Abstract
New benzolamide (H 2bz, 5-phenylsulfonamide-1,3,4-thiadiazole-2-sulfonamide) zinc(II) and copper(II) complexes with tris(2-benzimidazolyl-methylamine) (L) and ammonia are reported. The crystal structures of the Zn(II) complexes were determined. The [Zn(Hbz)L]ClO 4 ·H 2O compound crystallizes in the triclinic P 1 ̄ space group with a=11.006(1), b=14.777(2), c=14.918(2) Å, α=114.30(1), β=98.90(1), γ=107.36(1)° and Z=2. In this compound the Zn(II) has a distorted trigonal bipyramidal geometry. The {[Zn 2(bz) 2(NH 3) 4] ·2H 2O} ∞ crystallizes in the monoclinic space group C2/ c with a=23.530(3), b=10.4124(11), c=15.428(2) Å, β=110.591(9)° and Z=4. The metal centre is in a distorted tetrahedral [ZnN 4] environment. The benzolamide presents a different coordination behaviour in these complexes. In [Zn(Hbz)L]ClO 4 ·H 2O it acts as a monodentate ligand through the thiadiazole N atom contiguous to the deprotonated sulfonamido group, while in {[Zn 2(bz) 2(NH 3) 4] ·2H 2O} ∞ it behaves as a bridge joining two Zn(II) ions via the N atom of the thiadiazole ring and the N atom of the free sulfonamido group. The Cu(Hbz)L(NO 3) complex was also obtained and characterized. The electronic properties and the EPR of the copper-doped zinc complexes showed that the copper(II) ion adopts a square pyramidal geometry. Also, for the Zn(II) complexes the interaction Zn–benzolamide has been studied using extended-Hückel molecular-orbital (EHMO) calculations.
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