Simple Synthesis, Characterization and Structure of Diorganotin(IV) Complexes Containing the N-(2-Salicylidene)-N'-benzoylhydrazone Ligand

Abstract

Two diorganotin(IV) complexes of general formula R2Sn[2-OC6H4CH=NDN=C(O)Ph] (R = Ph, 1; R = Me, 2) have been synthesized from the corresponding diorganotin(IV) dichloride and the Schiff base derived from salicylaldehyde and benzoyl hydrazide. The two compounds have been characterized by elemental analysis, IR and NMR (1H, 13C, 15N, 119Sn) spectra, and their structures have been confirmed by single crystal X-ray structure analysis. Crystals of complex 1 re triclinic, space group P1̄ , a = 11.1631(5), b = 13.462(2), c = 16.511(1) Å , α = 106.193(9), β = 106.379(8), γ = 94.932(8)°, Z = 4, R1 = 0.0461, wR2 = 0.0939 for 13194 unique reflections. Crystals of 2 are monoclinic, space group P21, a = 10.2073(5), b = 14.645(2), c = 10.411(3) Å, β = 92.572(9)°, Z = 4, R1 = 0.0395, wR2 = 0.0835 for 5050 unique reflections. The central tin atom of either complex adopts a distorted trigonal bipyramidal coordination with two ligand oxygen atoms in axial positions, the nitrogen atom of the ligand and two organic groups on tin occupying equatorial sites. The δ(119Sn) values for the complexes 1 and 2 are -329.2 and -150.3, respectively, thus indicating penta-coordinated tin centres.

[N-Formyl-N′-(2-oxidobenzylidene)hydrazine-κ3O,N,O′]diphenyltin(IV)

“…The distortion can be rationalized in terms of the steric demands of the two chelate rings formed by the tridentate ligand. Similar structures have been found in the analogues in which the C1 position in (I) is substituted with Me ( = 0.59; Diouf et al, 1999) and Ph ( = 0.50 and 0.55 for the two independent molecules; Dey et al, 2003). The dihedral angles between the mean plane of the ligand and the C9 and C15 phenyl rings are 68.82 (9) and 56.13 (10) , respectively.…”

Understanding the structure of salicyl hydrazone metallocomplexes: crystal structure, AIM and Hirshfeld surface analysis of trichloro-(N-salicylidenebenzoylhydrazinato-N,O,O′)-tin(IV)

“…Both oxygen atoms and nitrogen atom of the L are situated in the equatorial plane of the tin, the Cl(1) is also situated in equatorial plane opposite to the N(1), and the Cl(2) and Cl (3) atoms are in axial positions of the octahedron. The L in 1 is a monoanion, while in the structures of SnLPh 2 (JACZOD) and SnLMe 2 (JACZUJ) it is a dianion [60]. From hereon, the CSD refcode is given in parenthesis.…”

Simplified synthesis, 1H, 13C, 15N, 119Sn NMR spectra and X-ray structures of diorganotin(IV) complexes containing the 4-phenyl-2,4-butanedionebenzoylhydrazone(2−) ligand

“…Journal of Organometallic Chemistry 689 (2004) 88-95 www.elsevier.com/locate/jorganchem These complexes, derived from the more flexible hydrazone ligand [4-phenyl-2,4-butanedionebenzoylhydrazone(2))], have been structurally characterised in both the solid and solution state by crystallography and NMR in continuation of our previous studies [10][11][12]. This structural comparison in both states will help to elucidate structure of new organotin(IV) complexes using NMR spectral results for which X-ray data are not available.…”

“…The C-Sn-C angle for 1 was calculated from the 1 J( 119 Sn, 13 C) value [19b] and was found to be 134.9°(cf. 120.81 (12)°in the X-ray study). For compound 2, the CSn-C angle was calculated using the equation 1 J( 119 Sn, 13 C) ¼ 10:7h À 778 [23] with the 1 J( 119 Sn, 13 In the 1 H NMR spectrum of 2, Sn-Me and CH 3 proton signals appear at d 0.80 and 2.57 ppm, respectively.…”

“…Recently the coordination modes of the ONO donor tridentate N-(2-carboxyphenyl)salicylideneimine dianion and N-(2-carboxyphenyl)-5 0 -bromosalicylideneimine dianion towards diorganotin have been reported [10,11]. However, hydrazone diorganotin(IV) complexes have been less widely studied [6,12]. Most of the above diorganotin(IV) complexes have synthesised using complex procedures under rigorously anhydrous conditions, e.g.…”