129715-55-5Relevant articles and documents
Synthesis and multinuclear magnetic resonance study of some tin(IV) complexes of pyridine-2-thiolate and related ligands, and the X-ray structural analysis of Sn(C5H4NS)4*C5H5NS
Damude, Leslie C.,Dean, Philip A. W.,Manivannan, Veeragathy,Srivastava, Radhey S.,Vittal, Jagadese J.
, p. 1323 - 1331 (2007/10/02)
Tin metal reacts with 2,2'-dithiobis(pyridine) in refluxing toluene to give the pyridine-2-thiolate complex Sn(C5H4NS)4, 1a.Multinuclear (77Se, 119Sn) magnetic resonance shows that ligand redistribution occurs in 1a:Sn(EPh)4 (E=S or Se) mixtures to give Sn(EPh)4-x(C5H4NS)x.From the pattern of the 119Sn chemical shifts of these series, compared with that of Sn(EPh)4-x(SR)x (R = simple alkyl or aryl group), the complexes are shown to be five-coordinate Sn(EPh)3(C5H4NS-N,S) when x=1 and six-coordinate Sn(EPh)4-x(C4H4NS-S)x-2(C5H4NS-N,S)2 when x = 2-4.Reaction of Sn(SPh)2 and (C5H4NS)2 yields pure Sn(SPh)2(C5H4NS)2.The 13C NMR spectrum of Sn(C5H4NS-S)2 (C5H4NS-N,S)2 is an exchange average down to 178 K, probably as a result of fluxionality.The series Sn(EPh)4-x(L')x (E=Se, L'=5-nitropyridine- or quinoline-2-thiolate, X = 0-4; E=S or Se, L' = pyridine-2-thiolate-N-oxide, X = 0-2) can be prepared in situ by redox between Sn(EPh)4 and the disulfide (L')2.Treatment of 1a with X2 (X=Br or E- gives SnX4-x(C5H4NS-N,S)x (x=2 or 3), which have been characterized by NMR, and provides a new synthesis of the known dihalo complexes. In a recrystallization of 1a from CH2Cl2:hexane Sn(C5H4NS)4*C5H5NS, 2, was obtained, probably as a result of hydrolysis.The structure of 2 has been solved by single crystal X-ray diffraction techniques.The compound crystallizes in the orthorhombic space group Pbca (No. 61) with a unit cell of dimensions a=17.132(2) Angstroem, b=15.337(2) Angstroem, c=21.268(3) Angstroem, and Z=8.Full-matrix least-squares on F led to agreement factors R=0.0439 and Rw=0.0426 for 3145 independent reflections with F0 > 2.5? (F0) and 206 variables.The molecule Sn(C5H4NS-S)2(C5H4NS-N,S)2 has highly distorted octahedral coordination about the tin atom, with the monodentate ligands in cis positions and the bidentate ligands attached with mutually cis nitrogen atoms.The Sn-S distances are 2.463(2)-2.542(2) Angstroem and the Sn-N distances are 2.332(2) and 2.324(2) Angstroem.The N-Sn-S angles in the chelate rings are 64.2(2) and 65.1(1) deg.The molecule of pyridine-2-thione in the lattice is hydrogen-bonded to the N atom of one of the monodentate ligands in the tin complex, with a N-H...N hydrogen bond distance of 1.92(7) Angstroem.
