Five-coordinated anionic tin(Ⅳ) complexes with the form [Ph 2Sn(μ 2-SCH 2COO)Cl]·[R nNH 4-n] were synthesized by the reaction of mercaptoacetic acid with diphenyltin dichloride in the presence of organic amines. All of the compounds synthesized were characterized by elemental analysis, IR, 1H NMR. The crystal structures of [C 5H 5NH][Ph 2Sn(μ 2-SCH 2COO)Cl](6) and [PhMeNH 2]· [Ph 2Sn(μ 2-SCH 2COO)Cl](8) were determined by X-ray diffraction. In the crystal structure, there were trigonal bipyramid geometries with five-coordinated tin atom and hydrogen-bonding interaction between anionic and cationic ions. Crystals of compound 6 were monoclinic, space group P2 1/n, a= 1.034 7(4) nm, b=1.396 8(5) nm, c=1.405 6(5) nm, β=95.366(6)°, Z=4; Crystals of compound 8 were monoclinic, space group P2 1/c, a=0.922 9(3) nm, b=1.334 5(5) nm, c= 1.838 5(7) nm, β=93.673(7)°, Z=4.
