Tetrahedral-Atom Zincophosphate Structures. Zinc Diethyl Phosphate,Zn(O2P(OC2H5)2)2x, a One-Dimensional Inorganic Polymer

摘要

The synthesis, structure and some properties of a new, anhydrous, zinc ethylphosphate are described. Zn(02P-(OC2H5)2)2 (ZnPOEt) crystallizes in the monoclinic space group C2/c (No. 15) with a = 22.176 (6) A, b = 8.042 (2) A, c = 9.088 (3) A, beta = 96.553 (8)deg, v = 1610 A3, Pcalc = 1.533 g/cu cm mu = 17.8 /cm, and Z = 4, with R(F sub o) = 6.94% for 658 observed reflections I > sigma(I). The novel structure consists of infinite 1-dimensional chains of vertex-linked zinc-oxygen and phosphorus-oxygen tetrahedra forming four-rings : two of the phosphate P-0 vertices are coordinated to ethyl (-C2H5) groups, and the herringbone crystal packing is determined by Van der Waals' forces between these terminal organic groups. Physical (TGA, DSC) and spectroscopic data (IR, 1H, and 31P NMR) are presented. The physical data show a melting, followed by a decomposition reaction, eventually resulting in Zn(PO3)2. ZnPOEt is soluble in, and recrystallizable from, several polar and nonpolar solvents: the NMR data suggest that ZnPOEt maintains a polymeric state in solution. ZnPOEt is contrasted with its sulfur containing analogue, Zn(S2P(OC2H5)2)2.