New drum and ladder organooxotin carboxylates

Article abstract of DOI:10.1021/ic00254a017

The hexameric n-butyloxotin cyclopentanoate [n-BuSn(O)O₂CC₅H₉]₆·C ₆H₆ (1) and hexameric n-butyloxotin cyclohexanoate [n-BuSn(O)O₂CC₆H₁₁]₆·C ₆H₆ (4) were prepared by reacting n-butylstannanoic acid with the corresponding carboxylic acid. X-ray analysis showed these new substances to have drum structures. Reaction of n-butyltin trichloride with the silver salt of cyclohexanecarboxylic acid gave the dimeric composition [(n-BuSn(O)O₂CC₆H₁₁)₂(n-BuSn(O ₂CC₆H₁₁)₃)]₂ (3). The synthesis of a novel chloro derivative, [(n-BuSn(O)O₂CPh)₂(n-BuSn(Cl)(O₂CPh) ₂)]₂ (2), also is reported. Both 2 and 3 have ladder or open-drum structures. Interconversion of the drum and ladder structures is established in solution by ¹¹⁹Sn NMR, and a possible mechanism for the hydrolysis of a ladder to a drum formulation is presented. 1 crystallizes in the monoclinic space group P2₁/n with a = 14.452 (3) A, b = 18.424 (4) A, c = 15.150 (4) A, β = 102.53 (2)°, and Z = 2. 2 crystallizes in the triclinic space group P1 with a = 12.900 (2) A, b = 14.416 (4) A, c = 14.420 (2) A, α = 110.99 (2)°, β = 96.89 (1)°, γ = 112.55 (2)°, and Z = 1. 3 crystallizes in the triclinic space group P1 with a = 13.877 (6) A, b = 15.126 (6) A, c = 15.148 (4) A, α = 116.19 (2)°, β = 103.31 (3)°, γ = 93.26 (3)°, and Z = 1. 4 crystallizes in the monoclinic space group P2₁/n with a = 14.592 (5) A, b = 19.342 (5) A, c = 15.526 (3) A, β = 97.85 (2)°, and Z = 2. The final conventional unweighted residuals were 0.048 (1), 0.029 (2), 0.114 (3), and 0.076 (4).