有機硫黄化合物の研究(第5報)cis-およびtrans-1-Thioniabicyclo-[4.4.0]decane Bromide結晶の熱異性化による2種の陽イオン異性体を含む異常結晶構造の生成

概要

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cis-1-Thioniabicyclo [4. 4. 0] decane bromide (cis-TBD-Br) and its trans isomer, both having distinctly different crystal modifications at room temperature, are transformed into the same crystalline modifications (α-phase) at high temperatures. An infrared absorption analysis carried out at 175°indicates that the α-phase contains both the cis-TBD and trans-TBD rings as its constituents approximately in the ratio 3 : 2. The lattice constants of the α-phase at 175°containing four formula units, C_9H_<17>SBr, are a=13.09,b=10.09,c=8.44 A. The space group corresponds to one of Fmmm, Fmm2 and F222. It is concluded that the two kinds of the isomeric ring ions are distributed statistically around four equivalent positions having a site symmetry (mmm, mm 2 or 222) given by the space group so that these ions should have statistical orientations. At room temperature, it decomposes gradually into its component crystals, cis- and trans-TBD-Br, but can be kept for several days in a desiccator over silica gel.
社団法人日本薬学会の論文
1981-01-25