Four solid complexes of alkaline earth picrates with N,N,N',N'-tetraphenyl-3,6,9-trioxaundecanediamide (TTD), M (Pic)(2)TTD (1, M = Mg; 2, M = Ca; 3, M = Sr; 4, M = Ba), have been prepared and characterized by elemental analysis, conductivity measurement, IR spectra, H-1 NMR spectra and TG-DTA techniques. Crystal structure of complex 3 shows that the Sr(II) ion is 9-coordinated by five oxygen atoms from TTD and four oxygen atoms from two bidentate picrates, and the coordination polyhedron is distorted tricapped trigonal prism. TTD as a pentadentate ligand forms a right-handed helical coordination structure. The chelating helical chain has a relative fixed radius and then shows a high coordination selectivity to metal ion. The high selectivity of TTD to alkaline earth ions is explained elementarily from the special coordination structures.