Synthesis of triorganostannate esters of dicarboxylic acids. Crystal structure of bis(dicyclohexylammonium)trisoxalatotetrakis(tri-n-butylstannate)*2 ethanol

Article abstract of DOI:10.1016/0022-328X(90)85077-C

Triphenyltin hydroxide has been shown to react with dicyclohexylammonium oxalate to give <(cyclo-C6H11)2NH2>⁺ <(C6H5)3SnOC(O)C(O)O>^-, and to give with dicyclohexylammonium malonate <(cyclo-C6H11)2NH2>⁺ <<(C6H5)3SnOC(O)CH2C(O)O>2H>^-.Bis(tri-n-butylin) oxide afforded 2<(cyclo-C6H11)2NH2>⁺ <<(n-C4H9)3Sn>43>^2- on treatment with dicyclohexylammonium malonate, but with dicyclohexylammonium oxalate it yielded a stannate which crystallized with two molecules of ethanol.A low-temperature X-ray diffraction study of this ethanol-containing stannate, 2<(cyclo-C6H11)2NH2>⁺ 2^2- revealed the presence of centrosymmetric chains, each consisting of four <(n-C4H9)3Sn>⁺ cations linked by three ^2- anions.The chains are hydrogen bonded by <(cyclo-C6H11)2NH2>⁺ cations and ethanol molecules into a three-dimensional lattice.The geometry around the ethanol-coordinated (Sn-O 2.465(4) Angstroem) terminal tin atom is essentially a trans-C3SnO2 trigonal bipyramid, but is distorted towards a C3SnO3 skew-trapezoidal bipyramid; the tin atom is part of a five-membered ring in which the O-Sn-O angle is 63.4(1) deg and Sn-O distances are 2.191(3) and 2.890(3) Angstroem.The geometry around the inner tin atom is a less distorted trans-C3SnO2 trigonal bipyramid; the four Sn-O-C-O (Sn...O 3.043(3) Angstroem) atoms do not form a ring owing to the small chelate bite.