X-ray crystal structure of cyclo-tetrakis(m-phenylenesulfide)

Synthesis of Polyfluorinated Thia- and Oxathiacalixarenes Based on Perfluoro-m-xylene

“…The sulphur atoms are located in the same plane practically without deviation. The C-S bond length 1.78 Å corresponds to the literature data for tetrathiacalixarenes [15,24]. The C-S-C angles are 100.6-100.7 • , and the torsion angles around the C-S bonds are 57.8-60.3 • .…”

“…The opposite aromatic nuclei are located almost parallel to each other, and the dihedral angles are 2.44 • and 4.69 • , respectively. It should be noted that the difference in the dihedral angles for the tetrathiacalixarenes described in the literature is significantly higher (2-130 • ) [15,24]. Crystallization of tetrathiacalixarene 1 from acetone or acetonitrile leads to the formation of complexes including 1 or 2 solvent molecules (Figure 1b).…”

“…According to X-ray analysis of the single crystal obtained from CH2Cl2, tetrathiacalixarene 1 is in the 1,3-alternate conformation, which is typical for tetrathiacalixarenes that do not have substituents in the inner cycle [13,15,24] (Figure 1a). The sulphur atoms are located in the same plane practically without deviation.…”

“…By column chromatography on silica gel using CCl 4 and CHCl 3 as eluents, 0.68 g of the solid product containing (GC-MS) 93% tetrathiacalixarene 1 was isolated. 5,11,17,23,25,26,27,6,10,12,16,18,22,24-octakis(trifluoromethyl)-2,8,14, 20-tetrathiapentacyclo[19.3.1.1 3,7 .1 9,13 .1 15,19 ]octacosa-1(25),3 (28),4,6,9(27),10,12,15(26),16,18, 21,23-dodecaene 1:…”

“…mp 304.6-304.9 • C. 19 F NMR ((CD 3 ) 2 CO): δ −112.1 (septet d, 4F, J F(5)-2CF3(4,6) = 33 Hz, J F(5)-F(28) = 15 Hz, F-5,11,17,23), −91.6 (m, 4F, F-25,26,27,28), −53.5 (dd, 24F, J CF3(4)-F(5) = 33 Hz, J CF3(4)-F(28) = 7 Hz, CF 3 (4,6,10,12,16,18,22,24)). 13 10)-F(11) = 28 Hz, CF 3 (10,24)), −55.3 (dd, 6F, J CF3(12)-F(11) = 36 Hz, J CF3(12)-F(27) = 6 Hz, CF 3 (12,22)), −55.1 (dd, 6F, J CF3(16)-F(17) = 36 Hz, J CF3(16)-F(26) = 4 Hz, CF 3 (16,18)). 19…”