrosymmetric dinuclear units, with end-to-end bridging NCS anionic ligands, Cl anions, and ethanol molecules. Two neutral molecules of L1 coordinate to Ni(II) through the pyrazole-ring N atoms and thiocarboxamide S atoms, which is in accordance with the HSAB model. The Ni(II) adopts distorted octahedral coordination, with thiocyanato N, and thiol S placed in the axial positions. Two pyrazolyl ligands show similar arrangement, except for the torsion angle NNCS (ÐN10N8C16S2 = 14.66°, ÐN12N9C18S5 = 32.44°), which indicates significant difference in the conformation of two chelate rings. Greater distortion of the chelate ring is associated with the longer axial NiS bond (d(Ni1S5) = 2.519 Å, d(Ni1S2) = 2.422 ...

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Transition metal complexes with pyrazole based ligands, part 18: new binuclear Cu(I), Cu(II) and Co(II) complexes with 3,5-dimethyl-1-thiocarboxamide pyrazole: synthesis, structural and magnetic studies

Cited by 32 publications

References 19 publications

Vibrational spectroscopic and theoretical study of 3,5-dimethyl-1-thiocarboxamide pyrazole (L) and the complexes Co2L2Cl4, Cu2L2Cl4 and Cu2L2Br2

Vibrational spectroscopic and theoretical study of 3,5-dimethyl-1-thiocarboxamide pyrazole (L) and the complexes Co2L2Cl4, Cu2L2Cl4 and Cu2L2Br2

Transition metal complexes with pyrazole-based ligands

Crystal structure of bis(μ2-thiocyanato)tetrakis(3,5-dimethyl-1- (thiocarbamoyl)pyrazole)dinickel(II) dichloride ethanol disolvate, [Ni(NCS)2(C6H6N3S)4][Cl]2 · 2C2H5OH

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