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The crystal and molecular structures of four Me 3 Sn(O 2 CCH 3− x  Cl  x  ),  x  = 0 – 3, compounds have been determined at 200 K. The colorless crystals of [Me 3 Sn(O 2 CCH 3 )] are orthorhombic, space group  Pnma  with unit cell dimensions  a  = 10.569(4) Å,  b  = 7.876(9) Å,  c  = 9.719(9) Å,  V  = 809(1) Å 3 ,  Z  = 4 and  D  x  = 1.829 Mg m −3 . The colorless crystals of [Me 3 Sn · (O 2 CCH 2 Cl)] are monoclinic, space group  P 2 1 / c  with unit cell dimensions  a  = 12.564(6) Å,  b  = 10.093(5) Å,  c  = 14.44(1) Å,  β  = 98.62(5)°,  V  = 1810(1) Å 3 ,  Z  = 8 and  D  x  = 1.888 Mg m −3 . Crystals of colourless [Me 3 Sn · (O 2 CCHCl 2 )] are monoclinic, space group  P 2 1 / n  with unit cell dimensions  a  = 10.013(5) Å,  b  = 16.60(1) Å,  c  = 12.467(6) Å,  β  = 103.71(4)°,  V  = 2012(1) Å 3 ,  Z  = 8 and  D  x  = 1.925 Mg m −3 . The colorless crystals of [Me 3 Sn(O 2 CCl 3 )] are monoclinic, space group  P 2 1 / n  with unit cell dimensions  a  = 9.124(4) Å,  b  = 9.941(6) Å,  c  = 12.119(5) Å,  β  = 102.22(4)°,  V  = 1074.3(8) Å 3 ,  Z  = 4 and  D  x  = 2.016 Mg m −3 . The structures were solved by direct methods and each refined by a full-matrix least-squares procedure to final  R  = 0.034 using 876 reflections for [Me 3 Sn(O 2 CCH 3 )]; to  R  = 0.041 using 2556 reflections for [Me 3 Sn(O 2 CCH 2 Cl)]; to  R  = 0.045 using 3301 reflections for [Me 3 Sn(O 2 CCHCl 2 )]; and to final  R  = 0.038 reflections for [Me 3 Sn(O 2 CCl 3 )]. Each of the four structures adopts a similar polymeric motif owing to the presence of bidentate bridging carboxylate ligands. This arrangement leads to the presence of  trans -R 3 SnO 2  tin atom geometries. There is no apparent correlation between the  pK a values of the carboxylate ligands and the derived interatomic parameters, suggesting that crystal packing effects may exert an influence on these parameters. The solution structures of these compounds are shown by spectroscopy (infrared,  1 H NMR) to be monomeric with tetrahedral tin atom geometries.

Structural systematics of the triorganotin carboxylates: The crystal and molecular structures of polymeric Me 3 Sn(O 2 CCH 3− x Cl x ); x = 0 – 3