Synthesis, Vibrational Spectra, and Crystal and Molecular Structure of 1,5-Bis[2-(dihydroxyphosphinyl)phenoxy]-3- oxapentane Dihydrate[(HO)_2(O)P(C_6H_4)(OCH_2CH_2)_2O(C_6H_4)P(O)(OH)_2(H_2O)] · H_2O

摘要

A modified method of synthesis of a phosphoryl podand, 1,5-bis[2-(dihydroxyphosphinyl)phe-noxy]-3-oxapentane (L), has been developed. The IR spectra of this podand and its dehydrate (L [L . H_2O] . H_2O (I) have been studied, the structure of I has been determined by X-ray crystallography. The crystals are orthorhombic, a = 9.4006(19) A, b = 25.494(5) A, c = 8.4264(17) A, V = 2019.5(7) A~3, Z = 4, space group Pna2_1, R = 0.0512 for 3016 reflections with I ＞ 2σ(I). Compound I is a host–guest molecular complex. Phos- phoryl podand L acts as a host molecule, and one of the water molecules (H_2O(11)) is a guest. This molecule forms one donor and one acceptor intramolecular hydrogen bond with hydroxyl groups of two phosphoryl groups (O(8)H(4) and O(3)H(2)) and combines them into an 18-membered macrocyclic ring, acting as a kind of “lock.” The H_2O(11) molecule forms a second donor intramolecular hydrogen bond with the O(5) ether atom. The neutral molecular complexes are linked by hydrogen bonds directly and through the second water molecule (H_2O(10)) into chains running along the c axis.