The reaction of bis(tri-n-butyltin)oxide, [nBu3Sn]2O, with HO2C-C6H4-4-CF3 (R fTol-CO2H) affords a coordination polymer [nBu 3SnO2C-RfTol]n (1). 1 undergoes hydrolysis in the presence of atmospheric moisture, at room temperature, resulting in the formation of the diorgano stannoxane [{nBu2SnO 2C-RfTol}2O]2 (2). The transformation of 1 to 2 is accompanied by a Sn-C bond cleavage reaction. Formation of 2 also occurs in a direct reaction, involving [nBu 3Sn]2O and RfTol-CO2H in the presence of water. 2 can also be prepared in a 1:1 reaction of di-n-butyltin oxide, [nBu2SnO]n with RfTol-CO2H. The conversion of 2 from 1 was monitored by 119Sn NMR spectroscopy over a period of eight days. The molecular structure of 2 reveals a tetranuclear assembly consisting of two pairs of structurally distinct six-coordinate tin atoms. Extensive hydrogen-bonding interactions (C-H···O, C-H···F) and weak F···F interactions involving organo-fluorine atoms in the crystal structure result in the formation of a three-dimensional supramolecular architecture for 2. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.