SYNTHESIS AND CRYSTAL-STRUCTURE OF THE AD DUCTS [DB-18C6]CENTER-DOT-CH3CN-CENTER-DOT-CH3CSOH AND [DC-18C6](CH3CSOH)(2) AS WELL AS OF THE SALT-LIKE COMPOUNDS [CS(B-15C5)(2)]CH3CSS AND [CS(DB-18C6)](2)S-5(DMF)(2)

The reaction products of crown ethers, cesium, and sulfur in aprotic s olvents like acetonitrile and dimethylformamide strongly depend on the reaction conditions. Using CH3CN as a solvent, sometimes neutral host -guest adducts crystallize only, e.g., [dibenzo-18C6]. CH3CN . CH3CSOH (monoclinic, S.G. P2(1)/c, Z = 4, a = 9.73(1) Angstrom, b = 22.03(1) Angstrom, c = 11.86(1) Angstrom, beta = 91.8(1)degrees) or [dicyclohex yl-18C6](CH3CSOH)(2) (monoclinic, S.G. P2(1)/n, Z = 2, a = 7.75(1) Ang strom, b = 10.32(1) Angstrom, c = 17.73(1) Angstrom, beta = 95.7(1)deg rees). The monothioacetic acid, CH3CSOH, must be regarded as the first product of the hydrolysis of CH3CN. Furthermore, another product of t his kind of hydrolysis, CH3CSSH, is obtained too. Therefore, we also o btain the salt-like compound [Cs(benzo-15C5)(2)]CH3CSS (monoclinic, S. G. C2/c, Z = 4, a = 16.05(1) Angstrom, b = 16.73(1) Angstrom, c = 13.1 1(1) Angstrom, beta = 106.3(1)degrees). If the solvent DMF is used, th e pentasulfide [Cs(dibenzo-18C6)]S-2(5)(DMF)(2) crystallizes (monoclin ic, S.G. P2(1)/n, Z = 4, a = 14.79(1) Angstrom, b = 14.24(1) Angstrom, c = 25.74(1) Angstrom, beta = 92.7(1)degrees). The S-5(2-) anions sho w the cis-conformation.