Synthesis, Vibrational Spectra, and Crystal Structure of the Aqueous Complex of Sodium Perchlorate with 1,5-Bis[2-(diphenylphosphinyl)phenoxy]-3-oxapentane (L), [Na_2(mu-L)(H_2O)(ClO_4)_2]

摘要

The sodium perchlorate complex with 1,5-bis[2-(diphenylphosphinyl)phenoxy]-3-oxapentane (L) of composition 2Na(ClO_4) centre dot L centre dot H_2O was synthesized, and its vibrational spectra were examined. The crystal structure of the complex was established by X-ray diffraction. The crystals are monoclinic, a = 26.675(5) A, b = 9.277(2) A, c = 22.469(4) A, alpha = 122.41(3) deg, V = 4693(2) A~3, Z=4, space group Cc, R =0.125 for 1197 reflections with I> 2 sigma (I). The crystal structure of 2Na(ClO_4) centre dot L centre dot H_2O consists of discrete binuclear molecular complexes. The podand L acts as a bridge and links two Na atoms through the phosphoryl oxygen atoms. One metal atom (Na(2)) closes the 16-membered metallacycle, whereas the second metal atom (Na(1)) occupies the position in the cavity. The coordination sphere of the Na(1) atom is formed by two phosphoryl oxygen atoms, two O atoms of the perchlorate group (Na(1)-O, 2.22(5) and 2.82(5) A), the ether oxygen atom (Na(1)-O, 2.80(4) A), and one of the anisole oxygen atoms of the podand L (Na(1)-O, 2.76(3) A). The coordination sphere of the Na(2) atom is composed of two phosphoryl oxygen atoms, the oxygen atom of the water molecule (Na(2)-O, 2.30(6) A), and two oxygen atoms of the second perchlorate group (Na(2)-O, 2.66(5) and 2.51(6) A). The Na-O(phosphoryl) bond lengths are in the range of 2.22-2.39(3) A.