HYDROGEN-BONDING IN 2-HYDROXYBENZOIC, 2-HYDROXYTHIOBENZOIC, AND 2-HYDROXYDITHIOBENZOIC ACID - A STRUCTURAL AND SPECTROSCOPIC STUDY

X-ray structural data are reported for 2-hydroxythiobenzoic acid (T = 200 K; P2(1)/a; a = 14.903(5) Angstrom, b = 5.203(3) Angstrom, c = 9.1 14(6) Angstrom, beta = 92.40(4)degrees; Z = 4; R = 0.049) and 2-hydrox ydithiobenzoic acid (T = 297 K; P2(1)/a; a = 14.416(3) Angstrom, b = 1 3.447(3) Angstrom, c = 3.947(1) Angstrom, beta = 90.96(2)degrees; Z = 4; R = 0.047). In 2-hydroxythiobenzoic acid, each two molecules form c yclic dimers via S-H...O=C hydrogen bonds, analogous to the associatio n pattern of 2-hydroxybenzoic acid. In 2-hydroxydithiobenzoic acid, th e molecules are linked to chains by S-H...O(H)-C hydrogen bonds. Solid state IR, and solution IR and NMR spectroscopic data of 2-hydroxybenz oic acid, 2-hydroxythiobenzoic acid, and 2-hydroxydithiobenzoic acid a re summarized. The main characteristics of the intramolecularly associ ated phenolic O-H groups of the three title compounds are <(nu)over ba r>(OH) = 3230, 3120, 2750 cm(-1) for the solids, <(nu)over bar>(OH) = 3210, 3185, 2945 cm(-1) for solutions (CCl4), and delta(OH) = 10.21, 1 0.53, 12.20 ppm for solutions (CCl4:CDCl3 = 5:1).