Syntheses, Crystal Structures And Properties Of Metal Complexes Containing Bzdmpzm

In the past decades, much attention has been devoted to metal coordination complexes with pyrazoly alkane ligands because of their structural diversity, and their potential applications in catalysis, optics, magnetics. We deliberately selected bis(4-benzyl-3,5-dimethyl-1H-pyrazol-1-yl)methane (bzdmpzm) as ligand, to react with metal ions, resulting in the formation of nine coordination complexes [(bzdmpzm)Cu(μ-I)]₂ (1), [(bzdmpzm)Cu(μ-SCN)]n (2), [(bzdmpzm)Ag(NO₃)]₂ (3), Co(bzdmpzm)Cl₂ (4), Hg(bzdmpzm)I2 (5), Ni(bzdmpzm)Cl₂ (6), Cd(bzdmpzm)2Cl₂ (7) and [Cu(bzdmpzm)2Br]Br (8), {[Cu(dmpzm)₂]₂[Cu(dmpz)(μ-maleato)2]}[ClO₄]₂·3H₂O (9·3H₂O). These complexes were characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction analysis.Complex 1 consists of two [(bzdmpzm)Cu] fragments bridged by two iodides, forming a dimeric structure. Each Cu atom is tetrahedrally coordinated by two N atoms of one bzdmpzm ligand and two bridging iodide ions. 2 contains a unique 1D scolopendra-like chain of [(bzdmpzm)Cu] units linked by pairs of thiocyanates. Each Cu atom in 2 is also tetrahedrally coordinated by two N atoms from one bzdmpzm ligand, one N atom fromμ-SCN and one S atom from anotherμ-SCN. In 3, two [AgNO₃] fragments are connected by two bzdmpzm ligands froming circle structure. In mononuclear complexes 4, 5 and 6, each atom is coordinated by two N atoms of one bzdmpzm ligand and two I or Cl atoms, forming a distorted tetrahedral coordination geometry. In 7, the Cu center is coordinated by four N atoms of two bzdmpzm and one Br atom to form a severely distorted trigonal bipyramidal geometry. Each Cd atom in 8 adopts a distorted octahedral geometry defined by two Cl atoms, four nitrogen atoms of bzdmpzm group. 9 may be viewed as having a unique centrosymmetric sandwich structure in which two [Cu(dmpzm)₂] fragments are linked by [(dmpz)Cu(μ-maleato)₂]. The terminal Cu atom is coordinated by four N atoms from two dmpzm ligands and one O atom from maleato ligand form a severely distorted trigonal bipyramidal geometry. The tetrahedral coordination sphere of internal Cu atom is completed by two N atoms from dmpz molecules and two O atoms from twoμ-maleato ligand.