Structural chemistry of organotin carboxylates XV. Diorganostannate esters of dicyclohexylammonium hydrogen oxalate. Synthesis, crystal structure and in vitro antitumour activity of bis(dicyclohexyl‐ammonium) bisoxalatodi‐n‐butylstannate and bis(dicyclohexylammonium) μ‐oxalatobis(aquadi‐n‐butyloxalatostannate)

Dicyclohexylamine, oxalic acid dihydrate and di‐n‐butyltin oxide were reacted in 2:2:1 or 2:3:2 stoichiometries in ethanol solution to yield, respectively bis(dicyclohexylammonium) bisoxalatodi‐n‐butylstannate (1) and bis(dicyclohexylammonium) μ‐oxalatobis(aquadi‐n‐butyloxalatostannate) (2); the hydrate was also obtained upon recrystallization of 1 from moist acetonitrile solution. The crystal structures of the two ammonium stannates have been determined at room temperature. In 1, the tin atom in the dianion exists in a skewtrapezoidal bipyramidal geometry with the basal plane being defined by two bidentate oxalate ligands; each ligand forms asymmetric SnO bonds [SnO 2.348(4), 2.110(4) Å and 2.112(4), 2.363(4) Å]. The apical sites are occupied by the two organo groups disposed over the weaker SnO bonds. In 2, the two tin centres of the dianion are connected via a tetradentate oxalate ligand situated about a centre of inversion and each tin atom exists in a pentagonal bipyramidal geometry. The pentagonal plane is defined by four oxygen atoms, two from the central ligand [SnO 2.282(4), 2.473(4)Å] and two from a ‘terminal’ oxalate ligand [SnO 2.239(4), 2.210(4)Å], and the fifth site is occupied by a water molecule of crystallization [SnO 2.422(4)Å]; the apical sites are filled by the n‐butyl groups. Both compounds feature extended hydrogen‐bonded networks involving the oxygen atoms of the dianion and the N‐bound hydrogen atoms. Crystals of 1 are monoclinic, space group P 2 1 / n , with cell dimensions a = 13.408(3), b = 22.461(4), c = 13.996(2)Å, β = 100.97(2) ° ; full‐matrix least‐squares refinement on 3305 reflections with I ≥2.5σ( I ) converged to R = 0.042 and R w = 0.046. Crystals of 2 are monoclinic, space group P 2 1 /n, a = 13.729(3), b = 14.694(2), c = 14.889(2)Å, β = 104.83(2) º ; refinement on 2093 reflections converged to R = 0.030 and R w = 0.031. The two di‐n‐butylstannates were screened in vitro against the mammary MCF‐7 and WiDr colon carcinoma cell lines, and were found to be as active as cisplatin, a clinically used antineoplastic drug.