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In recent decade, it has been established that many higher fullerenes obeying the isolated pentagon rule (IPR) were susceptible to skeletal transformations forming structures with fused pentagons or even with heptagon in the carbon skeleton upon chlorination [1-2]. It was assumed that the chlorination of the most common fullerenes C60 and C70 leads to the formation of exclusively IPR-chlorides up to D3d-C60Cl30 and C70Cl28, respectively. However, the possibility of Stone-Wales rearrangements and the formation of non-IPR structures of fullerene C60 under harsh chlorination conditions was shown in ref. [3]. Single crystal X-ray diffraction revealed three chlorides with non-IPR frameworks: D2d-1805C60Cl24, C2v-1810C60Cl24, and D5-1794C60Cl20. In this work, optimization of the synthesis of non-IPR derivatives of C60 was carried out under chlorination with SbCl5. The impact of initial substrates, time of synthesis, and temperature on chlorination products was studied. After HPLC separation of the products, the crystals of two non-IPR isomers C60Cl24 and non-IPR chloride 1809С60Cl16 (Fig. 1, a) were investigated by single crystal X-ray diffraction. Both non-IPR C60Cl24 (Fig. 1, b and c) isomers were further characterized by IR spectroscopy. To receive more information on the products of the syntheses, high-temperature trifluoromethylation of the chlorination products was applied followed by HPLC separation. In this way, 1810C60(CF3)14 (Fig. 1, d) was isolated and studied by X-ray diffraction and IR spectroscopy. Molecular structures as well as chlorination and trifluoromethylation patterns of the isolated compounds are discussed in more detail.