Crystal and solution structures of di-n-butyltin(IV) complexes of 5-[(E)-2-(4-methoxyphenyl)-1-diazenyl]quinolin-8-ol and benzoic acid derivatives: En route to elegant self-assembly via modulation of the tin coordination geometry

Reactions of nBu2SnCl(L1) (1), where L1 = acid residue of 5-[(E)-2-(4-methoxyphenyl)-1-diazenyl]quinolin-8-ol, with various substituted benzoic acids in refluxing toluene, in the presence of triethylamine, yielded dimeric mixed ligand di-n-butyltin(IV) complexes of composition [nBu2Sn(L1)(L2–6)]2 where L2 = benzene carboxylate (2), L3 = 2-[(E)-2-(2-hydroxy-5-methylphenyl)-1-diazenyl]benzoate (3), L4 = 5-[(E)-2-(4-methylphenyl)-1-diazenyl]-2-hydroxybenzoate (4), L5 = 2-{(E)-4-hydroxy-3-[(E)-4-chlorophenyliminomethyl]-phenyldiazenyl}benzoate (5) and L6 = 2-[(E)-(3-formyl-4-hydroxyphenyl)-diazenyl]benzoate (6). All complexes (1–6) have been characterized by elemental analyses, IR, 1H, 13C and 117Sn NMR and 119Sn Mössbauer spectroscopy and their structures were determined by X-ray crystallography, complemented by 117Sn CP-MAS NMR spectroscopy studies in the solid state. The crystal structure of 1 reveals a distorted trigonal bipyramidal coordination geometry around the Sn-atom where the Cl- and N-atoms of ligand L1 occupy the axial positions. In complexes 2–5, the molecules are centrosymmetric dimers in which the Sn-atoms are connected by asymmetric μ-O bridges through the quinoline O-atom to give an Sn2O2 core. The differences in the Sn–O bond lengths within the bridge range from 0.28 to 0.48 Å, with the longer of the Sn–O distances being in the range 2.56–2.68 Å and the most symmetrical bridge being in 5. The carboxylate group is almost symmetrically bidentate coordinated to the tin atom in 5 (Sn–O distances of 2.327(2) and 2.441(2) Å), unlike the other complexes in which the distance of the carboxylate carbonyl O-atom from the tin atom is in the range 2.92–3.03 Å. The structure of 5 displays a more regular pentagonal bipyramidal coordination geometry about each tin atom than in 2–4. In contrast, the centrosymmetric dimeric structure of 6 involves asymmetric carboxylate bridges, resulting in a different Sn2C2O4 motif. The Sn–O bond lengths in the bridge differ by about 0.6 Å, with the longer distance involving the carboxylate carbonyl O-atom (2.683(2) and 2.798(2) Å for two molecules in the asymmetric unit). The carboxylate carbonyl O-atom has a second, even longer intramolecular contact to the Sn-atom to which the carboxylate group is primarily coordinated, with these Sn⋯O distances being as high as 3.085(2) and 2.898(2) Å. If the secondary interactions are considered, all the di-n-butyltin(IV) complexes (2–6) display a distorted pentagonal bipyramidal arrangement about each tin atom in which the n-butyl groups occupy the axial positions.

Di-n-butyltin(IV) complexes [nBu2Sn(L)(Lx)]2 (L = 5-[(E)-2-(4-methoxyphenyl)-1-diazenyl]quinolin-8-ol and Lx = substituted benzoic acids) is described. The crystal structures of the complexes reveal two different types motifs viz., Sn2O2 and Sn2C2O4 as a result of a strong modulation of the tin coordination geometry as a function of the substituent pattern on the various benzoates.Figure optionsDownload as PowerPoint slide