P4O7 AND P4O6S, COMPARISON OF MOLECULAR AND CRYSTAL-STRUCTURE

Single crystals of P4O6S were grown for the first time. By X-ray diffraction the space group (P2(1)/c), the unit cell [a = 813.5(1), b = 938.3(1), c = 993.1(1) pm; beta = 90.27(1)-degrees], and the crystal and molecular structure have been determined. As compared to P4O7, the geometry of the P4O6 cage remains virtually unchanged upon substitution of the terminal oxygen atom by a sulfur atom. Calculated charge distributions clearly confirm the experimental results. With the exception of P(1), to which the additional chalcogen atom is attached, the effective charges at all other atoms seem not to be affected by an exchange of the terminal oxygen atom by a sulfur atom.