Introduction.Previous work has shown that octaphenylcyclotetrasiloxane is polymorphic, occurring in monoclinic and triclinic forms and also as a benzene solvate (Hyde, Frevel, Nutting, Petrie & Purcell, 1947). As part of an investigation of the structure and conformation of cyclosiloxanes and related species, we have begun a crystallographic study of this system. Here we report the analysis of the monoclinic form.The compound was prepared by the condensation of phenylsilanediol in alkaline medium and recrystallized from benzene-95% ethanol to obtain colourless needles. The cell parameters were initially determined from photographs and subsequently refined on a Nonius CAD-4 diffractometer from the setting angles for 25 reflections. The intensities of 7191 reflections (3 < 0 < 60 °) were recorded on the diffractometer with Ni-filtered Cu K~ radiation, an 09--20 scan technique and a crystal 0.40 x 0.15 x 0.12 mm. Two reference reflections, measured periodically, showed only minor fluctuations. The intensities were corrected for Lp factors but not for absorption. 4009 unique reflections with F o > 3a(Fo) were considered observed and used in the analysis.The structure was determined by direct methods and refined by a full-matrix least-squares procedure to a