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24 Ralf Steudel · Bodo Eckert Fig. 5 The crystal structure of orthorhombic S8 projected parallel to the c-axis showing the so-called crankshaft structure. The direction of the a- and b-axis of the crystal in- cludes an angle of about 45 to the mean plane of the molecules in each layer [8] of S8 (<55 kJ mol1), obtained by ab-initio quantum chemical calculations, have been reported [69, 79]. These will be discussed below. 2.2.1.3.1 Orthorhombic a-S8 Although several early attempts had been made to analyze the structure of this allotrope, the first correct description of the crystalline as well as of the molecular structure was given by Warren and Burwell in 1935 [82], which was later improved by Abrahams in 1955 [83]. The most recent examination of the structure of a-S8 by Rettig and Trotter in 1987 confirmed the results of the earlier studies with a somewhat higher precision [80]. The history of the attempts to characterize the structure of a-S8 up to the 1970s has been discussed by Donohue [8]. In a-S8 the molecules crystallize in the orthorhombic space group Fddd–D2h24. The octamers are arranged in two layers each perpendicular to the crystal c axis forming a so called “crankshaft structure” (Fig. 5). The primitive cell contains four molecules on sites of C2 symmetry. Four non-PDF Image | Topics in Current Chemistry
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