Structural, spectroscopic and computational studies of the HgL2Cl2 complex (L = 3,5-dimethyl-1-thiocarboxamide pyrazole) and the crystal structure of L

In the present paper we report the synthesis as well as the structural and vibrational characterisation of the HgL2Cl2 complex (L = 3,5-dimethyl-1-thiocarboxamide). The crystal and molecular structures of both L and the HgL2Cl2 complex were determined by single-crystal X-ray diffraction. The coordination propensity of L to HgCl2 was explored by quantum chemical calculations. We found the preference of the monodentate coordination of L to HgCl2 through the sulfur atom (instead of the “pyridine” nitrogen) to be in agreement with Pearson’s acid–base character of the atoms involved and the steric effects. The vibrational properties of HgL2Cl2 were evaluated by a joint FT-IR and quantum chemical analysis. In addition, the thermal decomposition of the complex and ligand is reported.

[1]  M. N. Ponnuswamy,et al.  Design, synthesis and anti-microbial activity of 1H-pyrazole carboxylates. , 2004, Bioorganic & medicinal chemistry letters.

[2]  S. Baek,et al.  Selective Nonsteroidal Anti-Inflammatory Drugs Induce Thymosin β-4 and Alter Actin Cytoskeletal Organization in Human Colorectal Cancer Cells , 2004, Journal of Pharmacology and Experimental Therapeutics.

[3]  J. S. Evans,et al.  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 , 2004 .

[4]  J. Howard,et al.  Transition metal complexes with pyrazole-based ligands. XIX. Di­aqua­bis(3,5-di­methyl-1H-pyrazole-1-carbox­amidine-κ2N,N′)­metal(II) ­dinitrate, with metal = Co and Ni , 2004 .

[5]  J. Howard,et al.  Synthesis, characterization and crystal structure of a novel Ni(II) complex, Ni(L-H)2 (L = 3,5-dimethyl-1-thiocarboxamidopyrazole) , 2004 .

[6]  A. Rauter,et al.  Synthesis of New Pseudo‐C‐Nucleosides Containing Pyrazole Rings in their Structure , 2004 .

[7]  Richard I. Cooper,et al.  CRYSTALS version 12: software for guided crystal structure analysis , 2003 .

[8]  Ž. Jaćimović,et al.  Reaction of copper(II) with 1-carboxamide-3,5-dimethylpyrazole, 1-carboxamidine-3,5-dimethylpyrazole, 4-acetyl-3-amino-5-methylpyrazole and 5-amino-4-carboxamide-1-phenylpyrazole ☆ , 2003 .

[9]  F. Allen.  The Cambridge Structural Database: a quarter of a million crystal structures and rising. , 2002, Acta crystallographica. Section B, Structural science.

[10]  J. Reedijk,et al.  Synthesis and catalytic activities of copper(II) complexes derived from a tridentate pyrazole-containing ligand. X-ray crystal structure of [Cu2(μ-dpzhp-O,N,N′)2][Cu(MeOH)Cl3]2 , 2001 .

[11]  C. Pettinari,et al.  Structure and volatility of copper complexes containing pyrazolyl-based ligands , 2001 .

[12]  S. Gál,et al.  Transition Metal Complexes with Pyrazole-based Ligands. Part 8. Characterization and thermal decomposition of zinc(II) complexes with di- and trisubstituted pyrazoles , 2001 .

[13]  R. Mukherjee.  Coordination chemistry with pyrazole-based chelating ligands: molecular structural aspects , 2000 .

[14]  Ž. Jaćimović,et al.  Transition Metal Complexes with Pyrazole-Based Ligands 7. Zn(II), Co(II), Mn(II) and Cu(II) complexes with 3-amino-5-methylpyrazole , 1999 .

[15]  J. Elguero,et al.  A structural study of pyrazole-1-carboxamides by X-ray crystallography and 13C CPMAS NMR spectroscopy , 1999 .

[16]  J. Madarász,et al.  Transition metal complexes with pyrazole-based ligands. Part 6.: Synthesis, characterization and thermal decomposition of cadmium complexes with 3(5)-amino-5(3)-methylpyrazole , 1998 .

[17]  G. Deacon,et al.  Another Surprise from Pyrazolate Ligands. , 1998, Angewandte Chemie.

[18]  H. Bergh,et al.  Growth of Copper Films by Metal Organic Vapor Deposition Using (Pyrazolylborate)copper(I) Compounds , 1997 .

[19]  E. Solomon,et al.  Multicopper Oxidases and Oxygenases. , 1996, Chemical reviews.

[20]  Charles W. Bock,et al.  Energies and Geometries of Isographic Hydrogen-Bonded Networks. 1. The (8) Graph Set , 1996 .

[21]  Maria Cristina Burla,et al.  SIR92 – a program for automatic solution of crystal structures by direct methods , 1994 .

[22]  Gernot Frenking,et al.  A set of f-polarization functions for pseudo-potential basis sets of the transition metals ScCu, YAg and LaAu , 1993 .

[23]  S. Trofimenko.  Recent advances in poly(pyrazolyl)borate (scorpionate) chemistry , 1993 .

[24]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[25]  N. Juranić,et al.  Metal complexes with pyrazole-derived ligands Part I. Synthesis and crystal structures of 3-amino-4-acetyl-5-methylpyrazole (L) and of the tetrahedral complexes ZnL2(NO3)2 and ML2Cl2 (M=Cu(II), Hg(II)) , 1991 .

[26]  T. N. Sorrell.  Synthetic models for binuclear copper proteins , 1989 .

[27]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[28]  T. Ho.  Hard soft acids bases (HSAB) principle and organic chemistry , 1975 .

[29]  S. F. Boys,et al.  The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors , 1970 .

[30]  R. Pearson,et al.  Application of the Principle of Hard and Soft Acids and Bases to Organic Chemistry , 1967 .

[31]  Ralph G. Pearson,et al.  HARD AND SOFT ACIDS AND BASES , 1963 .

[32]  Ž. Jaćimović,et al.  Transition Metal Complexes with Pyrazole Based Ligands , 2003 .

[33]  M. Drew,et al.  Unusual behaviour of the thioether function of the ligand 1,8-bis(3,5-dimethyl-1-pyrazolyl)-3,6-dithiaoctane (bddo) towards transition-metal salts. X-Ray structures of a green and a red modification of [Cu(bddo)Cl2] , 1990 .

[34]  W. R. Wadt,et al.  Ab initio effective core potentials for molecular calculations , 1984 .

[35]  C. Swahn,et al.  The Structure of Pyrazole, C3H4N2, at 295 K and 108 K as determined by X-Ray Diffraction. , 1973 .