Structure determination of lithium chloroacetate, lithium bromoacetate and lithium iodoacetate by powder diffraction

Abstract

Most halogenoacetates of alkali salts readily undergo a thermally induced polymerization reaction to poly-(hydroxyacetic acid) in the solid state. The lithium salts represent a remarkable exception. The crystal structures of lithium chloroacetate, lithium bromoacetate and lithium iodoacetate were determined ab initio from synchrotron powder diffraction data. The three compounds are isostructural and differ considerably from the structures of sodium chloroacetate and silver chloroacetate, two compounds that undergo polymerization. Most likely, the strong polarizing effect of the small lithium cation is responsible for the unfavorable crystal structure in which each lithium cation is coordinated to four O atoms from four different halogenoacetate molecules. Lithium chloroacetate: a = 9.3882 (9), b = 4.8452 (4), c = 9.0119 (7) Å, β = 94.330 (5)°; lithium bromoacetate: a = 9.7165 (11), b = 4.8610 (6), c = 9.0228 (11) Å, β = 93.946 (5)°; lithium iodoacetate: a = 10.1812 (10), b = 4.8922 (8), c = 9.0468 (10) Å, β = 93.251 (5)°, all crystallizing in space group P21/c with Z = 4.