Di-µ2-chlorido-dichloridobis(dimethylformamide)tetrakis[µ3-1-(2-oxidobenzoyl)-2-(2-oxo-2-phenylethanethioyl)hydrazine-1,2-diido]octacopper(II) dimethylformamide disolvate.

The title compound, [Cu8(C15H10N3O3S)4Cl4(C3H7NO)2]·2C3H7NO, consisting of eight Cu(II) cations, four trianionic 1-(2-oxidobenzoyl)-2-(2-oxo-2-phenylethanethioyl)hydrazine-1,2-diide ligands, four chloride ligands and two coordinated and two solvent dimethylformamide molecules, crystallizes with the octanuclear molecule located on an inversion centre. The two halves of the molecule are connected by two bridging Cl atoms. This is the first example of an octanuclear complex based on a thiosemicarbazone-derived ligand.

Syntheses and structures of discrete copper(II) and cadmium(II) supramolecular complexes based on 1,4-diacylthiosemicarbazone ligands.

Thiosemicarbazides and their metal complexes have attracted considerable interest because of their biological activities and their flexibility, which allows the ligands to bend and rotate freely to accommodate the coordination geometries of various metal centres. Discrete copper(II) and cadmium(II) complexes have been prepared by crystallization of N-[2-(2-hydroxybenzoyl)hydrazinecarbonothioyl]propanamide (H3L) with Cu(CH3COO)2 or Cd(NO3)2 in a dimethylformamide/methanol mixed-solvent system at room temperature, affording the complexes di-µ-acetato-bis{µ4-1-[(2-oxidophenyl)carbonyl]-2-(propanamidomethanethioyl)hydrazine-1,2-diido}tetracopper(II) dimethylformamide disolvate, [Cu4(C11H10N3O3S)2(C2H3O2)2]·2C3H7NO, (I), and bis{µ2-[(2-hydroxyphenyl)formamido](propanamidomethanethioyl)azanido}bis[(4,4'-bipyridine)nitratocadmium(II)] dihydrate, [Cd2(C11H12N3O3S)2(NO3)2(C10H8N2)2]·2H2O, (II). Complex (I) consists of four Cu(II) cations, two µ4-bridging trianionic ligands and two µ2-bridging acetate ligands, while complex (II) is composed of two Cd(II) cations, two µ2-bridging monoanionic ligands, two nitrate ligands and two 4,4'-bipyridine ligands. These discrete complexes are connected by hydrogen bonds and van der Waals interactions to form a three-dimensional supramolecular architecture. Compared with (I), the phenolic hydroxy group and hydrazide N atom of the thiosemicarbazide ligand of (II) are not involved in coordination and lead to a binuclear Cd(II) complex. This different coordination mode may be attributed to the larger ionic radius of the Cd(II) ion compared with the Cu(II) ion.

A copper(I) coordination polymer incorporation the corrosion inhibitor 1H-benzotriazole: poly[µ3-benzotriazolato-κ(3)N(1):N(2):N(3)-copper(I)].

The title complex, [Cu(C6H4N3)]n, was synthesized by the reaction of cupric nitrate, 1H-benzotriazole (BTAH) and aqueous ammonia under hydrothermal conditions. The asymmetric unit contains three crystallographically independent Cu(I) cations and two 1H-benzotriazolate ligands. Two of the Cu(I) cations, one with a linear two-coordinated geometry and one with a four-coordinated tetrahedral geometry, are located on sites with crystallographically imposed twofold symmetry. The third Cu(I) cation, with a planar three-coordinated geometry, is on a general position. Two Cu(I) cations are doubly bridged by two BTA(-) ligands to afford a noncentrosymmetric planar [Cu2(BTA)2] subunit, and two [Cu2(BTA)2] subunits are arranged in an antiparallel manner to form a centrosymmetric [Cu2(BTA)2]2 secondary building unit (SBU). The SBUs are connected in a crosswise manner via the sharing of four-coordinated Cu(I) cations, Cu-N bonding and bridging by two-coordinate Cu(I) cations, resulting in a one-dimensional chain along the c axis. These one-dimensional chains are further linked by C-H···π and weak van der Waals interactions to form a three-dimensional supramolecular architecture.