Permanent URL to this publication: http://dx.doi.org/10.5167/uzh-21186
Basu Baul, T S; Mizar, A; Pauli, A; Ruisi, G; Willem, R; Biesemans, M; Linden, A (2009). 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. Journal of Organometallic Chemistry, 694(14):2142-2152.
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-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 0.28-0.48 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 Sn-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 Sn-atom is in the range 2.92-3.03 Å. The structure of 5 displays a more regular pentagonal bipyramidal coordination geometry about each Sn-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 Sn-atom in which the n-butyl groups occupy the axial positions.
|Item Type:||Journal Article, refereed, original work|
|Communities & Collections:||07 Faculty of Science > Institute of Organic Chemistry|
|Uncontrolled Keywords:||5-[(E)-2-(4-methoxyphenyl)-1-diazenyl]quinolin-8-ol; di-n-butyltin(IV) complexes; benzoic acid; mixed ligands; solution and solid state tin-NMR; Crystal structure|
|Deposited On:||13 Oct 2009 12:03|
|Last Modified:||23 Nov 2012 13:32|
|Funders:||Department of Science and Technology,New Delhi, India (Grant Nos. SR/S1/IC-03/2005), University Grants Commission, New Delhi,India through SAP-DSA, Phase-III, Fund for Scientific Research Flanders, Belgium (FWO) (Grants No. G.0064.07 and G.0469.06), Research Council of the VUB for a Concerted Research Action funding (GOA31), Università di Palermo, Italy|
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