Molecular structures of P4O6 and P4O8

Abstract

The electron-diffraction pattern from gaseous P₄O₆ has been recorded over the range s= 1.24 to 50.00 Å^–1. Structure analysis gave results which show no deviation from the accepted tetrahedral cage structure. The final molecular parameters are: P—O = 1.638 ± 0.003 Å, ∠P—O—P = 126.4 ± 0.7°. The comparable parameters in P₄O₈, as determined by least-squares refinement using Jost's new crystallographic data are P—O = 1.633 ± 0.010 Å, ∠P—O—P = 130.1 ± 0.9°. A survey is made of the dimensions of the four oxides P₄O₆, P₄O₈, P₄O₉, P₄O₁₀. Four different P—O bonds are distinguished and their mean lengths determined: P—O (peripheral)= 1.424 ± 0.004 Å; P_v—O (bridge)= 1.595 ± 0.004 Å; P_III—O(P_III)= 1.637 ± 0.004 Å; P_III—O(P_v)= 1.666 ± 0.008 Å. The dimensions of P₄O₇ are predicted.