Metastable β-phase of benzophenone:: independent structure determinations via X-ray powder diffraction and single crystal studies

Benzophenone was the first organic molecular material to be identified as polymorphic. It is well known that benzophenone crystallizes in a stable orthorhombic alpha-form (m.p. 321 K) with space group P2(1)2(1)2(1) and a = 10.28, b = 12.12, c = 7.99 Angstrom, [Girdwood (1998). Ph.D. thesis. Strathclyde University, Glasgow, Scotland]. Here we report two separate structure determinations of the metastable beta-form (m.p. 297-299 K). Crystalline material of the metastable polymorph was obtained from a melt supercooled to similar to 243 K. The structure was determined from X-ray powder diffraction data by employing a novel, computational systematic search procedure to identify trial packing arrangements for subsequent refinement. Unit-cell and space-group information, determined from indexing the powder diffraction data, was used to define the search space. The structure was also determined from single-crystal diffraction data at room temperature and at 223 K. The metastable phase is monoclinic with space group C2/c and a = 16.22, b = 8.15, c = 16.33 Angstrom, beta = 112.91 degrees (at 223 K). The structures derived from the individual techniques are qualitatively the same. They are compared both with each other and with the stable polymorph and other benzophenone derivatives.