Experimental. The ligand DTM ligand, 2,2'-[methylenebis(thio)]bis(1,3-thiazole), was
synthesized according to the literature method of Zhang et al. (2003)
by the reaction of 2-thiothiazole and dibromomethane catalyzed by KOH (yield
67%; m.p. 343–345 K). Spectroscopic analysis: IR (KBr, ν, cm-1): 3094 (w),
3076 (m), 3005 (w), 1479 (m), 1392 (m), 1332 (m),
1305 (w), 1213 (m), 1150 (w), 1069 (m), 1026 (s), 807
(w), 725 (s), 594 (m); 1H NMR (CDCl3, δ, p.p.m.): 5.00 (s,
2H), 7.27 (d, J = 3.6 Hz, 2H), 7.72 (d, J = 3.6 Hz, 2H). To prepare compound
(I), DTM (25 mg, 0.1 mmol) and CoCl2·6H2O (24 mg, 0.1 mmol) were
added to acetonitrile (6 ml). The reaction mixture was stirred at room
temperature for 20 min. The precipitate which formed was filtered off, washed
with acetonitrile and dissolved in hot acetonitrile (15 ml). Blue block-shaped
single crystals of (I), suitable for X-ray analysis, were grown by slow
evaporation of the solvent (yield 75%; m.p. 531–533 K). Analysis, calculated
for C7H6Cl2CoN2S4: C 22.34, H 1.60, N 7.45%; found: C 22.29, H 1.69,
N 7.52%. Spectroscopic analysis: IR (KBr, ν, cm-1): 3190 (w), 3086 (w),
2957 (w), 2903 (w), 1491 (m), 1391 (w), 1347 (m), 1302
(m), 1212 (w), 1149 (s), 1082 (s), 847 (w), 761
(s). Spectroscopic analysis: IR (KBr, ν, cm-1): 3094 (w), 3076 (m),
3005 (w), 1479 (m), 1392 (m), 1332 (m), 1305
(w), 1213 (m), 1150 (w), 1069 (m), 1026
(s), 807 (w), 725 (s), 594 (m); 1H NMR (CDCl3,
δ, p.p.m.): 5.00 (s, 2H), 7.27 (d, J = 3.6 Hz, 2H), 7.72
(d, J = 3.6 Hz, 2H). Spectroscopic analysis: IR (KBr, ν,
cm-1): 3190 (w), 3086 (w), 2957 (w), 2903 (w),
1491 (m), 1391 (w), 1347 (m), 1302 (m), 1212
(w), 1149 (s), 1082 (s), 847 (w), 761 (s). |