Synthesis and structural characterization of a new supermolecular compound: H3PW12O40 center dot 6C(14)H(20)O(5)center dot 16H(2)O (C14H20O5 = benzo-15-crown-5)

The new supermolecular compound, H3PW12O40.6C(40)H(2)O(5). 6H(2)O (C14H20O5 = benzo-15-crown-5), was synthesized in methanol solution and structurally characterized by elemental analysis, IR, LH NMR and single crystal X-ray d iffraction. It was shown that PW12O403-(L anions possess alpha -Keggin stru cture with crystallographic disorder. The disorder averages the W-W distanc es and W-O-b/c-W angles, but the vibrational ellipsoids of oxygen atoms are not elongated obviously. In the compound, water blocks are formed, which a re hydrogen-bonded to crown ether molecules. Since crown ether molecules fe tter the movement of water molecules and oxonium ions, the conductivity is lower (rho (r.t.) < 10(-7) S cm(-1)). The compound crystallizes in the tric linic space group P<(1)over bar> with a = 14.154(3), b = 15.598(3), c = 18. 023(3) Angstrom, alpha = 67.17(3), beta = 89.83(3), gamma = 83.27(3)degrees , V = 3638.1(13) Angstrom (3), Z = 1 and R1(wR2) = 0.0655(0.1701). (C) 2000 Elsevier Science B.V. All rights reserved.